JP4968883B2 - Remote plasma processing equipment - Google Patents

Description

  The present invention relates to a remote plasma processing apparatus.

In the so-called remote plasma type plasma treatment, for example, as described in Patent Documents 1 and 2, two metal electrodes whose at least one electrode is coated with a solid dielectric are arranged to face each other, and an interelectrode gap is formed. A gas is flowed to activate the gas. At this time, each solid dielectric layer is formed as a sprayed film by spraying a ceramic film such as alumina on a metal electrode.
JP2004-006586 JP2004-319285

  However, in such a conventional remote plasma processing apparatus, it is necessary to adjust the gap interval between the pair of opposed metal electrodes by a movable mechanism of the metal electrodes. However, since the discharge gap interval is adjusted by the electrode driving mechanism, the adjustment work requires labor. In addition, the gap interval may vary due to vibration or the like. Furthermore, if the area of the metal electrode is increased to increase the throughput, it becomes difficult to keep the discharge gap interval uniform throughout the electrode. In addition, the ceramic sprayed film has low density and the particles are easily peeled off, so that particles are likely to be generated. There is a tendency to cause destruction.

  An object of the present invention is to stably maintain a constant electrode gap without an electrode driving mechanism in a plasma process in which a gas is introduced into a gap between a pair of electrodes and the gas is activated and discharged. In other words, peeling from the solid dielectric layer and generation of particles are suppressed.

A remote plasma processing apparatus according to the present invention includes a first electrode layer, a first ceramic layer embedded with the first electrode layer, and having protrusions and grooves formed between the protrusions at both ends on the surface side. A second electrode layer, a second ceramic layer embedded in the second electrode layer, having a protrusion at both ends on the surface side and a groove formed between the protrusions, and a first ceramic layer for holding the first ceramic layer One electrode holding member, a second electrode holding member that holds the second ceramic layer, and an outlet opening that is provided outside the first holding member and the second holding member and opens on the workpiece The surface of the first ceramic layer and the surface of the second ceramic layer are arranged to face each other, and gas is formed by the grooves of the first ceramic layer and the grooves of the second ceramic layer. the channel is formed, the gas flow path, Serial and from the upstream by the distance between the projections is narrowed at both ends tapered toward the downstream of the outlet, the gas flow using a discharge by application of a voltage to the first electrode layer and the second electrode layer The process gas introduced into the passage is activated, the activated process gas is discharged from the discharge port, and a shield gas is allowed to flow between the gas shield and the first holding member and the second holding member. The process gas activated from the outlet opening is caused to flow toward the object to be processed.

According to the present invention, the first electrode layer and the second electrode layer are respectively embedded in the ceramic so as not to be exposed. The first ceramic layer and the second ceramic layer are arranged to face each other, thereby defining a gap therebetween. Therefore, ceramics have a smaller thermal expansion than metal, so the gap between electrodes due to thermal expansion is small, so there is no need to adjust the gap between metal electrodes using a movable mechanism, and the gap can vary due to vibrations, etc. Therefore, it is possible to increase the processing amount by increasing the area of the metal electrode. In addition, as in the case of a sprayed film, generation of particles due to separation from the surface or degranulation during plasma generation can be suppressed. Further, since the metal electrode is embedded and fixed in the ceramic, it is not necessary to prevent the deformation by thickening the metal electrode.
Moreover, the object to be processed can be installed near the opening of the gas flow path that becomes narrower toward the outlet opening, and the activated gas is prevented from flowing out to the outside, so that the activated gas is concentrated on the object to be processed. Can be promoted and the processing efficiency can be improved.

Both the first ceramic layer and the second ceramic layer are provided with protrusions and grooves formed between the protrusions . The gap dimension is determined by the depth of each groove.

  In addition, an inactive region where the first electrode is not provided can be provided under the first surface, and an inactive region where the second electrode is not provided can be provided under the second surface. Such an inactive region shall be provided other than the edge portion or the peripheral portion of the first ceramic layer and the second ceramic layer. If an electrode for generating plasma is provided, the total heat generation amount increases, and cooling may be difficult. By providing an inactive region as in this embodiment, the amount of heat generated by the entire apparatus can be reduced.

  In addition, a first electrode holder that holds the first ceramic layer and a second electrode holder that holds the second ceramic plate are provided.

  A gas shield is provided around the first ceramic layer and the second ceramic layer. Accordingly, it is possible to shield the activated gas discharged from the plasma processing discharge hole so as not to be diffused to the outside, thereby improving the processing efficiency of the object.

FIG. 1 is a view showing a plasma treatment 10 according to a reference embodiment, FIG. 2 (a) is a front view showing a ceramic layer 1A (1B), and FIG. 2 (b) is a plan view.

  Corresponding electrode layers 2A and 2B are embedded in the pair of opposing ceramic layers 1A and 1B, respectively. The ceramic layers 1A and 1B are sandwiched and held by holding members 12A and 12B, respectively. Terminals 3A and 3B are connected to the electrode layers 2A and 2B, respectively, and the terminals 3A and 3B protrude from the holding members 12A and 12B and are connected to the power source 5.

  A gap 7 having a constant width is formed between the surface 1a of the ceramic layer 1A and the surface 1c of the ceramic layer 1B which face each other. A processing gas is supplied to the gap 7 as indicated by an arrow 8 and power is supplied from the power source 5 to the electrode layers 2A and 2B to generate plasma and activate it. The activated processing gas is discharged from the discharge port as indicated by an arrow 9 and is jetted onto the workpiece 6 to perform a predetermined process on the substrate 6.

FIG. 3A is a longitudinal sectional view showing a plasma processing apparatus 10A according to a reference embodiment, and FIG. 3B is a transverse sectional view. The same reference numerals are given to the portions shown in FIG. 1, and the description thereof may be omitted.

  In the apparatus 10A of this example, a spacer 13 is sandwiched between the first ceramic layer 1A and the second ceramic layer 1B, and the spacer 13 is fixed to both the ceramic layers 1A and 1B. ing. A gap 7 is formed between the first ceramic layer and the second ceramic layer, and a processing gas is introduced into the gap 7 for activation treatment. The size of the gap 7 is determined by the size of the spacer 13.

  4A is a longitudinal sectional view showing a plasma processing apparatus of a comparative example, and FIG. 4B is a transverse sectional view of the apparatus of FIG. 4A. In this example, the ceramic sprayed film 17 is formed so as to cover the first metal electrode layer and the second metal electrode layer 16, respectively. A spacer 13 is sandwiched between a pair of sprayed coatings 17 facing each other, and the gap 7 is defined.

Fig.5 (a) is a front view which shows the ceramic layer of the apparatus based on a reference form, FIG.5 (b) is a top view similarly. FIG. 6A is a longitudinal sectional view showing a device 10B according to this embodiment, and FIG. 6B is a transverse sectional view of the device 10B.

  Projections 14 as shown in FIGS. 5A and 5B are formed on the surface sides of the first ceramic layer 2A and the second ceramic layer 2B, respectively, and a groove 15 is formed inside the projection 14. Is formed. Then, the protrusions 14 on the first ceramic layer 2 </ b> A and the protrusions 14 on the second ceramic layer 2 </ b> B are made to face each other, thereby integrating the grooves on the surface of each ceramic layer to form the gap 7. The size of the gap 7 is determined by the depth of the groove.

Fig.7 (a) is a front view which shows the ceramic layer of the apparatus based on a reference form, FIG.7 (b) is a top view similarly. FIG. 8A is a longitudinal sectional view showing a device 10C according to another embodiment, and FIG. 8B is a transverse sectional view of the device 10C. In the apparatus 10C of this example, protrusions 14 are formed along the edges of the surfaces 1a and 1c of the ceramic layers 1A and 1B. At the same time, elongated straight central protrusions (spacer portions) 16 are also provided on the surfaces of the ceramic layers 1A and 1B.

  At the stage where the two ceramic layers are butted and joined as shown in FIG. 8, the gap 7 is divided into two flow paths by the protrusions 16. In this case, even when the surface area of the ceramic layer is increased by the protrusions 16, the variation in the width of the gap 7 can be more effectively suppressed.

Fig.9 (a) is a front view which shows the ceramic layer of the apparatus based on a reference form, FIG.9 (b) is a top view similarly. FIG. 10A is a longitudinal sectional view showing a device 10D according to another embodiment, and FIG. 10B is a transverse sectional view of the device 10D. In the apparatus 10D of this example, the protrusion 14 is formed along the edge of the surface of each ceramic layer 1A, 1B.

  Along with this, an inactive region 18 where the first electrode 2A and the second electrode 2B are not provided is provided on the upper side (gas supply side) of the ceramic layer 1A (1B). Thereby, excessive heating of the entire apparatus can be prevented and cooling can be promoted.

Fig.11 (a) is a front view which shows the ceramic layer which can be used by this invention, FIG.11 (b) is a top view similarly. In the apparatus of this example, protrusions 19 are provided on the surfaces of the ceramic layers 2A and 2B. As a result, the gas flow path 20 is gradually narrowed from the upstream toward the downstream, and the width is minimized at the discharge port 21 at the tip of the flow path 20. By forming the planar projections 19 and the grooves 20 as described above, the activated gas can be concentrated toward the opening 21. Therefore, by installing the object to be processed near the opening 21, the processing efficiency of the object to be processed can be further improved.

FIG. 12 is a longitudinal sectional view of an apparatus using the gas shield of the present invention. This apparatus itself is substantially the same as the apparatus 10 of FIG. However, in the apparatus 10E of this example, the gas shield 23 is provided outside the holding members 12A and 12B. Then, a shielding gas is allowed to flow as indicated by an arrow D between the gas shield 23 and the holding member. The gas shield 23 is also provided with an outlet opening 23a, and an activated gas is allowed to flow in the center of the opening 23a as indicated by an arrow 9. Then, a shield gas is caused to flow around the activated gas 9 as indicated by an arrow E. As a result, the activated gas can be prevented from flowing out, the concentration of the activated gas 9 on the workpiece 6 can be promoted, and the processing efficiency can be improved.

  In the present invention, the gap interval is not particularly limited, but it is usually preferably 0.05 to 3 mm, more preferably 0.1 to 0.5 mm.

  The height of the protrusion provided on the surface of each ceramic layer is not particularly limited, and is set according to the gap size described above.

  In a preferred embodiment, an induction storage type pulse power supply is used as a pulse power supply for applying a voltage. This makes it possible to generate a streamer discharge with a high current density. As a result, the amount of radicals generated in the plasma jet is large, and the treatment effect can be improved.

  In a preferred embodiment, an electrostatic induction thyristor element is used as the switching element of the pulse power supply. This is less likely to cause malfunction due to noise and element destruction, and is easy to maintain, so that productivity can be improved.

  Examples of the electrode layer include those made of simple metals such as silver, copper, and aluminum, alloys such as stainless steel and brass, and intermetallic compounds. The electrode layer preferably has a structure in which the distance between the counter electrodes is substantially constant in order to avoid occurrence of arc discharge due to electric field concentration. Examples of the electrode structure satisfying this condition include a parallel plate type, a cylindrical opposed flat plate type, a spherical opposed flat plate type, a hyperboloid opposed flat plate type, and a coaxial cylindrical type structure.

  The material of the ceramic layer is not particularly limited as long as it has durability against plasma, and examples thereof include alumina, zirconia, and cordierite. Each ceramic layer is preferably a sintered body.

  The material of the spacer provided between the ceramic layers is not particularly limited, and examples thereof include alumina, zirconia, and cordierite.

  In this invention, the planar pattern of each electrode layer is not specifically limited, It can design according to the kind of catalyst and the kind of reaction. For example, the planar pattern of the electrodes can be comb-like or mesh-like.

  In the case where the electrode layer has a net shape or a comb shape, it is preferable that the through holes are formed in a mesh shape or regularly formed in the gaps between the comb teeth. In this embodiment, the shape of the mesh is not particularly limited, and may be a circle, an ellipse, a racetrack shape, a quadrangle, a polygon such as a triangle, or the like. The shape of the comb-teeth of the comb-like electrode is not particularly limited, but is preferably a rectangle or a parallelogram.

  In the present invention, a voltage is applied between the counter electrode layers to generate plasma. At this time, the waveform of the voltage is not particularly limited, and may be any of a sine wave, an impulse type, a square wave type (rectangular wave type), and a damped oscillation type. A DC bias voltage can be applied simultaneously.

  The shorter the voltage rise time, the more efficiently the ionization of gas during plasma generation. From this point of view, it is preferable that a pulse voltage is applied and its rise time is 0.05 microsecond or less. In reality, the rise time of the pulse is 0.1 microsecond or more due to the transient time due to the operation time of the switching element used in the pulse generation circuit and the circuit impedance. The rise time is a time during which the voltage change is continuously positive.

  Further, the falling time of the pulse electric field is preferably steep, and is preferably 0.05 microseconds or less.

  The frequency of the pulse electric field is preferably 0.5 kHz to 100 kHz. If it is less than 0.5 kHz, the plasma density is low, so that the process takes too much time. If it exceeds 100 kHz, arc discharge tends to occur.

  The pulse voltage as described above can be applied by a steep pulse generating power source. As such a power source, an induction accumulation type pulse power source using an electrostatic induction thyristor element that does not require a magnetic compression mechanism, a thyratron equipped with a magnetic compression mechanism, a gap switch, an IGBT element, a MOF-FET element, an electrostatic induction A capacity storage type pulse power source using a thyristor element can be exemplified. As the pulse power source for applying the pulse voltage, an induction accumulation type pulse power source is particularly preferable.

  The object to be processed by the plasma generated by the present invention is not particularly limited. Hereinafter, the surface treatment method of the substrate will be described in detail.

  Examples of the object to be processed include polyethylene, polypropylene, polystyrene, polycarbonate, polyethylene terephthalate, polytetrafluoroethylene, plastics such as acrylic resin, glass, ceramic, metal, and the like. Examples of the shape of the substrate include a plate shape and a film shape, but are not particularly limited thereto. According to the surface treatment method of the present invention, it is possible to easily cope with the treatment of substrates having various shapes.

  By using a fluorine-containing compound gas as the treatment gas, it is possible to form a fluorine-containing group on the surface of the substrate to reduce the surface energy and obtain a water-repellent surface.

Fluorine element-containing compounds include carbon tetrafluoride (CF4) and carbon hexafluoride (C2 F6).
), Propylene hexafluoride (CF3)
Fluorine-carbon compounds such as CFCF2) and cyclofluorobutane octafluoride (C4 F8), carbon trifluoride (CClF3)
) And the like, and fluorine-sulfur compounds such as sulfur hexafluoride (SF6). From the viewpoint of safety, it is preferable to use carbon tetrafluoride, carbon hexafluoride, hexafluoropropylene, and octafluorocyclobutane that do not generate hydrogen fluoride, which is a harmful gas.

  Using the following oxygen element-containing compounds, nitrogen element-containing compounds, and sulfur element-containing compounds as processing gases, surface functional energy is formed by forming hydrophilic functional groups such as carbonyl groups, hydroxyl groups, and amino groups on the substrate surface. The surface can be increased to obtain a hydrophilic surface.

  Examples of oxygen element-containing compounds include oxygen, ozone, water, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, metanal, and ethanal. Examples include organic compounds containing oxygen elements such as aldehydes. These may be used alone or in admixture of two or more. Further, the oxygen element-containing compound may be mixed with a gas of a hydrocarbon compound such as methane or ethane. Moreover, hydrophilization is accelerated | stimulated by adding a fluorine element containing compound in 50 volume% or less of the said oxygen element containing compound. What is necessary is just to use the same thing as the said illustration as a fluorine element containing compound.

  Nitrogen, ammonia, etc. are mentioned as a nitrogen element containing compound. You may mix and use the said nitrogen element containing compound and hydrogen.

  Examples of the sulfur element-containing compound include sulfur dioxide and sulfur trioxide. Moreover, sulfuric acid can be vaporized and used. These may be used alone or in admixture of two or more.

  A hydrophilic polymer film can also be deposited by performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a sulfonate group, a primary or secondary or tertiary amino group, an amide group, a quaternary ammonium base, a carboxylic acid group, and a carboxylic acid group. Can be mentioned. Similarly, a hydrophilic polymer film can be deposited using a monomer having a polyethylene glycol chain.

  Examples of the monomer include acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, sodium styrenesulfonate, allyl alcohol, allylamine, polyethylene. Examples include glycol dimethacrylic acid ester and polyethylene glycol diacrylic acid ester. These monomers are used alone or in combination.

  Since the hydrophilic monomer is generally a solid, a substance dissolved in a solvent is vaporized by means such as reduced pressure. Examples of the solvent include organic solvents such as methanol, ethanol, and acetone, water, and mixtures thereof.

  Furthermore, a metal oxide thin film such as SiO2, TiO2 or SnO2 is formed using a processing gas such as metal metal-hydrogen compound, metal-halogen compound, metal alcoholate such as Si, Ti, Sn, etc. Can be provided with electrical and optical functions.

  Examples of the shielding gas include helium, neon, argon, xenon and other rare gases, nitrogen gas, and the like. These may be used alone or in admixture of two or more.

  The pressure of the processing gas is not less than atmospheric pressure, but is preferably 0.2 MPa or more, more preferably 0.4 MPa or more.

( Reference Example 1)
The apparatus described with reference to FIGS. 1, 2, and 3 was manufactured, and the glass substrate was subjected to plasma treatment.
Specifically, the ceramic layers 1A and 1B were made of alumina having a purity of 99.9% or more, and the dimensions were 90 mm in length, 50 mm in width, and 1 mm in thickness. The positions of the metal electrode layers 2A and 2B were 0.5 mm from the surface of the ceramic layer, and the material was molybdenum metal. The electrode layer had a thickness of about 50 μm, and an edge portion (peripheral portion) of the ceramic layer was provided with a region having no metal electrode layer over a width of 1 mm.

  Between the ceramic layers 1A and 1B, a spacer 3 made of alumina having a purity of 99.9% or more was sandwiched to form a gap. The dimensions of the spacer were 50 mm in length, 10 mm in width, and 0.3 mm in thickness. Further, the holding members 12A and 12B were made of alumina having a purity of 99.9% or more, 90 mm in length, 50 mm in width, and 10 mm in thickness. The diameter φ of the terminal hole 11 was 3.5 mm. The cylindrical holes 3A and 3B made of SUS304 having a diameter of 3 mm and a length of 15 mm were pressed against the terminal holes 11 and brought into contact with the contact holes of the electrodes by an external spring mechanism.

  A pulse power source 5 was connected to the plasma processing unit thus obtained, and the glass substrate 6 was subjected to plasma processing using a processing gas 8. An inductive accumulation type pulse power source was used as the pulse power source. The pulse width of the pulse voltage was 1 μs, the pulse voltage was 8 kV, the pulse energy was 8 mJ × 12 kHz, and the output was 96 W. The treatment gas was high-purity nitrogen gas (99.999%), the flow rate was 25 L / min, and the object to be treated was Tempax glass φ60 × 1 mm (initial water contact angle 55 degrees). The distance to the workpiece was 1 mm. The workpiece was processed by moving it at a speed of 5 cm / sec on the moving stage.

  As a result, the water contact angle before and after the treatment decreased from the initial 55 degrees to 12 degrees after the treatment. The number of particles of 10 microns or less adhered to the substrate was 35. In addition, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test.

(Comparative Example 1)
A plasma processing apparatus as described with reference to FIG. 4 was produced. An alumina sprayed film 17 having a thickness of 0.5 mm was formed on a 90 × 50 × 3 mm metal electrode (made of SUS304) 16 by a ceramic spraying method to produce an electrode. Two electrode units were prepared, and a gap was formed using a spacer 13 (thickness 0.3 mm). The same evaluation was performed using the same pulse power source, processing gas, and workpiece as in Reference Example 1.

As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 12 degrees after the treatment. The number of adhered particles of 10 microns or less was 256, which was remarkably increased as compared with Reference Example 1. In addition, during the 1000 hours continuous operation test, the alumina sprayed film resulted in dielectric breakdown.

( Reference Example 2)
As described with reference to FIGS. 5 and 6, the ceramic layers 1 </ b> A and 1 </ b> B used in Reference Example 1 were grooved, and the two were opposed to each other, and the plasma processing apparatus shown in FIG. 6 was manufactured. However, the depth of each groove was 0.15 mm, and the gap interval of the discharge space was 0.3 mm. In this case, the alumina spacer used in Reference Example 1 is not used.

About the apparatus obtained in this way, the same evaluation was performed using the same pulse power supply, process gas, and to-be-processed object as the reference example 1. FIG. As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 12 degrees after the treatment. The number of particles of 10 microns or less attached to the substrate was 30. When a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test. Thus, a processing effect equivalent to that of the processing apparatus shown in Reference Example 1 was obtained, and an apparatus excellent in maintainability that did not require adjustment of the electrode interval by a spacer or the like could be obtained.

( Reference Example 3)
A plasma processing apparatus similar to that of Reference Example 2 was produced, and the same measurement was performed. However, the depth of the groove in the ceramic layer was 0.05 mm, and the gap interval was 0.1 mm. The same evaluation was performed using the same pulse power source, processing gas, and workpiece as in Reference Example 1.

As a result, the contact angle of the glass substrate after the plasma treatment was 5 degrees lower than that of Reference Example 1. That is, it became possible to realize a plasma processing section having a short gap interval by using a ceramic molded body electrode subjected to groove processing, and as a result, an apparatus having a high processing effect could be obtained. The number of particles of 10 microns or less adhered to the substrate was 32. Furthermore, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test.

(Comparative Example 2)
A plasma processing apparatus having a discharge gap of 0.1 mm was manufactured using the electrode using the ceramic sprayed film of Comparative Example 1 and an alumina spacer (thickness: 0.1 mm). When plasma treatment was attempted under the same conditions as in Reference Example 1, the spacer cracked during energization, resulting in dielectric breakdown. That is, it has been found that it is difficult to stably generate plasma using a thin spacer such as a spacer having a thickness of 0.1 mm.

( Reference Example 3)
As shown in FIG. 7, in forming the groove 14 on the surface of the ceramic layer, the spacer portion 16 for keeping the gap interval uniform was formed. The dimensions of the ceramic layer were larger than those in Reference Example 1, and were 180 mm long and 50 mm wide. The width of the spacer portion 16 was 1 mm.

Two obtained ceramic layers were made to face each other to form a discharge space, and the plasma processing apparatus shown in FIG. 8 was obtained. The depth of the groove 14 was 0.15 mm, and the gap interval of the discharge space was 0.3 mm. In this case, the alumina spacer used in Reference Example 1 is not used.

Using this apparatus, the substrate was plasma-treated in the same manner as in Reference Example 1. However, since the electrode width was doubled from 90 mm to 180 mm as compared with Reference Example 1, the flow rate of nitrogen gas was doubled to 50 L / min. As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 12 degrees after the treatment. The number of particles of 10 microns or less adhered to the substrate was 32. Furthermore, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test. Further, the processing uniformity in the width direction was ± 15%.

( Reference Example 4)
A plasma processing apparatus similar to that of Reference Example 3 was produced. However, the spacer portion 16 was not left in the groove processing. As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 12 degrees after the treatment. The number of particles of 10 microns or less adhered to the substrate was 32. Furthermore, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test. However, it was found that the processing uniformity in the width direction increased to ± 25%.
That is, by providing the spacer portion 16 in the groove processing, it is possible to obtain an apparatus with higher processing uniformity even when the plasma processing portion is enlarged.

( Reference Example 5)
A plasma processing apparatus was produced in the same manner as in Reference Example 1. However, as shown in FIG. 9, in order to increase the cooling effect of the electrode, a buried metal layer was partially formed on the electrode surface, and an inactive region 18 in which the electrode layer was not buried was provided except for the peripheral portion. The dimensions of the ceramic electrode were 90 mm long, 70 mm wide, and 1 mm thick. The width of the inactivated region 18 was 20 mm. Two obtained ceramic layers were opposed to each other to form a discharge space, and a plasma processing apparatus was manufactured. The depth of the groove 14 was 0.15 mm, and the gap interval of the discharge space was 0.3 mm. In this case, the alumina spacer used in Reference Example 1 is not used. The same evaluation was performed using the same pulse power source, processing gas, and workpiece as in Reference Example 1.

As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 13 degrees after the treatment. The number of particles of 10 microns or less adhered to the substrate was 32. Furthermore, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test. When the electrode temperature was measured, the surface temperature was 95 ° C. in the case of Reference Example 1 whereas it was 70 ° C. in this example, and the amount of cooling water could be reduced.

( Reference Example 6)
A plasma processing apparatus was produced in the same manner as in Reference Example 5. However, the metal electrode layer and the groove were formed in the shape as shown in FIG. As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 13 degrees after the treatment. The number of particles of 10 microns or less adhered to the substrate was 32. Furthermore, when a 1000-hour continuous energization test was performed, the insulation resistance between the electrodes did not change before and after the test. As a result, it is possible to realize a plasma processing apparatus with high cooling efficiency while at the same time strengthening the blowing of plasma.

( Reference Example 7)
As shown in FIG. 12, an apparatus having a mechanism for shielding the activated processing gas from both sides with another gas was manufactured. That is, the same plasma processing apparatus as in Reference Example 1 was produced. And the gas shield 23 of SUS304 was attached. The distance from the processing unit main body was 5 mm. Further, as the shielding gas, two systems of nitrogen gas (flow rate 10 L / min) were used. The effect was confirmed in the same manner as in Reference Example 1.

As a result, the contact angle of the glass substrate before and after the plasma treatment was changed from the initial 55 degrees to 8 degrees after the treatment. That is, it was confirmed that the treatment effect was higher due to the gas shield effect than in the case of Reference Example 1.

It is a fragmentary sectional view showing roughly plasma treatment apparatus 10 concerning a reference form. (A) is a front view which shows electrode unit 4A, 4B, (b) is a top view of an electrode unit. (A) is a longitudinal sectional view schematically showing a plasma processing apparatus 10A according to a reference embodiment, and (b) is a transverse sectional view schematically showing the apparatus 10A. (A) is a longitudinal cross-sectional view which shows schematically the plasma processing apparatus which concerns on a comparative example, (b) is a cross-sectional view which shows the apparatus of (a) roughly. (A) is a front view which shows electrode unit 4A, 4B used with the apparatus of FIG. 6, (b) is a top view of an electrode unit. (A) is a longitudinal cross-sectional view which shows roughly the plasma processing apparatus 10B which concerns on a reference form, (b) is a cross-sectional view which shows the apparatus 10B schematically. (A) is a front view which shows electrode unit 4A, 4B used with the apparatus of FIG. 8, (b) is a top view of an electrode unit. (A) is a longitudinal cross-sectional view schematically showing a plasma processing apparatus 10C according to a reference embodiment, and (b) is a cross-sectional view schematically showing the apparatus 10C. (A) is a front view which shows electrode unit 4A, 4B used with the apparatus of FIG. 10, (b) is a top view of an electrode unit. (A) is a longitudinal sectional view schematically showing the plasma processing apparatus 10D, and (b) is a transverse sectional view schematically showing the apparatus 10D. (A) is a front view which shows electrode unit 4A, 4B applicable to this invention , (b) is a top view of an electrode unit. It is a longitudinal cross-sectional view which shows roughly the plasma processing apparatus 10E using the gas shield which can be applied to this invention.

  1A, 1B Ceramic layer 1a, 1c Surface 1b Back surface 2A, 2B Electrode layer 3A, 3B Terminal 4A, 4B Electrode unit 6 Processed object 7 Gap 8 Process gas 9 Activated gas 10, 10A, 10B, 10C, 10D, 10E Plasma processing apparatus 13 Spacer 14 Projection 15 Groove 16 Spacer part

Claims (2)

A first ceramic layer having a first electrode layer, a first ceramic layer embedded in the first electrode layer, and having protrusions and grooves formed between the protrusions on both ends of the surface side; the second electrode layer; A second ceramic layer having an electrode layer embedded therein and having protrusions and grooves formed between the protrusions on both ends of the surface side; a first electrode holding member for holding the first ceramic layer; and the second electrode A second electrode holding member that holds the ceramic layer; and a gas shield that is provided outside the first holding member and the second holding member and has an outlet opening that opens on the workpiece. A remote plasma processing apparatus,
The surface of the first ceramic layer and the surface of the second ceramic layer are arranged to face each other, and gas flow is caused by the grooves of the first ceramic layer and the grooves of the second ceramic layer. A path is formed, and the gas flow path is narrowed from the upstream to the downstream outlet as the distance between the protrusions at both ends is reduced , and the first electrode layer and the second electrode The process gas introduced into the gas flow path is activated using discharge by applying a voltage to the electrode layer, and the activated process gas is discharged from the discharge port, and the gas shield and the first holding A remote gas characterized by flowing the process gas activated from the outlet opening of the gas shield toward the object to be processed while flowing a shield gas between the member and the second holding member. Expression Zuma processing apparatus. An inert region not provided with the first electrode is provided under the surface of the first ceramic layer, and the second electrode is provided under the surface of the second ceramic layer. 2. A device according to claim 1, characterized in that there is no inactive region.

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