JPH07288194A - Plasma treatment apparatus - Google Patents

Abstract

PURPOSE:To lower the production cost and shorten the production time by surrounding and covering the outer circumference of an insulating member to become an electrode and applying high frequency electric power to the electrode through a high frequency electric power introducing means. CONSTITUTION:High frequency output is introduced through a matching circuit 111 into a conductive part 114 of a high frequency electric power introducing means 115 composed of an insulating member and the conductive member in layered structure. High frequency electric power is applied to a second electrode 106 through an insulating part 113. The insulating member to be a second electrode side is made to surround the outer circumference of the electrode 106 and cover the introducing means 115. Teflon and copper are used respectively for the insulating part 113 of the introducing means 115 and the conductive part 114, the length of the introducing means 115 in the cylinder axial direction is made 0.1 times ' that of the electrode 106 in the cylinder axial direction, and film formation is carried out under prescribed conditions. Then, raw material gases are introduced into a deposition chamber 101 and gas evacuation speed is adjusted to give prescribed pressure. The value calculated by deduction of reflected electric power from the sent high frequency electric power is adjust to be a desired value and when a desired film is formed, glow discharge is stopped.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crystalline or non-single crystalline functional deposition useful for electrophotographic photoreceptor devices as semiconductor devices, image input line sensors, imaging devices, photovoltaic devices, and the like. More specifically, the present invention relates to a plasma CVD apparatus capable of favorably forming a film, a semiconductor device, a sputtering apparatus capable of suitably forming an insulating film as an optical element, a metal wiring, etc., or a plasma processing apparatus such as an etching apparatus for a semiconductor device, etc. Is a plasma processing apparatus and processing method for processing a substrate using plasma as an excitation source.
The present invention relates to a plasma processing apparatus that can suitably use a high frequency of Hz or less.

[0002]

2. Description of the Related Art There are various methods for plasma processing apparatuses used in semiconductors and the like, depending on their respective applications. For example, in film formation, an oxide film and a nitride film are formed using a plasma CVD apparatus or a plasma CVD method, an amorphous silicon semiconductor film, a metal wiring film using a sputtering apparatus or a sputtering method, an etching apparatus and a method are used. A variety of devices and methods are used that take advantage of their features such as microfabrication technology.

Further, in recent years, there has been a strong demand for improvement in film quality and processing capacity, and various measures have been studied.

In particular, a plasma process using high frequency power has a high discharge stability and can be used for forming an insulating material such as an oxide film or a nitride film.

Conventionally, 13.56 MHz is generally used as the oscillation frequency of the discharge high frequency power source used in plasma processes such as plasma CVD. Plasma C, which is commonly used in the conventional deposition film formation
An example of the VD device is shown in FIG. The plasma CVD apparatus shown in FIG. 5 is a film forming apparatus suitable for forming an amorphous silicon film (hereinafter referred to as “a-Si film”) on a cylindrical electrophotographic photosensitive member substrate. Hereinafter, a method for forming an a-Si film using this apparatus will be described.

A reaction vessel 501 capable of depressurizing is formed into a cylindrical shape, which serves as a second electrode 506, and a first electrode which also serves as a counter electrode in the reaction vessel 501 and which also serves as a film-forming substrate (substrate for electrophotographic photoreceptor). An electrode 502 is arranged. Auxiliary substrates 507 and 508 are attached to the first electrode 502 and form a part of the first electrode. In order to improve the uniformity of the film thickness and the film characteristics, the dimension of the second electrode 506 in the cylindrical axis direction is set to the first electrode 502 and the auxiliary bases 507 and 5.
The length is set to be substantially the same as the length 08 of the cylinder in the axial direction. The first electrode 502 is heated from the inside by a heater 503 inside. The high frequency power supply 512 is connected to the second electrode 506 at only one place via the matching circuit 511.
Reference numeral 505 is a vacuum exhaust port, 504 is a main valve, 510 is a source gas introducing valve, and 509 is a source gas introducing port.

A film-forming substrate also serving as a first electrode is installed in the deposition chamber 501, a main valve 504 is opened, and an exhaust port 5 is provided.
The deposition chamber 501 is once evacuated via 05. After that, the raw material gas introduction port 510 is opened, an inert gas is introduced, and the flow rate is adjusted so as to reach a predetermined pressure. Heating heater 50
3 is energized to heat the film formation substrate to a desired temperature of 100 to 400 ° C.

After that, a raw material gas for film formation, for example, a raw material gas such as silane gas, disilane gas, methane gas, ethane gas, or a doping gas such as diborane gas or phosphine gas is introduced through a raw material gas introduction valve 510, and from several mTorr. Adjust the pumping speed to maintain a pressure of a few Torr.

A high frequency power of 13.56 MHz is supplied from a high frequency power supply 512 to a second electrode 506 via a matching circuit 511.
To generate a plasma discharge between the second electrode 506 and the first electrode 502 to decompose the raw material gas, so that a-S is deposited on the film formation substrate 502 which also serves as the first electrode.
Deposit i-film. During this time, the first electrode is the heater 5
03, the temperature is maintained at about 100 to 400 ° C.

If necessary, the film formation substrate 502 may be rotated by a rotation mechanism (not shown) to improve the film thickness distribution in the circumferential direction.

The deposition rate for obtaining an a-Si film satisfying the performance of the electrophotographic photoreceptor by this film forming method is, for example, 1.
The deposition rate is about 0.5 to 6 μm per hour, and if the deposition rate is further increased, the characteristics of the photoconductor may not be obtained. Further, generally, when an a-Si film is used as an electrophotographic photoreceptor, a film thickness of at least 20 to 30 μm is required to obtain charging ability, and it takes a long time to manufacture the electrophotographic photoreceptor. I needed it. Therefore, there has been a strong demand for a technique for reducing the manufacturing time without deteriorating the characteristics of the photoconductor.

By the way, in recent years, a parallel plate type plasma CV is used.
There is a report of a plasma CVD method using a high frequency power source of 20 MHz or more using a D device (Plasma Chemistry and Pla
smaProcessing, Vol.7, No.3, (1987) p267-273), there is a possibility that the deposition rate can be improved without lowering the performance of the deposited film by increasing the discharge frequency higher than the conventional 13.56 MHz. Shown and noted. In addition, reports of increasing the frequency for discharge have also been made by sputtering, etc., and its superiority has been widely studied in recent years.

Therefore, in order to improve the deposition rate, the discharge frequency is changed to a high frequency power having a frequency higher than the conventional 13.56 MHz, and the deposition procedure is performed in the same manner as the conventional deposition. It was confirmed that it can be created with. However, in this case, it became clear that the following problems, which were not a problem at the discharge frequency of 13.56 MHz, might newly occur.

That is, when the film formation is carried out while rotating the film formation substrate, a film having characteristics substantially the same as those of the conventional film is deposited, and naturally the film thickness distribution in the circumferential direction is also uniform. I can. However, when the deposition film forming apparatus in which the rotation mechanism of the film formation substrate is omitted is used for the purpose of reducing the cost of the film formation furnace and reducing the complexity of maintenance, and the film formation substrate is subjected to film formation in a stationary state, It was found that the film thickness distribution in the circumferential direction was extremely large. In other words, although it did not appear on the surface when the film-forming substrate was rotated, the plasma state in the film-forming furnace was actually unevenly distributed in the circumferential direction, and the deposition rate also varied greatly depending on the location. Became clear.

Further, it was found that not only the deposition rate but also the electrophotographic characteristics of the deposited film differed considerably depending on the location in the circumferential direction. Since the unevenness of this characteristic cannot be explained only by the difference in the thickness of the deposited film, it is presumed that the quality of the deposited film itself is different in the circumferential direction. Further, in the portion where the film quality in the circumferential direction is good, the characteristics are superior to the photosensitive drum on which the film is formed by rotating the substrate to be processed, and conversely, in the portion where the film quality is inferior in the circumferential direction, the characteristics of the rotated drum are Turned out to be inferior. That is, it is presumed that, on the photosensitive drum formed by rotating the film-forming substrate, a film having inferior characteristics and a film having excellent characteristics are laminated, and average characteristics appear.

As described above, in the conventional film formation by the high frequency power having a frequency higher than 13.56 MHz, the film thickness distribution in the circumferential direction and the film characteristics are uneven when the film formation substrate is formed in a stationary state. As a result, image unevenness, which is a problem in practical use, may occur in a relatively large area work piece such as an electrophotographic photoreceptor.

Further, in the case of forming a film by rotating the substrate to be processed, it is inevitable to stack a film having excellent characteristics and a film having inferior characteristics due to uneven distribution of plasma, so that the total film characteristics will be improved. Due to the deterioration, there is a problem that the desired good film characteristics cannot be obtained.

Such unevenness of the deposition rate and the film characteristics is caused not only by the electrophotographic photoreceptor but also by the image input line sensor,
Crystalline materials useful for imaging devices, photovoltaic devices, etc.
Or, it becomes a big problem when a non-single crystalline functional deposited film is formed. Also, in other plasma processes such as dry etching and sputtering, similar process unevenness occurs when the discharge frequency is increased, and if it is left as it is, it becomes a serious problem in practical use.

[0019]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned problems of the prior art and to make a relatively large area of a substrate uniform at a high processing speed which cannot be achieved by the conventional plasma process. An object of the present invention is to provide a plasma processing apparatus capable of performing plasma processing.

Further, the manufacturing time is short and the cost is low,
For example, it is an object of the present invention to provide a plasma processing apparatus which is most suitable for manufacturing an electrophotographic photoreceptor having excellent image characteristics.

[0021]

A plasma processing apparatus according to the present invention which achieves the above object, is a cylinder that also serves as a film-forming substrate installed in a vacuum-tight deposition chamber provided with an exhaust unit and a source gas supply unit. The first electrode in the shape of a ring and the second electrode in the shape of a cylinder, which encloses the first electrode and is installed concentrically, applies high-frequency power with a frequency of 20 MHz to 450 MHz to the second electrode. In a plasma processing apparatus for generating a discharge between a first electrode and a second electrode, a high-frequency power introducing unit having a laminated structure of an insulating member and a conductive member is provided as a second electrode with the insulating member on the second electrode side. It is characterized in that the outer circumference of the electrode is covered with a single circumference so that the high frequency power is applied to the second electrode through the high frequency power introducing means.

[0022]

The present inventor has made the film-forming substrate 20 to 4 in a stationary state.
In order to solve the film thickness and film characteristic unevenness in the circumferential direction when the film formation was performed using a high frequency of 50 MHz, an intensive study was conducted.

First, an experiment was conducted to confirm the positional relationship between the film thickness unevenness and the position where the high frequency power is introduced. As a result, it was found that, contrary to the expectation, the film thickness distribution was generated regardless of the position where the high frequency power was introduced.
The reason for this is not clear at present, but when a high frequency in the so-called VHF region of 20 MHz or more and 450 MHz or less is used, the second electrode (cathode) applied
It is considered that the inductance component of cannot be ignored. However, if only the inductance is a problem, the deposition rate should be faster on the side to which the high frequency is applied and slower on the opposite side where the physical distance is longer than the application position. The fact that there is no correlation in the positional relationship means that not only the inductance of the second electrode is a problem in this frequency range, but also the capacitance between the second electrode and the first electrode may be a problem. There is a nature. In other words, the deposition furnace itself forms a series resonance circuit of inductance and capacitance in the frequency range of 20 to 450 MHz, and the high frequency power increases at the position satisfying the resonance condition ω = 1 / (L · C) ^1/2. It is speculated that the decomposition rate of the raw material gas will increase. Where ω is the angular velocity, L
Is inductance and C is capacitance.

Further, when the electric characteristics of the film deposited on the film-forming substrate after film formation were measured, it was found that the film at the place where the deposition rate was faster exhibited better properties than the film at the place where the deposition rate was slow. . Generally, the slower the deposition rate, the better the film properties,
In this case, it is considered that supplying sufficient high frequency energy to the source gas contributes to the improvement of the film characteristics.

From the above experiment, in the film formation using a high frequency of 20 to 450 MHz, if the power can be evenly applied in the circumferential direction of the second electrode, it is possible to rotate the film-forming substrate sufficiently in the circumferential direction. It was concluded that the film quality of the deposited film could be improved because the film thickness uniformity can be obtained and sufficient electric power can be supplied.

According to the present invention, based on the above findings, by covering the outer circumference of the second electrode with the insulating member over the entire circumference, and further covering the outer circumference of the insulating member with the conductive member over the entire circumference,
By satisfying the LC resonance condition over the entire circumference of the second electrode, it is intended to supply sufficient high frequency power in the entire circumferential direction.

The present invention will be described in detail below with reference to the drawings.

FIG. 1 schematically shows an example of an apparatus for carrying out the method of the present invention, which is suitable for forming a deposited film on a cylindrical substrate such as an electrophotographic photoreceptor. .
In FIG. 1, 101 is a deposition chamber for forming a deposited film, which is connected to an exhaust device (not shown) by a main valve 104. Reference numeral 109 is a raw material gas inlet for introducing the raw material gas into the deposition chamber, and introduces the raw material gas into the deposition chamber from a gas supply system (not shown). Reference numeral 102 denotes a first electrode which is also connected to the ground and serves as a film-forming substrate, and auxiliary substrates 107 and 108 are provided above and below the film-forming substrate. Reference numeral 103 is a heater for heating the substrate to a predetermined temperature. Further, the film-forming substrate may be rotated by a rotation mechanism (not shown) as necessary to further uniformize the film thickness in the circumferential direction. 112 is 20MHz to 450M
It is a high frequency power source for generating a high frequency of Hz, and the high frequency output is a high frequency power introducing means 115 through a matching circuit 111.
Is introduced into the conductive portion 114 of the
5 is applied to the second electrode 106 through the insulating portion 113. As shown, the second electrode 106 is located in the deposition chamber 101.
Of course, it may be used as the inner wall of the.

The conductive portion 114 of the high frequency power introducing means 115
Any material having high conductivity can be used as the material used for the above, but a material having a low magnetic permeability is preferable for the purpose of minimizing the inductance of the wiring itself. Specific materials include Cu, Al, Au, A
g, Pt, Pb, Ni, Co, Fe, Cr, Mo, Ti
And the like, and alloys thereof such as stainless steel are preferable.

Insulating part 113 of high frequency power introducing means 115
Any material can be used as long as it has a high insulating property, but a material used for the purpose of effectively transmitting high frequency power is preferably one having a high dielectric breakdown voltage and a small dielectric loss tangent. Specific materials include Teflon, alumina, silicon oxide, silicon carbide, silicon nitride, boron nitride, aluminum nitride, polystyrene and the like.

Further, the shape of the high-frequency power introducing means is preferably a shape having a surface area as large as possible in consideration of the skin effect of the high-frequency power, and a cylindrical flat plate shape in consideration of ease of matching and processing. Is optimal.

The size of the high-frequency power introducing means is appropriately determined in consideration of the wirings from the first and second electrodes and the matching circuit to the high-frequency power introducing means. It is preferable that the area is larger than 114.

Further, as shown in FIG. 2, the insulating portion 213 and the conductive portion 214 of the high frequency power introducing means may be laminated in a plurality of layers. By stacking over multiple layers,
It is possible to increase the freedom of the size of the high frequency power introducing means, and it is possible to make a more optimal high frequency power introducing means.

The high frequency power source used has an oscillation frequency of 2
Anything from 0 MHz to 450 MHz can be used. Also, the output is from 10W to over 5000W,
Any output can be suitably used as long as it can generate electric power suitable for the device. Further, the effect of the present invention can be obtained regardless of the output fluctuation rate of the high frequency power supply.

As the matching circuit used, any structure can be preferably used as long as it can match the high frequency power source and the load. Further, as a method for obtaining matching, an automatically adjusted method is suitable for avoiding complications during manufacturing, but even a manually adjusted method has no influence on the effect of the present invention. . Regarding the position where the matching circuit is placed, there is no problem in installing it anywhere within the range where matching can be achieved, but it should be placed so that the inductance of the wiring between the matching circuit and the high frequency power introducing means is as small as possible. Is desirable because it enables matching under a wide range of load conditions.

The material of the second electrode is Cu, Al, A
u, Ag, Pt, Pb, Ni, Co, Fe, Cr, M
Metals such as o and Ti, and alloys thereof such as stainless steel are preferable. The shape is preferably a cylindrical shape, but an elliptical shape or a polygonal shape may be used if necessary.
If necessary, the second electrode may be provided with a cooling means. As a specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

The first electrode of the present invention has a role as a film-forming substrate, and may be any material having a material and a shape according to the purpose of use. For example, regarding the shape, a cylindrical shape is preferable when it is used for an electrophotographic photoreceptor, but a flat plate shape or another shape may be used as necessary. In terms of material, Al, Cr, Mo, Au, In, Nb, T
Examples thereof include metals such as e, V, Ti, Pt, Pb, and Fe, and alloys thereof such as stainless steel. Also, sheets of synthetic resin such as polyester, polystyrene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyethylene, polyamide, glass,
It is also possible to use a substrate in which at least the surface of the electrically insulating substrate made of ceramic or the like on which the deposited film is formed is subjected to a conductive treatment. Further, it is desirable that the side opposite to the side on which the deposited film is formed be subjected to conductive treatment.

The surface shape of the substrate can be a smooth flat surface or an uneven surface. For example, in the case of performing image recording using a coherent light such as a laser beam on a light receiving member for electrophotography, in order to eliminate an image defect due to an interference fringe pattern appearing in a visible image, JP-A-Sho 60 is used. -1681
56, 60-178457 and 60-2.
It can be an uneven surface produced by a known method described in Japanese Patent No. 25854.

An example of the method of forming a deposited film according to the present invention is performed according to the following procedure.

First, auxiliary substrates 107 and 108 are attached to a film-forming substrate (also serving as the first electrode) 102 whose surface is mirror-finished by using a lathe, and a heater 103 for heating in the deposition chamber 101 is covered. Film-forming substrate 102 and auxiliary substrate 1
07 and 108 are inserted.

Next, the source gas introduction valve 110 is closed, the main valve 104 is opened, and the deposition chamber is once evacuated through the exhaust port 105, and then the source gas introduction valve 11 is used.
When 0 is opened, an inert gas for heating, for example, argon is introduced into the deposition chamber through the raw material gas inlet 109, and the flow rate of the heating gas is adjusted so that the deposition chamber has a desired pressure. Then, a temperature controller (not shown) is operated to heat the substrate 102 by the heater 103, and when the substrate 102 is heated to a desired temperature, the source gas introduction valve 110 is closed to stop the gas flow into the deposition chamber.

The source gas introduction valve 110 is used to form the deposited film.
Is opened and a predetermined source gas is introduced into the deposition chamber 101 through the source gas inlet 109, and a few mTorr to a few Torr
Adjust the evacuation rate to maintain the desired pressure of. After the pressure is stabilized, the high frequency power supply 112 is turned on to supply power with a frequency of 20 MHz to 450 MHz to cause glow discharge. At this time, the matching circuit 111 is adjusted so as to minimize the reflected wave. The value obtained by subtracting the reflected power from the high frequency incident power is adjusted to a desired value, the glow discharge is stopped when the desired film thickness is formed, and the source gas introduction valve 110 is closed to set the source gas deposition chamber 101.
Flow is stopped, the deposition chamber is once evacuated to a high vacuum, and then the layer formation is completed. When stacking deposited films having various functions, the above operation is repeated.

The source gas used in the present invention is, for example, Si when forming amorphous silicon.
Silicon hydride (silanes) in a gas state such as H ₄ , Si ₂ H ₆ or capable of being gasified is effectively used as a gas for supplying Si. Further, in addition to silicon hydride, a silicon compound containing a fluorine atom, a so-called silane derivative substituted with a fluorine atom, specifically, silicon fluoride such as SiF ₄ , Si ₂ F ₆ or SiH ₃ F is used. , SiH ₂ F ₂ , SiHF _{3 and} other fluorine-substituted silicon hydrides are also effective as the Si supply gas of the present invention. Further, any way no problem to be present invention used as diluted by these H ₂ as needed starting material gas for Si supply, the He, Ar, gas Ne or the like.

Further, in addition to the above-mentioned gas, an atom belonging to Group 3 of the periodic table or an atom belonging to Group 5 of the periodic table can be used as a so-called dopant, if necessary. For example, when using a boron atom (B),
Examples thereof include boron hydrides such as B ₂ H ₆ and B ₄ H ₁₀ and boron halides such as BF ₃ and BCl ₃ . When a phosphorus atom is used, PH ₃ , P ₂ H _{4 and} other hydrogenated phosphorus, PH ₄ I, PF
Phosphorus halides such as ₃ , PCl ₃ , PBr ₃ and PI ₃ can be used.

In addition, for example, when forming amorphous silicon carbide (a-SiC), in addition to the above-mentioned raw material gas, as a gas for introducing carbon atoms, C and H are constituent atoms, for example, carbon. A saturated hydrocarbon of the numbers 1 to 5,
Ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms and the like can be used. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C
₂ H ₆ ) etc., ethylene (C
₂ H ₄ ), propylene (C ₃ H ₆ ) and the like, acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), and the like.

When forming amorphous silicon oxide (a-SiO), for example, oxygen (O ₂ ), ozone (O ₃ ) can be used as a gas for introducing oxygen atoms in addition to the above-mentioned raw material gas. ), Nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O),
Nitrogen trioxide (N ₂ O ₃ ), Nitrogen dioxide (N ₂ O ₄ ), Nitrogen pentaoxide (N ₂ O ₅ ), Nitric oxide (NO ₃ ), Silicon atom (Si) and oxygen atom (O) Hydrogen For example, disiloxane (H ₃ SiOSi) having atoms (H) as constituent atoms
H ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ )
And other lower siloxanes and the like.

In the present invention, when amorphous silicon nitride (a-SiN) is formed, for example, nitrogen (N ₂ ) and ammonia can be used in addition to the above-mentioned raw material gas as a gas for introducing nitrogen atoms. Nitrogen compounds such as (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium (NH ₄ N ₃ ), etc., such as gaseous or gasifiable nitrogen, nitrogen compounds and azides. be able to. In addition to this, nitrogen trifluoride (F ₃
N), nitrogen tetrafluoride (F ₄ N ₂ ) and other nitrogen halide compounds.

Hereinafter, the present invention will be described in more detail with reference to Examples.

[0049]

【Example】

(Embodiment 1) In the deposited film forming apparatus shown in FIG. 1, a high frequency power source having an oscillation frequency of 105 MHz was installed, an a-Si film was formed on a cylindrical substrate made of aluminum, and an electrophotography having the layer structure shown in FIG. A photoconductor was prepared. The electrophotographic photoreceptor 301 shown in FIG. 3 includes a substrate 302, a lower blocking layer 303, a photoconductive layer 304, and a surface layer 305.

In this embodiment, Teflon is used for the insulating part 113 of the high-frequency power introducing means and copper is used for the conductive part 114, and the length of the high-frequency power introducing means in the cylinder axis direction is defined by the cylinder axis direction of the second electrode. The length is set to 0.1 times, and the film forming conditions are shown in Table 1.
A film was formed according to the manufacturing conditions shown in. Furthermore, single-crystal silicon substrates were placed at four locations in the circumferential direction on an aluminum cylindrical substrate, and a 1 μm a-Si film was formed according to the photoconductive layer manufacturing conditions shown in Table 1. A sample for infrared spectroscopy measurement was prepared.

In each film formation, the substrate was formed in a stationary state.

Comparative Example 1-1 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 1 except that the deposited film forming apparatus shown in FIG. 5 was used. did.

(Comparative Example 1-2) The high frequency power introducing means shown in FIG. 6 is composed only of the conductive part 614 made of copper, and the length of the high frequency power introducing means in the cylinder axis direction is the cylinder of the second electrode. An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 1 except that a deposited film forming apparatus having a length of 0.1 times in the axial direction was used.

The electrophotographic photoconductors and infrared spectroscopic measurement samples prepared in Example 1, Comparative Example 1-1 and Comparative Example 1-2 were evaluated by the following methods.

Film thickness distribution evaluation The film thickness at 16 locations in the circumferential direction of each photoconductor was measured by an eddy current type film thickness meter (manufactured by Kett Scientific Research Institute), and the difference between the maximum film thickness and the minimum film thickness was determined. The ratio of the film thickness distribution was calculated by dividing by the average film thickness. Then, the evaluation was performed with a relative value with the film thickness distribution ratio of the photosensitive drum of Comparative Example 1-1 being 1. That is, the smaller the value is, the more the film thickness unevenness is improved.

Electrophotographic characteristics Electrophotographic apparatus (NP manufactured by Canon Inc.) for each photoconductor
6060 was modified for experiment) and the charging ability was evaluated as follows as an initial electrophotographic characteristic.

The photoreceptive member for electrophotography was installed in a device for electrophotography, a high voltage of +6 kV was applied to a charger to perform corona charging, and the surface potential of the dark part of the photoreceptive member for electrophotography was measured. The ratio of the dark surface potential was calculated by dividing the difference between the maximum and minimum dark surface potentials by the average dark surface potential. Then, the evaluation was performed with a relative value with the dark area surface potential ratio of the photosensitive drum of Comparative Example 1-1 being 1. In other words, the smaller the numerical value is, the more the dark part surface potential unevenness is improved.

Furthermore, the average surface potential of the dark portion is normalized by dividing it by the average film thickness, and after removing the influence of the film thickness, the average surface potential of the dark portion is calculated, and the photosensitive drum of Comparative Example 1-1 is calculated. The evaluation was performed by the relative value obtained by dividing the average surface potential of the dark area of each by the average surface potential of each dark area. That is, the smaller the value is, the more the average dark surface potential is improved.

Evaluation of film quality distribution The manufactured infrared spectroscopic measurement sample was measured with an infrared spectrophotometer.
Installed on (Perkin Elmer 1720-X), 2
000 cm^-1Si-H appearing in the vicinity_n(N = 1 to 3)
Infrared absorption spectrum of Si-H at 2000 cm
^-1Depending on the neighborhood, Si-H₂And Si-H₃By 2
100 cm^-1Waveforms are separated into those due to the vicinity, and each infrared
Absorption cross-section ratio (2100 cm^-1Absorption cross section / 2
000 cm ^-1The absorption cross section in the vicinity) was determined. And the ratio
Evaluated by the relative value with the infrared absorption cross-section ratio of Comparative Example 1-1 being 1.
I went. In other words, the smaller the value, the more 2100 cm
^-1The absorption cross section in the vicinity is small and the film quality is improved.
Indicates.

The above results are summarized in Table 2. In both evaluations, the electrophotographic optical body and infrared spectroscopic measurement sample produced in Example 1 had a smaller circumferential distribution than the electrophotographic optical body and infrared spectroscopic measurement sample produced in Comparative Example 1. , The characteristics are also excellent.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film of good film quality can be formed.

[0062]

[Table 1]

[0063]

[Table 2] (Note) Relative value based on Comparative Example 1-1

Example 2 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that a high frequency power source with an oscillation frequency of 200 MHz was used.

(Comparative Example 2-1) Oscillation frequency 200 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-1, except that the high frequency power source of No. 1 was used.

(Comparative Example 2-2) Oscillation frequency 200 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-2 except that the high frequency power source of No. 1 was used.

The electrophotographic photosensitive member and the infrared spectroscopic measurement sample prepared in Example 2 and Comparative Example 2-2 were subjected to the same procedure as in Example 1 for the film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 3. As can be seen from Table 3, Example 2 of the present invention has a small distribution in the circumferential direction and is excellent in characteristics in any evaluation.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film of good film quality can be formed.

[0069]

[Table 3] (Note) Relative value based on Comparative Example 2-1

Example 3 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that a high frequency power source with an oscillation frequency of 300 MHz was used.

(Comparative Example 3-1) Oscillation frequency 300 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-1, except that the high frequency power source of No. 1 was used.

(Comparative Example 3-2) Oscillation frequency 300 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-2 except that the high frequency power source of No. 1 was used.

The electrophotographic photosensitive member and the infrared spectroscopic measurement sample prepared in Example 3 and Comparative Example 3-2 were subjected to the same procedure as in Example 1 for the film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 4. As can be seen from Table 4, Example 3 of the present invention has a small distribution in the circumferential direction and is excellent in characteristics in any evaluation.

From the above results, it has been found that according to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film of good film quality can be formed.

[0075]

[Table 4] (Note) Relative value based on Comparative Example 3-1

Example 4 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that a high frequency power source with an oscillation frequency of 450 MHz was used.

(Comparative Example 4-1) Oscillation frequency 450 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-1, except that the high frequency power source of No. 1 was used.

(Comparative Example 4-2) Oscillation frequency 450 MHz
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-2 except that the high frequency power source of No. 1 was used.

The electrophotographic photosensitive member and infrared spectroscopic measurement sample prepared in Example 4 and Comparative Example 4-2 were subjected to the same procedure as in Example 1 to obtain the film thickness distribution ratio, dark surface potential nonuniformity, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 5. As can be seen from Table 5, Example 4 of the present invention has a small circumferential distribution and excellent characteristics in any evaluation.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film of good film quality can be formed.

[0081]

[Table 5] (Note) Relative value based on Comparative Example 4-1

Example 5 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that a high frequency power source with an oscillation frequency of 50 MHz was used.

Comparative Example 5-1 An electrophotographic photoreceptor and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-1 except that a high frequency power source with an oscillation frequency of 50 MHz was used.

Comparative Example 5-2 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-2 except that a high frequency power source with an oscillation frequency of 50 MHz was used.

The electrophotographic photosensitive member and the infrared spectroscopic measurement sample prepared in Example 5 and Comparative Example 5-2 were subjected to the same procedure as in Example 1 to obtain a film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 6. As can be seen from Table 6, Example 5 of the present invention has a small circumferential distribution and is excellent in characteristics in any evaluation.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film with good film quality can be formed.

[0087]

[Table 6] (Note) Relative value based on Comparative Example 5-1

(Example 6) An electrophotographic photoreceptor and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that a high frequency power source with an oscillation frequency of 20 MHz was used.

(Comparative Example 6-1) An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-1 except that a high frequency power source with an oscillation frequency of 20 MHz was used.

Comparative Example 6-2 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Comparative Example 1-2 except that a high frequency power source with an oscillation frequency of 20 MHz was used.

The electrophotographic photosensitive member and infrared spectroscopic measurement sample prepared in Example 6 and Comparative Example 6-2 were subjected to the same procedure as in Example 1 to obtain a film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 7. As can be seen from Table 7, Example 6 of the present invention has a small distribution in the circumferential direction and is excellent in characteristics in any evaluation.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film of good film quality can be formed.

[0093]

[Table 7] (Note) Relative value based on Comparative Example 6-1

(Embodiment 7) In the deposited film forming apparatus shown in FIG. 2, a high frequency power source with an oscillation frequency of 105 MHz is installed, an a-Si film is formed on an aluminum cylindrical substrate, and the layer structure shown in FIG. A photoconductor for electrophotography was prepared.

In this embodiment, Teflon is used for the insulating part 213 of the high-frequency power introducing means, and copper is used for the conductive part 214 to provide two layers of the insulating part 213 and the conductive part 214. The length in the direction was set to 0.3 times the length in the cylinder axis direction of the second electrode, and film formation was performed according to the manufacturing conditions shown in Table 8 as film forming conditions.

Furthermore, single-crystal silicon substrates were placed at four circumferential positions on an aluminum cylindrical substrate, and a 1 μm a-Si film was formed according to the photoconductive layer manufacturing conditions shown in Table 8. Then, an infrared spectroscopy measurement sample was prepared.

In each film formation, the substrate was formed in a stationary state.

(Comparative Example 7-1) An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 7 except that the deposited film forming apparatus shown in FIG. 5 was used. did.

(Comparative Example 7-2) The high frequency power introducing means shown in FIG. 6 is composed only of the conductive portion 614 made of copper, and the length of the high frequency power introducing means in the cylindrical axis direction is defined by the cylindrical axis of the second electrode. An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 7, except that a deposited film forming apparatus having a length of 0.3 times the length was used.

The electrophotographic photoreceptors and infrared spectroscopic measurement samples prepared in Example 7 and Comparative Example 7-2 were subjected to the same procedure as in Example 1 to obtain a film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 9. As can be seen from Table 9, in any of the evaluations, Example 7 of the present invention has a small circumferential distribution and is excellent in characteristics.

From the above results, it was found that according to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film of good film quality can be formed.

[0102]

[Table 8]

[0103]

[Table 9] (Note) Relative value based on Comparative Example 7-1

Example 8 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that alumina ceramic was used for the insulating portion 113 of the high frequency power introducing means. did.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, dark surface potential unevenness, average dark surface potential, and infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

Example 9 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that silicon oxide was used for the insulating portion 113 of the high frequency power introducing means.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, dark surface potential nonuniformity, average dark surface potential, and infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

(Example 10) An electrophotographic photoreceptor and a sample for infrared spectroscopic measurement were prepared under the same conditions as in Example 7 except that silicon carbide was used for the insulating portion 213 of the high frequency power introducing means.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential nonuniformity, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film with good film quality can be formed. It has been found.

Example 11 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 7 except that silicon nitride was used for the insulating portion 213 of the high frequency power introducing means.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential nonuniformity, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

Example 12 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that boron nitride was used for the insulating portion 113 of the high frequency power introducing means.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential unevenness, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform, and a deposited film with good film quality can be formed. It has been found.

(Example 13) Example 7 was repeated except that aluminum nitride was used for the insulating portion 213 of the high frequency power introducing means.
Under the same conditions as above, an electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark part surface potential unevenness, the average dark part surface potential, and the infrared absorption cross section ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

Example 14 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 7 except that polystyrene was used for the insulating portion 213 of the high frequency power introducing means.

The electrophotographic photosensitive member thus prepared and the infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential unevenness, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

Example 15 In the deposited film forming apparatus shown in FIG. 1, a high frequency power source with an oscillation frequency of 105 MHz is installed, an a-Si film is formed on an aluminum cylindrical substrate, and the layer structure shown in FIG. A photoconductor for electrophotography was prepared.
In the electrophotographic photosensitive member 401 shown in FIG.
02, a lower blocking layer 403, a photoconductive layer 404, and an upper blocking layer 405 surface layer 406.

In this embodiment, Teflon is used for the insulating portion 113 of the high frequency power introducing means and copper is used for the conductive portion 114, and the conductive path 114 from the matching circuit 111 to the high frequency power introducing means is divided into two paths. The parts 114 were connected to two opposite parts.

Further, the length of the high frequency power introducing means in the cylinder axis direction is set to 0.2 times the length of the second electrode in the cylinder axis direction, and the film forming conditions are set according to the manufacturing conditions shown in Table 10. A film was formed.

Further, single-crystal silicon substrates were installed at four locations in the circumferential direction on a cylindrical base body made of aluminum, and 1 μm a-Si was formed according to the manufacturing conditions of the photoconductive layer shown in Table 10.
A film was formed to prepare a sample for infrared spectroscopy measurement.

In all the film formations, the substrate was formed in a stationary state.

(Comparative Example 15-1) Using the deposited film forming apparatus shown in FIG. 5, the matching circuit 511 to the second electrode 506 are divided into two paths, and the second electrodes 506 facing each other are divided into two paths.
An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same film forming conditions as in Example 15 except that the sample was connected to a place.

(Comparative Example 15-2) Using the deposited film forming apparatus shown in FIG. 6, the high-frequency power introducing means was made of copper as the conductive portion 61.
The matching circuit 611 is divided into two paths from the matching circuit 611 to the conductive portion 614 of the high frequency power introducing means, and the conductive portion 61 is divided into two paths.
Example 4 except that the length of the high-frequency power introducing means in the cylinder axis direction was 0.2 times the length of the second electrode in the cylinder axis direction. Under similar film forming conditions, a photoconductor for electrophotography and a sample for infrared spectroscopic measurement were prepared.

The electrophotographic photoreceptors and infrared spectroscopic measurement samples prepared in Example 15 and Comparative Example 15-2 were subjected to the same procedure as in Example 1 to obtain a film thickness distribution ratio, dark surface potential unevenness, and average dark surface potential. The infrared absorption cross-sectional area ratio was evaluated. The results are shown in Table 11. As can be seen from Table 11, Example 1 of the present invention
No. 5 has a small distribution in the circumferential direction in all evaluations and has excellent characteristics.

From the above results, it has been found that according to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film of good film quality can be formed.

[0127]

[Table 10]

[0128]

[Table 11] (Note) Relative value based on Comparative Example 15-1

Example 16 An electrophotographic photoconductor and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 15 except that the film was formed while rotating the substrate.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential nonuniformity, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

Example 17 An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Example 1 except that aluminum was used for the conductive portion 114 of the high frequency power introducing means.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, dark surface potential unevenness, average dark surface potential, and infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

(Embodiment 18) An electrophotographic photosensitive member and an infrared spectroscopic measurement sample were prepared under the same conditions as in Embodiment 15, except that the conductive portion 114 of the high frequency power introducing means was made of silver-plated copper. Was produced.

The prepared electrophotographic photosensitive member and infrared spectroscopic measurement sample were evaluated for the film thickness distribution ratio, the dark surface potential nonuniformity, the average dark surface potential, and the infrared absorption cross-sectional area ratio in the same procedure as in Example 1. However, as in Example 1, the distribution in the circumferential direction is small and the characteristics are excellent. According to the present invention, the film thickness in the circumferential direction can be made uniform and a deposited film with good film quality can be formed. It has been found.

[0135]

EFFECTS OF THE INVENTION Since the electric power can be uniformly supplied to the second electrode, the film thickness distribution in the circumferential direction can be reduced, and further, sufficient electric power can be supplied to the discharge space, so that the film characteristics of the deposited film can be improved. It is possible to improve.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a deposited film forming apparatus of the present invention.

FIG. 2 is a schematic view showing an example of another deposited film forming apparatus of the present invention.

FIG. 3 is a schematic view showing an example of the layer structure of an electrophotographic photosensitive member created by the deposited film forming apparatus of the present invention.

FIG. 4 is a schematic view showing an example of another layer structure of the electrophotographic photosensitive member created by the deposited film forming apparatus of the present invention.

FIG. 5 is a schematic view showing an example of a conventional deposited film forming apparatus.

FIG. 6 is a schematic view showing an example of a conventional deposited film forming apparatus.

[Explanation of symbols]

101, 201, 301, 401 deposition chamber, 102, 202, 302, 402 first electrode also serving as a film-forming substrate, 103, 203, 303, 403 heating heater, 104, 204, 304, 404 main valve, 105 , 205, 305, 405 Exhaust port, 106, 206, 306, 406 Second electrode also serving as inner wall of deposition chamber, 107, 108, 207, 208, 307, 308, 4
07,408 Auxiliary substrate, 109,209,309,409 Raw material gas introduction port, 110,210,310,410 Raw material gas introduction valve, 111,211,311,411 Matching device, 112,212,312,412 20MHz to 45
0 MHz high frequency power source, 113, 213 high frequency power introducing means insulating part, 114, 214 high frequency power introducing means conducting part, 301, 401 electrophotographic photoconductor, 302, 402 substrate, 303, 403 lower blocking layer, 304, 404 Photoconductive layer, 305,406 Surface layer, 405 Top blocking layer.

Claims (14)

[Claims] 1. A cylindrical first electrode, which also serves as a film-forming substrate, is installed in a vacuum-tight deposition chamber equipped with an exhaust means and a source gas supply means. And frequency 2 is applied to the cylindrical second electrode placed on the concentric circle.
In a plasma processing apparatus for generating a discharge between a first electrode and a second electrode by applying a high frequency power of 0 MHz to 450 MHz to a second electrode, a high frequency wave having a laminated structure of an insulating member and a conductive member. Power introduction means,
On the outer periphery of the second electrode with the insulating member on the second electrode side,
A plasma processing apparatus, characterized in that the outer periphery is covered with a circuit and the high frequency power is applied to the second electrode through the high frequency power introducing means. 2. The plasma processing apparatus according to claim 1, wherein the high-frequency power introduction means covers a part of the second electrode in the cylindrical axis direction. 3. The plasma processing apparatus according to claim 1, wherein the high-frequency power introduction means has a laminated structure of two or more layers of an insulating member and a conductive member. 4. A high frequency power source is branched into a plurality of circuits after passing through a matching unit, and is connected to two or more positions in the circumferential direction of the high frequency power introducing means. The plasma processing apparatus according to any one of 3 above. 5. The plasma processing apparatus according to claim 4, wherein the lengths of the wiring members from the matching unit to the respective supply points to the high frequency power introducing means are all equal. 6. The plasma processing apparatus according to claim 1, wherein the second electrode also serves as a furnace wall of the deposition chamber. 7. The plasma processing apparatus according to claim 1, wherein the film formation is performed with the first electrode stationary. 8. The plasma processing apparatus according to claim 1, wherein the film formation is performed with the first electrode rotated. 9. The insulating member of the high frequency power introducing means is made of Teflon.
The plasma processing apparatus according to claim 1. 10. The plasma processing apparatus according to claim 1, wherein the insulating member of the high frequency power introducing means is made of alumina ceramics. 11. The insulating member of the high frequency power introducing means is made of at least one of silicon oxide, silicon carbide and silicon nitride. Plasma processing equipment. 12. The plasma processing apparatus according to claim 1, wherein the insulating member of the high frequency power introducing means is made of at least one of boron nitride and aluminum nitride. 13. The plasma processing apparatus according to claim 1, wherein the insulating member of the high frequency power introducing means is made of polystyrene. 14. The plasma processing apparatus according to claim 1, wherein the deposited film forming apparatus is a plasma CVD apparatus.