JP2000008170A - Plasma cvd device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma CVD device capable of executing film formation onto a long-length substrate with a large area at a high film forming rate and capable of obtaining a thin film small in the generation of defects caused by the sticking of powder and having the uniformity of film characteristics. SOLUTION: In a plasma CVD device having a reaction vessel 1, a means 2 for of introducing a reaction gas into the reaction vessel, a means 3 for exhausting the reaction gas, a cylindrical substrate 4 to be film-formed arranged in the reaction vessel and means 7 to 9 applying high-frequency electric power of 30 to 600 MHz for generating plasma into the reaction vessel and executing film formation by a plasma CVD method, the outside of the cylindrical substrate 4 is provided with plural bar-shaped electric power feeding electrodes 5 and plural bar-shaped earth electrodes 6 at the positions on a circumference with a center axis same as that of the cylindrical substrate 4, and moreover, a mechanism 10 of rotating the cylindrical substrate 4 is provided. In this way, stable discharge is made possible on the space between the electric power feeding electrodes and the earth electrodes under low pressure of 0.1 to 10 Pa, and a film small in defects and good in uniformity can be obtd. at a high film forming rate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to the production of thin films for electronic devices such as photoreceptors for electrophotography, line sensors for image input, solar cells, semiconductor devices, etc., and is formed by plasma CVD (Chemical Vapor Deposition). The present invention relates to a plasma CVD apparatus for performing the above.

[0002]

2. Description of the Related Art Conventionally, various apparatuses and methods for forming a film by a plasma CVD method have been proposed.
JP-A-283449 discloses that a cylindrical substrate serving as a ground electrode and a cylindrical high-frequency electrode having a larger diameter coaxial with the axis of the cylindrical substrate are provided inside the reaction vessel, and coaxial with the axis outside the reaction vessel. , Plasma CVD equipped with a pair of electromagnetic coils
An apparatus is disclosed. In this system, during film formation, the negatively charged powder generated in the plasma rotates around the lines of magnetic force and does not move to the cylindrical substrate, so that it is possible to prevent the powder from being mixed into the film and to improve the film quality such as pinholes. Can be prevented from decreasing.

[0003] Japanese Patent Application Laid-Open No. 7-297142 discloses that
A plurality of cylindrical supports are arranged on concentric circles in a reaction vessel capable of vacuum sealing, and a rod-shaped cathode electrode and a gas roughened surface are provided in a space surrounded by these cylindrical supports. Introducing means is provided, and this cathode electrode has 20 MH
A plasma CVD apparatus for generating plasma by applying a high frequency power of z to 450 MHz is disclosed. In this apparatus, since no discharge interruption or abnormal discharge occurs during film formation, an electrophotographic photoreceptor having excellent electric characteristics and few image defects can be obtained.

Further, Japanese Patent Application Laid-Open No. Hei 8-107074 discloses that a plurality of cylindrical supports are arranged concentrically in a vacuum-tight reaction vessel, and a space surrounded by these cylindrical supports is provided. A rod-shaped first electrode, a rod-shaped grounded second electrode, and gas introducing means are provided, and high-frequency power of 20 MHz to 450 MHz is applied to the first electrode, and the first electrode and the second electrode are substantially separated from each other. Discloses a plasma CVD apparatus for generating plasma between electrodes. In this apparatus, an electrophotographic photosensitive member having excellent electric characteristics and few image defects can be obtained by stabilizing discharge during film formation.

[0005]

Conventionally, an amorphous silicon thin film, an amorphous silicon nitride thin film, an amorphous silicon carbide thin film on a long and large-area substrate such as an electrophotographic photoreceptor, an image input line sensor, and a solar cell. For forming amorphous carbon thin film, etc.
Coaxial cylindrical plasma C using high frequency of 3.56 MHz
VD devices have been used. With such an apparatus, an electrophotographic photosensitive member in which a thin film mainly composed of amorphous silicon is formed on an aluminum cylindrical substrate has been commercialized.

However, the system of this device is 5 to 8 μm / h
, And it takes a long time to obtain a film having a thickness of 30 to 80 μm, which is required as a photoreceptor film for electrophotography. The usable process pressure is 1
Since the pressure is 0 to 1000 Pa, the collision frequency between gas molecules is high, and the raw material gas molecular species in the plasma is polymerized to easily generate powder. When the powder adheres to the substrate, image defects are caused, which limits the improvement of manufacturing yield.

In the prior art described in the above-mentioned Japanese Patent Application Laid-Open No. 9-283449, such a coaxial cylindrical plasma CVD is used.
A countermeasure to prevent the polymer from adhering to the substrate is made by applying a DC magnetic field to the reaction chamber of the apparatus, and the effect is clearly shown. However, no measures have been taken to increase the film formation rate.

In order to prevent the generation of powder and increase the deposition rate, it is conceivable to use a plasma source that generates high-density plasma at a low process pressure at which collision frequency between gas molecules is reduced. As such a plasma source,
There is a plasma source using electromagnetic waves having a frequency higher than 13.56 MHz. For example, an example in which a plasma source using a 500 MHz electromagnetic wave is applied to an etching process has been reported (S. Samukawaetal, Jpn. J. Appl. Phys., Vol.
995) 6805), it is shown that a plasma having a high plasma density is generated in a pressure range of 0.66 to 13.3 Pa. Examples of the use of such high-frequency power having a frequency higher than 13.56 MHz for the production of an electrophotographic photoreceptor are described in Japanese Patent Application Laid-Open Nos. Hei 7-297142 and Hei 8-107074. This indicates that a high film formation rate and sufficient electrophotographic characteristics can be obtained.

However, these prior arts also have some problems. For example, in the case of the prior art described in Japanese Patent Application Laid-Open No. 7-297142, the earth electrode for the rod-shaped cathode electrode for supplying electric power is a plurality of rotating cylindrical supports provided so as to surround the cathode electrode. When a film is deposited on the cylindrical support or electric contact during rotation changes, the grounding state changes at high frequency, and the discharge becomes unstable. In the case of the prior art described in Japanese Patent Application Laid-Open No. H8-107074, in order to solve this problem, a bar-shaped ground electrode is provided independently near the cathode electrode, and substantially between the cathode electrode and the ground electrode. To generate a discharge. In this configuration, the discharge is stable as a whole, but it is difficult to make the distribution of plasma throughout the discharge space including the cathode electrode and the ground electrode always uniform, and a plurality of cylindrical supports arranged concentrically are used. It is necessary to revolve in addition to the rotation, resulting in a complicated device configuration.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in consideration of the above circumstances, and it is an object of the present invention to provide an amorphous silicon thin film, an amorphous silicon nitride, Thin films, amorphous silicon carbide thin films, amorphous silicon oxide thin films, etc. can be formed, and a high film formation rate can be obtained. Obtained plasma CVD with simple structure
An object (problem) is to provide a device.

[0011]

Means for Solving the Problems To achieve the above object, the invention according to claim 1 comprises a reaction vessel, means for introducing a reaction gas into the reaction vessel, means for exhausting the reaction gas, A film-forming cylindrical substrate placed in a reaction vessel, and a plasma generating 30 MHz to 600 m in the reaction vessel.
MHz means for applying high-frequency power of MHz.
In a plasma CVD apparatus for forming a film by the VD method,
A plurality of rod-shaped power supply electrodes and a plurality of rod-shaped ground electrodes are provided on the outer circumference of the cylindrical base at a position on the circumference having the same central axis as the cylindrical base, and a mechanism for rotating the cylindrical base is provided. It is characterized by being provided.

According to a second aspect of the present invention, in the plasma CVD apparatus according to the first aspect, the lengths of the power supply electrode and the ground electrode are approximately １ ／ or ／ of the wavelength of the high frequency. It is characterized by the following.

The invention according to claim 3 is the invention according to claim 1 or 2
Wherein the means for applying high-frequency power of 10 KHz to 20 MHz is provided to the cylindrical substrate.

The invention according to claim 4 is the invention according to claim 1 or 2
Or the plasma CVD apparatus according to 3, wherein a cylinder made of a dielectric material having the same central axis is provided outside or inside the circumference where the plurality of rod-shaped power supply electrodes and the plurality of rod-shaped ground electrodes are located. It is characterized by the following.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration and operation of the present invention will be described below in detail with reference to the drawings.

(Embodiment 1) FIG. 1 is a view showing a first embodiment of a plasma CVD apparatus according to the present invention. FIG. 1A is a schematic sectional view of a plasma CVD apparatus as viewed from above. (B) is a schematic sectional view of AA part of (A).
FIG. 1A is a view corresponding to a cross section taken along a line BB in FIG. The plasma CVD apparatus shown in FIG. 1 includes a reaction vessel 1 and a means for introducing a reaction gas into the reaction vessel 1 (for example, a gas introduction pipe 2 provided on an upper disk 1b of the reaction vessel 1 and a gas supply unit (not shown) Gas cylinder, etc.) and means for exhausting the reaction gas (for example, the lower disk 1 of the reaction vessel 1).
a), an evacuation pump (not shown) connected to the evacuation pipe 3), a film-forming cylindrical substrate 4 disposed in the reaction vessel 1, and plasma inside the reaction vessel 1. Means for applying high frequency power of 20 MHz to 600 MHz (for example, an ultrasonic power source 7, a matching device 8, a power supply 9)
And the like, and a film forming apparatus for forming a film by a plasma CVD method.
A plurality of rod-shaped power supply electrodes 5 and a plurality of rod-shaped ground electrodes 6 are provided at positions on the circumference having the same central axis as the center axis, and a cylindrical substrate rotating mechanism (a motor 10 a and a motor 10 a) for rotating the cylindrical substrate 4. Gears 10b, 10c, etc.) 10 are provided.

The materials of the power supply electrode 5 and the ground electrode 6 are aluminum (Al), copper (Cu), titanium (Ti), iron (Fe), chromium (Cr), nickel (Ni), gold ( Au), platinum (Pt), cobalt (C
o) and their alloys. The power is supplied to the power supply electrode 5 by branching from a single power supply (for example, an ultra-high frequency power supply 7) to each power supply electrode 5 via a matching unit 8 and a power supply 9 as shown in FIG. Otherwise,
As in the second embodiment shown in FIG. 2, a matching device 8 and a power distribution unit 11 (for example, a power distribution disk 11a covered with a dielectric member 11b) from a single or a small number of power sources (for example, an ultra-high frequency power supply 7). ), The power is supplied to the power supply electrode 5 by branching, or although not shown, the power is supplied to each power supply electrode 5 from a plurality of power sources individually. still,
In the first embodiment of FIG. 1 and the second embodiment of FIG. 2, a power supply unit (power supply unit 9, power distribution unit 1) to the power supply electrode 5 is provided.
Only the configuration of 1) is different, and the other configurations are the same.

The cross-sectional shape of the power supply electrode 5 and the ground electrode 6 in the plasma CVD apparatus shown in FIG. 1 or 2 may be circular or rectangular, and the shapes are not particularly limited. The distance between the power supply electrode 5 and the ground electrode 6 is
It is provided so as to be shorter than the distance between the power supply electrode 5 and the cylindrical substrate 4. For example, as shown in FIG. 1, the distance X1 between the power supply electrode 5 and the cylindrical base 4 and the distance X2 between the power supply electrode 5 and the ground electrode 6 have a relationship of X2 <X1.

The material of the film-forming cylindrical substrate 4 is not limited, and it may be plastic in addition to metal. The shape may be any shape as long as the outer shape is in a cylindrical space, and may be a polygonal prism in addition to a cylinder. When an electrophotographic photoreceptor is manufactured, a cylindrical substrate of Al is often used, and when an image input line sensor or a solar cell is manufactured, a plurality of aluminum, stainless steel, or other metal polygonal pillars are provided on a side surface. In some cases, a substrate is arranged.
Further, the cylindrical base 4 may be provided with a heating mechanism such as a resistance heater in the cylinder. Further, a lower portion of a support 4a for supporting the cylindrical substrate 4 is rotatably supported by a lower disk portion 1a of the reaction vessel 1, and a gear 10c is provided at an end of the support 4a outside the reaction vessel. And the gear 1
0c is engaged with the gear 10b on the motor 10a side. That is, the cylindrical base rotating mechanism 10 is constituted by the motor 10a and the gears 10b and 10c, and the cylindrical base 4 can be rotated via the gears 10b and 10c by the rotation of the motor 10a.

The reaction gas for film formation can be introduced from any place of the reaction vessel 1 (for example, the upper part of the upper disk 1b of the reaction vessel 1) through the gas introduction pipe 2 as shown in FIG. 1 or FIG. However, in addition, the earth electrode 6 may be formed of a tube having one or more holes so as to also serve as a gas introduction tube, and a reaction gas may be introduced through the earth electrode / gas introduction tube. Through these gas introduction pipes, SiH ₄ , Si ₂ H ₆ , CH ₄ , C ₂ H ₆ , C
₂ H ₂ , NH ₃ , NO, N ₂ O, CO ₂ , H ₂ , N ₂ , He,
A gas such as Ar, B ₂ H ₆ or PH ₃ is introduced to form an amorphous thin film containing silicon (Si) such as an amorphous silicon thin film, an amorphous silicon nitride thin film, an amorphous silicon carbide thin film, and an amorphous silicon oxide thin film.

In the plasma CVD apparatus of the present invention, by adopting the above-described apparatus configuration and electrode arrangement structure,
At a low pressure of 0.1 to 10 Pa, stable discharge can be substantially performed between the power supply electrode 5 and the ground electrode 6, and a film with few defects due to generation of dust and a film with good uniformity is highly formed. Obtained at speed. Further, by providing the mechanism 10 for rotating the cylindrical substrate 4, a film with good uniformity can be obtained. In addition, the reason why the plasma generation frequency is set to 20 MHz to 600 MHz in the plasma CVD apparatus of the present invention is that the plasma is stably generated in this region and the conventional one is not used.
Compared with the case where 3.56 MHz is used, the remarkable increase in the film formation rate is observed at 20 MHz or more,
This is because discharge becomes unstable at MHz or higher.

(Embodiment 2) Next, in the invention according to claim 2, the plasma C having the configuration shown in FIG.
In the VD device, the lengths of the power supply electrode 5 and the ground electrode 6 are approximately １ ／ of the wavelength in the high-frequency air.
Or 5/4. The length of this electrode does not need to be exactly 1/4 or 5/4 of the wavelength of the high frequency wave, but also includes a range of 80 to 120% (the length of the electrode is Y if shown in FIG. 1). ). According to the theory of the linear antenna, if the lengths of the power supply electrode 5 and the ground electrode 6 are approximately 1/4 or 5/4 of the wavelength of the high frequency, a standing wave of the electromagnetic wave stands and stabilizes in the discharge space. Large power input is possible. Therefore, stable high-density plasma can be generated, and a higher film-forming rate can be obtained.

(Embodiment 3) FIG. 3 is a view showing a third embodiment of a plasma CVD apparatus according to the present invention. FIG. 3A is a schematic sectional view of the plasma CVD apparatus as viewed from above. (B) is a schematic sectional view of AA part of (A).
FIG. 3A is a view corresponding to a cross section taken along line BB of FIG. Although the basic configuration of this plasma CVD apparatus is the same as that of FIG. 1, when the cylindrical substrate 4 is made of metal, means for applying a bias high-frequency power of 10 KHz to 20 MHz to the cylindrical substrate 4 (for example, a bias high-frequency power source 1)
2, a matching device 13, a carbon slider 14, etc.).

The rotating mechanism 10 is provided on the cylindrical base 4 as described above. As an example of the means for applying the bias high-frequency power to the rotating cylindrical base 4 as shown in FIG. A brass ring 4b conducting at high frequency is provided on a part of a support 4a on which the cylindrical base 4 is installed, and a carbon slider 14 is arranged in contact with the ring 4b in a band shape. There is a method of applying high frequency power from the bias high frequency power supply 12 via the matching unit 13.

When high-frequency power is applied to the cylindrical substrate 4 in the plasma, a sheath potential of several volts to several tens volts negative with respect to the plasma potential is generated according to the power. Since the powder generated in the plasma is often negatively charged, the sheath potential acts to prevent the powder from approaching the cylindrical substrate 4 (or the substrate on the substrate 4). Further, in the film formation method using such high-density plasma, the film formation rate is high, but the denseness of the film may be poor. In such a case,
By generating the sheath potential, a dense film can be obtained by hitting the cylindrical substrate 4 (or the substrate on the substrate 4) with more positively ionized gas.

(Embodiment 4) FIG. 4 is a view showing a fourth embodiment of a plasma CVD apparatus according to the present invention, wherein (A) is a schematic cross-sectional view of the plasma CVD apparatus as viewed from above. (B) is a schematic sectional view of AA part of (A).
FIG. 4A is a diagram corresponding to a cross section taken along line BB of FIG. The basic configuration of this plasma CVD apparatus is the same as that of FIG. 1, but outside or inside (outside in the illustrated example) on the circumference where the plurality of rod-shaped power supply electrodes 5 and the plurality of rod-shaped ground electrodes 6 are located. And a cylindrical member 15 made of a dielectric material having the same central axis (claim 4).

The dielectric cylinder 15 is preferably made of a material having a small dielectric loss, such as alumina, quartz,
Examples include silicon nitride, carbon nitride, and ethylene tetrafluoride. The dielectric cylinder 15 may also serve as the outer cylindrical wall of the reaction chamber in the reaction vessel 1 in some cases. Also, this dielectric cylinder 15
And the reaction vessel wall may be vacuum sealed via a rubber O-ring or the like. In FIG. 4, a cylinder 15 made of a dielectric material is provided outside the circumference where the power supply electrode 5 and the ground electrode 6 are located, and has the same central axis. This is an example in which the disk walls 1a and 1b are vacuum-sealed with an O-ring or the like. In the example of FIG. 4, a heating mechanism using a resistance heater 16 is provided in the cylinder of the cylindrical base 4.

As in the plasma CVD apparatus shown in FIG.
By providing the dielectric cylinder 15 with the same central axis outside the circumference where the power supply electrode 5 and the ground electrode 6 are located, the volume of the reaction vessel is substantially reduced, and the residence time of the reaction gas is reduced. . Therefore, the decomposed gas is discharged to the outside of the reaction vessel before the polymerization proceeds, so that the adhesion of the powder to the cylindrical substrate 4 (or the substrate on the substrate 4) is reduced.

[0029]

Next, a specific embodiment in which a film is formed using the plasma CVD apparatus according to the present invention will be described.

(Embodiment 1: Embodiments of Claims 1 and 2) FIG.
An example is shown in which an a-Si electrophotographic photoreceptor is manufactured using a plasma CVD apparatus having the configuration shown in FIG. First, the used apparatus will be described. A rotating mechanism 10 is provided in a cylindrical reaction vessel 1 made of stainless steel with the same central axis as the reaction vessel 1.
And a cylindrical stainless steel substrate support 4a having a heating mechanism (not shown). Further, on the circumference of a radius of 300 mm with the same central axis as the cylindrical reaction vessel 1,
Four power supply electrodes 5 are arranged from the upper disk 1b of the reaction vessel, and four earth electrodes 6 are arranged from the lower disk 1a of the reaction vessel. The length Y of the power supply electrode 5 and the ground electrode 6 is Y =
250 mm. In addition, power is supplied to the four power supply electrodes 5 from the ultrahigh frequency power supply 7 having a frequency of 300 MHz through a matching device 8 and a power supply 9 for branching power.

A gas introduction pipe 2 is arranged above the upper disk 1b of the reaction vessel 1. The gas introduction pipe 2 is connected to a gas supply unit (gas cylinder or the like) via a valve (not shown). An exhaust pipe 3 for exhausting gas is disposed on the lower disk 1a of the reaction vessel 1, and the exhaust pipe 3 is connected to a turbo molecular pump and a subsequent dry pump via a valve (not shown).

Next, a procedure for forming a photoreceptor film will be described. First, an Al cylindrical substrate 4 having an outer diameter of 100 mm and a length of 330 mm, which was degreased and washed with an organic solvent, was installed so as to surround the cylindrical stainless steel substrate support 4 a. The temperature of the cylindrical substrate 4 was raised to 250 ° C. while the inside of the reaction vessel 1 was evacuated to 7 × 10 to ⁴ Pa. Next, the charge injection preventing layer, the photoconductive layer, and the surface protection layer were sequentially laminated on the Al cylindrical substrate 4 while rotating the Al cylindrical substrate 4 at 15 rpm by the rotation mechanism 10. At this time, the film forming conditions of each layer are as shown in Table 1 below, and the average film forming speed of all the layers is 25 μm.
m / hr.

[0033]

[Table 1]

The electrophotographic photosensitive member prepared as described above was mounted on a semiconductor laser printer, and an image evaluation test was performed. The light amount is 30 μW / cm ² , 20 μW / cm ² ,
The light beam diameter was 10 μW / cm ² and the light beam diameter was 60 μm. The charging method was a scorotron method, and the applied voltage was +6 KV. Under this condition, a charging potential of +700 V was obtained. The development was performed by a magnetic brush development method using a two-component developer. The rotation speed (linear speed) of the photoconductor is 150
mm / s. The resulting image faithfully reproduces the pattern of eight black and white lines (each of white and black has a line width of 62.5 μm) per mm used as the original document, and has no image defects. Was.

Embodiment 2 An embodiment in which an a-Si type electrophotographic photoreceptor is manufactured by a plasma CVD apparatus having the structure shown in FIG. First, the used apparatus will be described. A cylindrical stainless steel substrate support 4a having a rotation mechanism 10 and a heating mechanism (not shown) having the same central axis as the reaction vessel 1 is arranged in the stainless steel cylindrical reaction vessel 1. 13.56 M is applied to the cylindrical stainless steel substrate support 4a from the bias high frequency power supply 12 via the matching unit 13 and the carbon slider 14.
Hz bias high frequency power can be supplied. Further, on the circumference having a radius of 300 mm with the same central axis as the cylindrical reaction vessel 1, 4
The power supply electrodes 5 and the four earth electrodes 6 from the lower disk 1a of the reaction vessel are arranged. The length of the power supply electrode 5 and the ground electrode 6 is 200 mm. In addition, the frequency 40
The configuration is such that power is supplied to the four power supply electrodes 5 from a 0 MHz ultrahigh frequency power supply 7 through a matching device 8 and a power supply 9 which branches the power.

A gas introduction pipe 2 is disposed above the upper disk 1b of the reaction vessel 1. The gas introduction pipe 2 is connected to a gas supply unit (gas cylinder or the like) via a valve (not shown). An exhaust pipe 3 for exhausting gas is disposed on the lower disk 1a of the reaction vessel 1, and the exhaust pipe 3 is connected to a turbo molecular pump and a subsequent dry pump via a valve (not shown).

Next, a procedure for forming a photoreceptor film will be described. First, an Al cylindrical substrate 4 having an outer diameter of 100 mm and a length of 330 mm, which was degreased and washed with an organic solvent, was installed so as to surround the cylindrical stainless steel substrate support 4 a. The temperature of the cylindrical substrate 4 was raised to 250 ° C. while the inside of the reaction vessel 1 was evacuated to 7 × 10 to ⁴ Pa. Next, the charge injection preventing layer, the photoconductive layer, and the surface protection layer were sequentially laminated on the Al cylindrical substrate 4 while rotating the Al cylindrical substrate 4 at 15 rpm by the rotation mechanism 10. At this time, the film forming conditions of each layer are as shown in Table 2 below, and the average film forming speed of all the layers is 28 μm.
m / hr.

[0038]

[Table 2]

The electrophotographic photosensitive member prepared as described above was mounted on a semiconductor laser printer, and an image evaluation test was performed under the same conditions as in Example 1 described above. The resulting image is 8 per mm used as the original document.
The pattern of the set of black and white lines (the line width of each of white and black was equivalent to 62.5 μm) was faithfully reproduced, and there was no image defect.

(Embodiment 3: Embodiment of Claim 4) An example is shown in which an a-Si type electrophotographic photoreceptor is manufactured using a plasma CVD apparatus having the structure shown in FIG. First, the used apparatus will be described. A cylindrical stainless steel substrate support 4a having a rotation mechanism 10 and a heating mechanism 16 having the same central axis as the reaction vessel 1 is arranged in the cylindrical reaction vessel 1 made of stainless steel. Further, four power supply electrodes 5 from the upper disk 1b of the reaction vessel and four earth electrodes 6 from the lower disk 1a of the reaction vessel are arranged on a circumference having a radius of 300 mm with the same central axis as the cylindrical reaction vessel 1. It is arranged. The length of the power supply electrode 5 and the ground electrode 6 is 250 mm.
Further, a matching device 8 is connected to an
The power is supplied to the four power supply electrodes 5 through a power supply 9 that branches the power.

Further, a cylindrical reaction vessel 1 made of stainless steel
The inner diameter of the reaction vessel 1 is 350 m
An alumina dielectric cylinder 15 having a thickness of 20 mm and a thickness of 20 mm is arranged. The dielectric cylinder 15 and the upper and lower disks 1b and 1a of the reaction vessel are vacuum-sealed using an O-ring. The space between the dielectric cylinder 15 and the cylindrical reaction vessel 1 is filled with N ₂ gas at atmospheric pressure in order to prevent generation of plasma in this space.

A gas introduction pipe 2 is disposed above the upper disk 1b of the reaction vessel 1. The gas introduction pipe 2 is connected to a gas supply unit (gas cylinder or the like) via a valve (not shown). An exhaust pipe 3 for exhausting gas is disposed on the lower disk 1a of the reaction vessel 1, and the exhaust pipe 3 is connected to a turbo molecular pump and a subsequent dry pump via a valve (not shown).

Next, a procedure for forming a photosensitive film will be described. First, an Al cylindrical substrate 4 having an outer diameter of 100 mm and a length of 330 mm, which was degreased and washed with an organic solvent, was installed so as to surround the cylindrical stainless steel substrate support 4 a. While the inside of the reaction vessel 1 was evacuated to 7 × 10 to ⁴ Pa, the temperature of the cylindrical substrate 4 was raised to 250 ° C. by the heater 16 of the heating mechanism. Next, the charge injection preventing layer, the photoconductive layer, and the surface protection layer were sequentially laminated on the Al cylindrical substrate 4 while rotating the Al cylindrical substrate 4 at 15 rpm by the rotation mechanism 10. At this time, the film forming conditions of each layer were the same as those in Table 1 shown in Example 1 described above, and the average film forming speed of all the layers was 27 μm / hr.

The electrophotographic photosensitive member prepared as described above was mounted on a semiconductor laser printer, and an image evaluation test was performed under the same conditions as in Example 1 described above. The resulting image is 8 per mm used as the original document.
The pattern of the set of black and white lines (the line width of each of white and black was equivalent to 62.5 μm) was faithfully reproduced, and there was no image defect.

[0045]

As described above, according to the first aspect of the present invention, there is provided a reaction vessel, a means for introducing a reaction gas into the reaction vessel, a means for exhausting the reaction gas, and a device disposed in the reaction vessel. A cylindrical substrate to be deposited, and means for applying high-frequency power of 30 MHz to 600 MHz for generating plasma in the reaction vessel, wherein the cylindrical substrate is formed by a plasma CVD method. By providing a plurality of rod-shaped power supply electrodes and a plurality of rod-shaped ground electrodes at positions on the circumference having the same central axis as that of the cylindrical base outside the base, and by providing a mechanism for rotating the cylindrical base. At a low pressure of 0.1 to 10 Pa, a stable discharge can be substantially performed between the power supply electrode and the ground electrode, and a film having few defects due to generation of dust and a film having good uniformity has a high film forming rate. Obtained. Furthermore, a film with good uniformity can be obtained by rotating the cylindrical substrate.

According to a second aspect of the present invention, in the plasma CVD apparatus according to the first aspect, the lengths of the power supply electrode and the ground electrode are approximately １ ／ or ／ of the wavelength of the high frequency wave. As a result, a standing wave of an electromagnetic wave is generated in the discharge space, and a large amount of power can be supplied stably. Therefore, it is possible to stably generate high-density plasma,
A higher deposition rate can be obtained.

The invention according to claim 3 is the invention according to claim 1 or 2
Wherein the means for applying a bias high-frequency power of 10 KHz to 20 MHz is provided to the cylindrical substrate, so that a sheath potential of several volts to several tens volts negative with respect to the plasma potential depending on the power. Can be caused. Since the powder generated in the plasma is often negatively charged, the sheath potential can prevent the powder from approaching the substrate (or the substrate on the substrate). In addition, in the film formation method using such high-density plasma, the film formation rate is high, but the film density may be inferior. In such a case, the ionization is positively performed by generating a sheath potential. The denser the gas, the more the gas hits the substrate, and a dense film can be obtained.

The invention according to claim 4 is the invention according to claim 1 or 2
Or the plasma CVD apparatus according to 3, wherein a cylinder made of a dielectric material is provided outside or inside the circumference on which the plurality of rod-shaped power supply electrodes and the plurality of rod-shaped ground electrodes are located with the same central axis. This substantially reduces the volume of the reaction vessel and shortens the residence time of the reaction gas, so that the gas decomposed in the reaction vessel is discharged to the outside of the reaction vessel before polymerization proceeds. Therefore, the amount of powder adhering to the substrate (or the substrate on the substrate) is reduced, and the number of defects in the formed film is reduced.

[Brief description of the drawings]

FIG. 1 is a diagram showing a first embodiment of the present invention,
(A) is a schematic cross-sectional view of the plasma CVD apparatus viewed from above,
(B) is a schematic sectional view of AA part of (A).

FIG. 2 is a diagram showing a second embodiment of the present invention,
(A) is a schematic cross-sectional view of the plasma CVD apparatus viewed from above,
(B) is a schematic sectional view of AA part of (A).

FIG. 3 is a diagram showing a third embodiment of the present invention;
(A) is a schematic cross-sectional view of the plasma CVD apparatus viewed from above,
(B) is a schematic sectional view of AA part of (A).

FIG. 4 is a diagram showing a fourth embodiment of the present invention;
(A) is a schematic cross-sectional view of the plasma CVD apparatus viewed from above,
(B) is a schematic sectional view of AA part of (A).

[Explanation of symbols]

 1: Reaction vessel 1a: Lower disc of reaction vessel 1b: Upper disc of reaction vessel 2: Gas introduction pipe 3: Exhaust pipe 4: Cylindrical base 4a: Support of cylindrical base 4b: Ring 5: Power supply electrode 6: Ground electrode 7: Ultra high frequency power supply 8: Matching device 9: Power supply 10: Cylindrical substrate rotating mechanism 10a: Motor 10b, 10c: Gear 11: Power distribution section 11a: Power distribution disk 11b: Dielectric member 12: Bias high frequency power supply 13: Matching device 14: Carbon slider 15: Dielectric cylinder 16: Heater (heating mechanism)

Claims (4)

[Claims] 1. A reaction vessel, means for introducing a reaction gas into the reaction vessel, means for exhausting the reaction gas, a film-forming cylindrical substrate disposed in the reaction vessel, and A plasma CVD apparatus for forming a film by a plasma CVD method, which has means for applying a high-frequency power of 30 MHz to 600 MHz for generating plasma to the plasma, wherein a circle having the same central axis as the cylindrical substrate outside the cylindrical substrate. A plasma CVD apparatus, comprising: a plurality of rod-shaped power supply electrodes and a plurality of rod-shaped ground electrodes provided at circumferential positions; and a mechanism for rotating the cylindrical substrate. 2. The plasma CVD apparatus according to claim 1, wherein the lengths of the power supply electrode and the ground electrode are approximately 1/4 or 5/4 of the wavelength of the high frequency. 3. The method according to claim 1, wherein the cylindrical substrate has a frequency of 10 KHz to 20 MHz.
3. The plasma CVD apparatus according to claim 1, further comprising means for applying the high-frequency power. 4. A cylinder made of a dielectric material having the same central axis is provided outside or inside the circumference where the plurality of rod-shaped power supply electrodes and the plurality of rod-shaped ground electrodes are located. Item C. The plasma C according to item 1, 2 or 3.
VD device.