JPH10183354A - Deposited film forming apparatus and deposited film forming method - Google Patents

Abstract

(57) Abstract: In forming an a-Si-based photoconductor using a high-frequency-PCVD method, an image defect is suppressed, and other electrophotographic characteristics of an a-Si-based electrophotographic photoconductor are reduced. Provided are a deposited film forming apparatus and a deposited film forming method which can be stably manufactured at a low cost. SOLUTION: In a deposition film forming apparatus by a plasma CVD method having means for disposing a plurality of substrates 105 so as to surround a film formation space in a reaction vessel 101, at least a part of the reaction vessel 101 is made of a conductive material. And a method for forming a deposited film using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film forming apparatus and a deposited film forming method using a plasma CVD method, and particularly to amorphous silicon for electrophotography (hereinafter referred to as a-Si).
The present invention relates to an apparatus and a method useful for manufacturing a photosensitive member.

[0002]

2. Description of the Related Art As a photoconductive material for forming a photoreceptor for electrophotography, it has a high sensitivity, a high SN ratio [photocurrent (Ip) / dark current (Id)], and is suitable for the spectral characteristics of an electromagnetic wave to be irradiated. Characteristics such as having an absorption spectrum, fast photoresponsiveness, having a desired dark resistance value, and being harmless to the human body during use are required. Especially,
In the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-pollution during use is important.

[0003] Hydrogenated amorphous silicon (hereinafter referred to as "a-Si:
H "). For example, Japanese Patent Publication No. 60-350
No. 59 describes an application as a light receiving member for electrophotography.

In such an electrophotographic photosensitive member, generally, a conductive support is heated to 50 ° C. to 350 ° C.
Vacuum evaporation method, sputtering method, ion plating method, thermal CVD method, optical CVD method, plasma C
A photoconductive layer made of a-Si is formed by a film forming method such as a VD method. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support has been put to practical use as a suitable method.

In Japanese Patent Application Laid-Open No. 56-83746, a conductive support and a-Si containing a halogen atom as a constituent atom (hereinafter referred to as "a-Si: X") are disclosed.
An electrophotographic photoconductor comprising a photoconductive layer has been proposed.
In this publication, a-Si contains 1 to 40 atom% of halogen atoms, whereby high heat resistance is obtained and good electrical and optical properties can be obtained as a photoconductive layer of an electrophotographic photoreceptor. And

Japanese Patent Application Laid-Open No. Sho 57-115556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has an electrical property such as a dark resistance value, a photosensitivity, and a photoresponsive property. In order to improve the use environment characteristics such as optical and photoconductive characteristics and moisture resistance, as well as the stability over time, silicon atoms and carbon atoms are deposited on a photoconductive layer composed of an amorphous material containing silicon atoms as a base material. A technique of providing a surface barrier layer made of a non-photoconductive amorphous material containing atoms is described. Further, Japanese Unexamined Patent Publication No. 60-67951
Japanese Patent Application Laid-Open No. 62-1 describes a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated.
Japanese Patent No. 68161 describes a technique in which an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements is used as a surface layer.

On the other hand, Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the surface of the photoreceptor is maintained at 30 to 40.degree. By performing such an image forming process, there is disclosed a technique for preventing a reduction in surface resistance due to the adsorption of moisture on the surface of a photoreceptor and an image deletion caused thereby.

Japanese Patent Application Laid-Open No. 63-149381 discloses a microwave plasma CVD method in which a plurality of cylindrical substrates are arranged concentrically and microwave power is supplied to a discharge space surrounded by the cylindrical substrates. Hereinafter, a technique of forming an amorphous film on a base by "MW-PCVD" is described.

With these techniques, a-Si for electrophotography
The electrical, optical and photoconductive properties of the photoreceptor and the environmental properties in use have been improved, and the image quality has been improved accordingly.

An apparatus and a method for manufacturing such an a-Si photosensitive member are roughly as follows.

FIG. 2 is a schematic diagram showing an example of an apparatus for manufacturing an electrophotographic light-receiving member by an RF plasma CVD method (hereinafter abbreviated as "RF-PCVD") using an RF band frequency as a power source. It is. This device is roughly divided into
Deposition device 2100, source gas supply device 2200, exhaust device (not shown) for reducing the pressure inside reaction vessel 2111
It is composed of Reaction vessel 2 in deposition apparatus 2100
Inside 111, a cylindrical support 2112, a heater 2113 for heating the support, and a raw material gas introduction pipe 2114 are installed, and a high-frequency matching box 2115 is further connected.

The source gas supply device 2200 includes SiH ₄ ,
Cylinders 2221 to 2226 and valves 2231 to 22 for source gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , and PH _3.
36, 2224 to 2246, 2251 to 2256 and mass flow controllers 2211 to 2216, and the cylinders for each source gas are connected to a gas introduction pipe 2114 in the reaction vessel 2111 via a valve 2260.

The formation of a deposited film using this apparatus can be performed, for example, as follows.

First, the cylindrical support 2112 is set in the reaction vessel 2111, and the inside of the reaction vessel 2111 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the cylindrical support 211 is heated by the heater 2113 for heating the support.
2 is controlled to a predetermined temperature of 200 ° C. to 350 ° C. In order to allow the source gas for forming a deposited film to flow into the reaction vessel 2111, the valves 2231 to 2237 of the gas cylinder are used.
First, the main valve 2118 is opened after confirming that the leak valve 2117 of the reaction vessel is closed, and that the inflow valves 2241 to 2246, the outflow valves 2251 to 2256, and the auxiliary valve 2260 are open. The reaction vessel 2111 and the inside of the gas pipe 2116 are exhausted.

Next, the reading of the vacuum system 2119 is about 5 × 10 ^−6.
When reaching Torr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed. After that, gas cylinder 2
Each gas is supplied to the valves 2231 to 2222 by 221 to 2226.
36 is opened and introduced, and each gas pressure is adjusted to ² kg / cm ² by the pressure adjusters 2261 to 2266. Next, the inflow valves 2241 to 2246 are gradually opened to introduce each gas into the mass flow controllers 2211 to 2216.

After the preparation for film formation is completed as described above,
Each layer is formed by the following procedure.

When the temperature of the cylindrical support 2112 reaches a predetermined temperature, necessary ones of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 2221 to 2226 to the gas introduction pipe 2.
It is introduced into the reaction vessel 2111 via 114. Next, each source gas is adjusted by the mass flow controllers 2211 to 2216 so as to have a predetermined flow rate. that time,
The opening of the main valve 2118 is adjusted while watching the vacuum gauge 2119 so that the pressure in the reaction vessel 2111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable,
An RF power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and RF power is introduced into the reaction vessel 2111 through the high frequency matching box 2115 to generate glow discharge. The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and the cylindrical support 2
A deposition film mainly containing predetermined silicon is formed on the substrate 112. After the desired film thickness is formed,
The supply of RF power is stopped, the outflow valve is closed, and the flow of gas into the reaction vessel is stopped, thereby completing the formation of the deposited film.

By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed.
In order to avoid remaining in the pipe from the outflow valves 2251 to 2256 to the reaction vessel 2111, the outflow valves 2251 to 2256 are closed, the auxiliary valve 2260 is opened, and the main valve 2118 is fully opened to temporarily apply high vacuum to the system. The operation of exhausting air is performed as needed.

In order to make the film formation uniform, it is also effective to rotate the support 2112 at a predetermined speed by a driving device (not shown) during the layer formation. Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the production conditions of each layer.

On the other hand, the development of the deposited film forming apparatus shown in FIG. 3 which can form a plurality of photoconductors at the same time and has extremely high productivity is also underway. FIG. 3A is a schematic sectional view, and FIG.
FIG. 3 is a schematic cross-sectional view taken along a cutting line BB ′ in FIG. An exhaust pipe 304 is integrally formed on the side surface of the reaction vessel 301, and the other end of the exhaust pipe 304 is connected to an exhaust device (not shown). Waveguides 303 are attached to the upper and lower surfaces of the reaction vessel 301, respectively, and the other end of each waveguide 303 is connected to a microwave power supply (not shown). A dielectric window 302 is hermetically sealed at the end of each waveguide 303 on the reaction vessel 301 side.

Six cylindrical substrates 305 on which a deposited film is formed are arranged so as to be parallel to each other so as to surround the center of the reaction vessel 301. Each cylindrical base 30
5 is held by a rotating shaft 308 and is heated by a heating element 307. When the motor 309 is driven, the rotation shaft 308 rotates via the reduction gear 310, and the cylindrical base 305 rotates around its center axis in the generatrix direction.

There is a space surrounded by a cylindrical substrate 305 and each dielectric window 302 in the reaction vessel 301, and this space becomes a film formation space 306. In addition, two adjacent cylindrical substrates 3
Material gas introduction pipes 351 are provided in the gaps between the reference gases 05. The source gas introduction pipe 351 introduces a source gas into the film formation space 306.

When an electrophotographic photosensitive member is manufactured using this apparatus, first, the inside of the reaction vessel 301 is kept at 10 ^-7 Torr.
Then, the cylindrical body 305 is heated and maintained at a desired temperature by the heating element 207.

Then, through a raw material gas introduction pipe 351,
Source gas is introduced into the reaction vessel 201. Simultaneously with this, a frequency of 500 MHz or more, preferably 2.45 G
A microwave of Hz is incident on the reaction vessel 301 through the waveguide 303 and the dielectric window 302. As a result, a glow discharge occurs in the film formation space 306, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 305. At this time, by rotating the motor 309, a deposited film can be formed over the entire circumference of the cylindrical substrate 305.

In addition to such a conventional a-Si photoconductor manufacturing apparatus and manufacturing method, in recent years, VHF plasma CVD (hereinafter referred to as "VHF-P
(Abbreviated as “CVD”) has attracted attention, and the development of an a-Si photoconductor manufacturing apparatus using the method has been actively promoted. This is because the VHF-PCVD method is expected to achieve a high film deposition rate and a high-quality a-Si film, so that it is possible to simultaneously reduce the cost and quality of the product. For example, JP-A-6-287760 discloses a
An apparatus and a method that can be used for manufacturing a Si-based photoconductor are disclosed.

An apparatus and a method for manufacturing an a-Si photosensitive member using the VHF-PCVD method are as follows, for example.

FIG. 4 is a schematic diagram showing an example of an apparatus for manufacturing a light receiving member for electrophotography by the VHF plasma CVD method. FIG. 4A is a schematic sectional view, and FIG.
It is a schematic sectional drawing which follows the cutting line BB 'of (a). An exhaust pipe 412 is integrally formed on the side surface of the reaction vessel 401, and the other end of the exhaust pipe 412 is connected to an exhaust device (not shown). Eight cylindrical substrates 405 on which a deposited film is formed are arranged so as to be parallel to each other so as to surround the center of the reaction vessel 401. Each cylindrical base 405 is held by a rotating shaft 408 and is heated by a heating element 407. When the motor 409 is driven, the rotation shaft 408 rotates via the reduction gear 410, and the cylindrical base 405 rotates around its center axis in the generatrix direction.

A source gas is supplied from a source gas supply unit 413 to a film forming space 406 surrounded by eight cylindrical substrates 405. The VHF power is supplied from the VHF power supply 403 via the matching box 404 to the high-frequency power introduction unit 402.
The film is supplied to the film formation space 406.

The formation of a deposited film using such an apparatus can be performed according to the following procedure.

First, the cylindrical substrate 40 is placed in the reaction vessel 401.
5 and the inside of the reaction vessel 401 is exhausted through an exhaust pipe 412 by an exhaust device (not shown). Subsequently, the heating element 40
7 heats and controls the cylindrical substrate 405 to a predetermined temperature of about 200 ° C. to 300 ° C.

When the temperature of the cylindrical substrate 405 reaches a predetermined temperature, the source gas is introduced into the reaction vessel 401 via the source gas supply means 413. After confirming that the flow rate of the raw material gas has reached the set flow rate and that the pressure in the reaction vessel 401 has been stabilized, a predetermined VHF is supplied from the high-frequency power supply 403 to the high-frequency introducing means 402 via the matching box 404.
Supply power. Glow discharge occurs in the film formation space by the VHF power radiated into the film formation space from the high-frequency introducing means 402, and the source gas is excited and dissociated to cause the cylindrical substrate 40
5, a deposited film is formed. After the formation of the desired film thickness, the supply of the VHF power is stopped, the supply of the source gas is stopped, and the formation of the deposited film is completed. By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

During formation of the deposited film, the deposited film is formed over the entire surface of the cylindrical substrate by rotating the cylindrical substrate 405 at a predetermined speed by the motor 409 via the rotating shaft 408.

With the above-described conventional method and apparatus, a good a-Si-based photoreceptor is formed. Especially VHF-PCVD
According to the method, it is possible to shorten the manufacturing time of the a-Si based photoconductor and to improve the electrical characteristics of the manufactured a-Si based photoconductor, because of the features of improving the film deposition rate and improving the quality of the film. For this reason, the VHF-PCVD method has been attracting attention as an extremely effective manufacturing method in order to reduce the price and improve the quality of a copy image required in the current market.

[0035]

However, this V
At present, there is still room for improvement in the HF-PCVD method from the viewpoint of reducing image defects. The image defect is caused by dust adhering to the substrate during formation of the deposited film, which becomes a nucleus and abnormally grows the deposited film. Such a deposited film abnormally grown portion (hereinafter referred to as “structural defect”) appears as a protrusion on the surface of the photoconductor,
Image defects such as black spots and white spots are generated on the copied image. Such image defects greatly impair the quality of the copied image, and early improvement is desired in order to meet future market requirements.

An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a high-frequency-PCV
In the formation of an a-Si-based photoreceptor using the method D, formation of a deposited film capable of stably producing an a-Si-based electrophotographic photoreceptor having low image defects and excellent other electrophotographic characteristics at low cost. An object of the present invention is to provide an apparatus and a method for forming a deposited film.

[0037]

The inventor of the present invention has made intensive studies to achieve the above object, and as a result, a plurality of cylindrical substrates have been formed in a reaction vessel as shown in FIG. In a high frequency-PCVD apparatus which is arranged on the same circumference and introduces a raw material gas and high frequency power into a film forming space to form a deposited film on a substrate, a nucleus of a structural defect formed on the substrate is located at a specific location. Found that the number of adsorption was particularly large. That is, when the position directly opposite to the center of the film forming space of the cylindrical substrate is set to 0 degree, and the position in the circumferential direction of the cylindrical substrate is defined by the central angle on the central axis of the cylindrical substrate, ± 45 to 60 degrees is more than the vicinity of 0 degree It has been found that a nucleus is adsorbed more at a position near a nearby adjacent substrate (hereinafter referred to as “substrate slope”).

Furthermore, the reason why the adsorption of nuclei is increased on the slope portion of the substrate is that the plasma characteristics (electron temperature, electron density, plasma potential) in the vicinity of this region sharply increase toward the outside of the film formation space. It has been found that the absorption of nuclei on the slope of the substrate can be significantly suppressed by suppressing the rapid change of the plasma characteristics.

At the same time, such a sudden change in the plasma characteristics in the region near the substrate facing the film formation space may be caused by using an electrically floating auxiliary member at least partially composed of a conductive material in an appropriate space in the reaction vessel. It has been found that it can be suppressed by installing it at a location, and the present invention has been completed.

That is, the present invention relates to an apparatus for forming a deposited film by a plasma CVD method having means for arranging a plurality of substrates so as to surround a film forming space in a reaction vessel. A deposited film forming apparatus characterized in that an electrically floating auxiliary member made of a material is provided.

A preferred embodiment of the present invention is a means for arranging a plurality of cylindrical substrates on the same circumference so as to surround a film formation space in a vacuum-tight reaction vessel, a source gas supply means,
A glow discharge is generated in the reaction vessel by introducing high-frequency power from the high-frequency power introduction unit to the source gas supplied from the source gas supply unit. The deposition film forming apparatus according to the present invention, wherein the deposition member is formed by a plasma CVD method, and the installation position of the auxiliary member is outside the deposition space from a cylindrical surface passing through the central axes of the plurality of cylindrical substrates. It is.

Further, according to the present invention, a plurality of substrates are arranged in a reaction vessel so as to surround a film formation space, and the plasma CVD is performed.
A method of forming a deposited film by a method, wherein the deposited film is formed in a reaction vessel provided with an electrically floating auxiliary member at least partially made of a conductive material. .

According to the present invention, the number of dusts adsorbed on the substrate, more precisely, the number of dusts adsorbed on the substrate on the slope of the substrate can be reduced, and good deposition with reduced structural defects can be achieved. A film can be formed. In addition, the present invention uses
It is particularly useful in the manufacture of an i-type electrophotographic photoreceptor, but is not limited thereto, and is also effective in forming other deposited films.

In the present invention, the details for obtaining such effects are not clear, but are considered to be roughly due to the following reasons.

During the formation of the deposited film, separation occurs on the wall surface of the film formation space, and fragments thereof are scattered as dust in the film formation space.
A part of the scattered dust reaches the substrate, and a part of the scattered dust is adsorbed on the substrate to become a core of a structural defect. That is, assuming that the density of dust reaching the substrate is n [pieces / cm ² ] and the probability of dust adsorbing on the substrate surface is R, the nucleus density N [pieces / cm ² ] on the substrate surface is N = n × R .. (Equation 1). It is presumed that the adsorption rate R is determined by the amount of charge that dust has when it reaches the surface of the substrate, or the amount of retained charge immediately after it reaches the surface of the substrate.

In the conventional apparatus for manufacturing an a-Si photoreceptor as shown in FIG. 4, since the plasma characteristics greatly differ in the circumferential direction in the vicinity of the substrate, it is considered that the charge amount of the dust upon reaching the substrate is also different. It is considered that the amount of charge of the dust at the time of reaching the substrate is large in the slope portion of the substrate, the cloning force on the surface of the substrate is increased, and the adsorption rate R is increased.

In the present invention, an electrically floating auxiliary member at least partly made of a conductive material is provided in the reaction vessel, and the installation position of the auxiliary member passes through the central axes of the plurality of cylindrical substrates. It is located outside the deposition space from the cylindrical surface. With such a configuration, a part of the high-frequency power introduced into the deposition space by the high-frequency power introduction unit is transmitted to the auxiliary member, and the auxiliary member radiates the transmitted high-frequency power to the vicinity of the auxiliary member. I do.

By arranging the auxiliary members in a required number and at an appropriate position, the high-frequency electric field in the vicinity of the slope of the substrate is strengthened, and at the same time, plasma is generated outside the film formation space where plasma has not been generated. The sudden change in plasma characteristics in the vicinity of the base slope is alleviated. As a result, adsorption of dust on the slope portion of the base is suppressed, and structural defects are reduced.

When the present invention is used, a sharp change in plasma characteristics occurs in a region corresponding to the back side of the substrate when viewed from the film formation space, but no increase in structural defects is found in that region. This is because most of the dust, which is the nucleus of the structural defect, is generated by film peeling on the wall surface of the deposition space, and the dust cannot reach the region corresponding to the back surface of the substrate with respect to the deposition space. it is conceivable that.

As a means for obtaining such an effect separately from the present invention, it is conceivable to newly install a high-frequency electrode near the slope of the base. However, in the case of such a configuration, a new high-frequency power source is prepared for each high-frequency electrode, or a conventional high-frequency power transmission line is branched and a new transmission line is newly extended for all newly installed high-frequency electrodes. There is a need. These increase the cost, complexity, and size of the device, leading to an increase in manufacturing cost and a decrease in productivity. The present invention can achieve the above effects without causing such adverse effects.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the frequency of high-frequency power introduced into a film formation space is 50 MHz to 450 MHz.
A particularly large effect can be obtained when z. Although the reason why the effect becomes remarkable in such a frequency range is not clear at present, it is considered that the reason is roughly as follows.

As the frequency becomes lower than 50 MHz, the high frequency power transmitted to the auxiliary member decreases, and the high frequency power radiated from the auxiliary member also decreases. As a result, it is considered that the rapid change in the plasma characteristics near the slope of the substrate is not sufficiently relaxed, and the effect of suppressing structural defects is also insufficient. On the other hand, as the frequency becomes higher than 450 MHz, the emission of the high-frequency power from the auxiliary member becomes non-uniform, and the plasma characteristics in the vicinity of the base slope are also non-uniform in the base bus line direction. As a result,
It is considered that a portion where the effect of suppressing structural defects is insufficient in the direction of the base line of the substrate.

In the present invention, the position at which the auxiliary member is set is preferably such that at least a part of the auxiliary member is outside the film-forming space from a cylindrical surface passing through the central axes of the plurality of cylindrical substrates, and more preferably, at least a plurality of cylindrical members. The inside is defined as the cylindrical surface surrounding the base so as to be in contact therewith.

It is necessary that at least a part of the auxiliary member is formed of a conductive member. Considering that the effect is exerted over the entire generatrix direction of the base, the auxiliary member has a certain degree of conductivity in the generatrix direction of the base. Preferably, a member is present. In this case, the conductive members need not be integrated, and for example, a disk-shaped conductive member may be provided discontinuously in the length direction. There is no particular limitation on the conductive material that can be used for the conductive member, but a material that can withstand the use environment such as strength, temperature, and plasma is preferable. For example, Al, Ti,
Examples thereof include metals such as Cr, Fe, Ni, and Cu, and alloys of these metals such as stainless steel.

Although there is no particular limitation on the shape of the auxiliary member, it is preferable that the conductive member has a shape in which the conductive member can exist in a certain area in the generatrix direction of the base as described above.

From the viewpoint of preventing film peeling from the auxiliary member, it is desirable that the surface of the auxiliary member is covered with ceramic. At this time, the ceramic does not necessarily need to be formed of one material member, and a plurality of material members may be used in combination. As the ceramic material covering the auxiliary member surface, alumina, alumina nitride, silicon nitride, boron nitride, zircon, cordierite, zircon cordierite, silicon oxide, beryllium oxide, mica-based ceramics, quartz glass, pyrex glass, and the like are used.

The present invention in which such effects are obtained will be described in detail with reference to the drawings. FIG. 1 shows a-
It is the schematic which showed an example of the Si type | system | group photoconductor manufacturing apparatus. 1A is a schematic cross-sectional view, and FIG. 1B is a schematic cross-sectional view along a cutting line BB ′ in FIG. 1A.

In FIG. 1, 101 is a reaction vessel, 112
Is an exhaust pipe integrally formed on the side surface of the reaction vessel 101,
Reference numeral 105 denotes a cylindrical substrate, 106 denotes a film forming space, 107 denotes a heating element, 108 denotes a rotating shaft, and 109 denotes a motor. The high-frequency power supplied from the high-frequency power supply 103 is supplied to the reaction vessel 101 from the high-frequency power introduction unit 102 via the matching box 104. Part of the high-frequency power supplied into the reaction vessel 101 excites the auxiliary member 111 at least partly made of a conductive material, and causes the auxiliary member 111 to act as an auxiliary electrode. Reference numeral 113 denotes a source gas supply unit that supplies a desired source gas into the reaction vessel 101.

The formation of a deposited film by the apparatus for manufacturing an a-Si photoreceptor according to the present invention can be carried out according to the following procedure.

First, the cylindrical substrate 10 is placed in the reaction vessel 101.
5, the inside of the reaction vessel 101 is exhausted through an exhaust pipe 112 by an exhaust device (not shown). Subsequently, the rotating shaft 10
The cylindrical body 105 is heated to a predetermined temperature of about 200 ° C. to 300 ° C. by the heating element 107 while the cylindrical body 105 is rotated at a predetermined speed by the motor 109 via the heating element 107.
Control.

When the temperature of the cylindrical substrate 105 reaches a predetermined temperature, the raw material gas is introduced into the reaction vessel 101 via the raw material gas supply means 113. After confirming that the flow rate of the raw material gas has reached the set flow rate and that the pressure in the reaction vessel 101 has stabilized, the output value of the high-frequency power supply 103 is set to a desired power, and the high-frequency power introduction means is provided via the matching box 104. The high frequency power is supplied to 102. Glow discharge is generated in the film formation space by the high frequency power radiated from the high frequency power introduction means 102 into the film formation space, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 105. After the desired film thickness is formed, the supply of the high-frequency power is stopped, the supply of the source gas is stopped, and the formation of the deposited film is completed. By repeating the same operation several times,
A light-receiving layer having a desired multilayer structure is formed. In addition, between the respective layers, once the formation of one layer is completed as described above, the discharge is completely stopped once, and after the settings are changed to the gas flow rate and the pressure of the next layer, the discharge is generated again. The formation of the next layer may be performed, or a plurality of layers may be formed continuously by gradually changing the gas flow rate, pressure, and high frequency power to the set values of the next layer within a certain period of time after completion of formation of one layer. May be.

The a- which can be prepared using the present invention as described above
The layer configuration of the Si-based photoconductor is, for example, as follows.

FIG. 5 is a schematic configuration diagram for explaining the layer configuration. Electrophotographic photoreceptor 500 shown in FIG.
Is provided with a photoconductive layer 502 made of a-Si: H, X and having photoconductivity on a support 501.

The photoconductor 500 for electrophotography shown in FIG.
Is composed of a photoconductive layer 502 made of a-Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 503 on a support 501.

The electrophotographic photosensitive member 500 shown in FIG.
Is composed of a photoconductive layer 502 made of a-Si: H, X and having photoconductivity, an amorphous silicon-based surface layer 503, and an amorphous silicon-based charge injection blocking layer 504 on a support 501. I have.

The electrophotographic photosensitive member 500 shown in FIG.
Has a photoconductive layer 502 provided on a support 501. The photoconductive layer 502 includes a charge generation layer 505 and a charge transport layer 506 made of a-Si: H, X.
An amorphous silicon-based surface layer 503 is provided thereon.

[Support] The support 501 of the photoreceptor may be either conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, T
Metals such as e, V, Ti, Pt, Pd, and Fe and alloys thereof, for example, stainless steel and the like. Also, at least the surface of the electrically insulating support such as a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least on the side on which the light-receiving layer is formed, such as a glass or ceramic. Can be used.

The shape of the support 501 can be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness thereof is appropriately determined so as to form the electrophotographic photosensitive member 500 as desired. Decide, electrophotographic photoreceptor 5
When flexibility as 00 is required, the support 50
The thickness can be reduced as much as possible within a range where the function as 1 can be sufficiently exhibited. However, the support 501 is usually 1 in terms of production, handling, mechanical strength and the like.
0 μm or more.

[Photoconductive Layer] The photoconductive layer 502 is
1 is formed by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. Photoconductive layer 502
In order to form hydrogen, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying H that can supply hydrogen atoms (H) and / or halogen atoms (X) are basically used. X is supplied in a desired gas state into a reaction vessel in which the inside can be reduced in pressure to generate a glow discharge in the reaction vessel, which is previously set at a predetermined position. A-S on a predetermined support 501
i: A layer composed of H and X is formed.

It is necessary that the photoconductive layer 502 contains a hydrogen atom and / or a halogen atom, which compensates for dangling bonds of silicon atoms and improves the quality of the layer. In addition, it is indispensable for improving the charge retention characteristics. Therefore, the content of the hydrogen atom or the halogen atom or the sum of the hydrogen atom and the halogen atom is preferably 10 to 40 atom%, more preferably 15 to 25 atom%, based on the sum of the silicon atom and the hydrogen atom and / or the halogen atom. It is desirable to be.

Substances that can serve as a Si supply gas include:
Silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like, which can be gasified, can be used effectively. SiH ₄ , S in terms of ease of handling and good Si supply efficiency
i ₂ H ₆ is mentioned as a preferable example.

In order to structurally introduce hydrogen atoms into the formed photoconductive layer 502 to make it easier to control the introduction ratio of hydrogen atoms, and to obtain good film characteristics, It is also effective to form a layer by mixing a desired amount of gas of H ₂ and / or He or a silicon compound containing hydrogen atom. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

Examples of the effective source gas for supplying a halogen atom include a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an intermediate compound containing a halogen, and a silane derivative substituted with a halogen. Can be Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be preferably used include fluorine gas (F ₂ ) and Br.
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , IF
_{7 and the} like. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, Si
Silicon fluoride such as F ₄ and Si ₂ F ₆ can be mentioned as a preferable example.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 502, for example, the temperature of the support 501, a raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the amount of the substance introduced into the reaction vessel, the discharge power and the like.

It is preferable that the photoconductive layer 502 contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the photoconductive layer 502 in a state of being distributed uniformly and evenly, or even if there is a portion contained in a non-uniform state in the layer thickness direction. Good.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors.
An atom belonging to Group IIIb of the Periodic Table giving p-type conduction properties (hereinafter abbreviated as "IIIb group atom") or an atom belonging to Group Vb of the Periodic Table giving n-type conduction properties (hereinafter "Group Vb atom") Abbreviated as ").

Examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

Control of conductivity contained in photoconductive layer 502
The content of the atoms to be^-2~ 1
× 10^Four Atomic ppm, more preferably 5 × 10^-2~ 5x
10 ^Three Atomic ppm, optimally 1 × 10^-1~ 1 × 10^Three original
Desirably, it is ppm.

In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a material for introducing a group IIIb atom or a group Vb atom is introduced at the time of forming a layer. What is necessary is just to introduce the raw material for use together with another gas for forming the photoconductive layer 502 into the reaction vessel in a gaseous state. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a material which can be gaseous at ordinary temperature and pressure or which can be easily gasified at least under layer forming conditions is used. desirable.

As a raw material for introducing a group IIIb atom, specifically, for introducing a boron atom, B _{2
H 6, B 4 H 10,} B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12,
B ₆ H _{1 4} borohydride such as, BF _3, BCl _3, BBr boron halides such as _3. In addition, AlC
l ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TIC
l ₃ and the like can also be mentioned.

Effective as a raw material for introducing group Vb atoms
Is used for introducing phosphorus atoms._Three, P_TwoH
_Four Phosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three, P
Cl _Five, PBr_Three, PBr_Five, PI_Three Such as phosphorous halide
No. In addition, AsH_Three, AsF_Three, AsCl_Three, A
sBr_Three, AsF_Five, SbH_Three, SbF_Three, SbF_Five, Sb
Cl_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_Three etc
Are also effective starting materials for introducing group Vb atoms.
I can do it.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He if necessary.

Further, carbon atoms and / or
Alternatively, it is also effective to contain an oxygen atom and / or a nitrogen atom. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms.
× 10 ^-5 to 10 atomic%, more preferably 1 × 10 ^-4 to 8
Atomic%, optimally 1 × 10 ^{−3 to} 5 atomic% is desirable. Carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer,
There may be a portion having a non-uniform distribution such that the content changes in the thickness direction of the photoconductive layer.

The layer thickness of the photoconductive layer 502 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic properties and economic effects, and is preferably 1 to 100 μm, more preferably 20 to 50 μm, and most preferably 20 to 50 μm. Is 23 to 45 μm
It is desirable that

In order to form the photoconductive layer 502 having desired film characteristics, a mixing ratio of a gas for supplying Si and a diluting gas is determined.
It is necessary to appropriately set the gas pressure in the reaction vessel, the discharge power, and the temperature of the support. The optimum flow rate of H ₂ and / or He used as the diluent gas is appropriately selected according to the layer design. An optimum range of the gas pressure in the reaction vessel is also appropriately selected in accordance with the layer design. In a normal case, the gas pressure is 1 × 10 ^-4 Torr, preferably 5 × 10 ^{-4 to} 5 × 10 ^-4.
Torr, most preferably 1 × 10 ^{−3 to} 1 Torr.

Desirable numerical ranges of the temperature and the gas pressure of the support for forming the photoconductive layer include the above-mentioned ranges. However, the conditions are not usually determined separately and independently, but have desired characteristics. It is desirable to determine the optimum value based on mutual and organic relationships to form the light receiving member.

[Surface layer] As described above, the support 501
It is preferable to further form an amorphous silicon-based surface layer 503 on the photoconductive layer 502 formed thereon. The surface layer 503 is provided mainly for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

The surface layer 503 can be made of any material as long as it is an amorphous silicon material. For example, a hydrogen atom (H) and / or a halogen atom (X) can be used.
And further contains a carbon atom containing amorphous silicon (hereinafter referred to as "a-SiC: H, X"), a hydrogen atom (H) and / or a halogen atom (X), and further contains an oxygen atom Amorphous silicon (hereinafter referred to as “a-SiO: H, X”), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X), and further containing a nitrogen atom (hereinafter “a-SiN”). : H, X "), a hydrogen atom (H)
And / or amorphous silicon containing a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as “a-SiCON: H,
X)) is suitably used.

The surface layer 503 is manufactured by a vacuum deposition film forming method with appropriate setting of numerical parameters of film forming parameters so as to obtain desired characteristics. For example, a-Si
In order to form the surface layer 503 made of C: H, X, a raw material gas for supplying Si that can supply silicon atoms (Si) and a raw material for supplying C that can supply carbon atoms (C) are basically used. A gas and a source gas for supplying H, which can supply hydrogen atoms (H), and / or a source gas, for supplying X, which can supply halogen atoms (X), are mixed with a desired gas in a reaction vessel capable of reducing the pressure inside. The state is introduced to generate a glow discharge in the reaction vessel, and a-SiC: H, X is formed on a support 501 on which a photoconductive layer 502 previously set at a predetermined position is formed.
May be formed.

As the material of the surface layer, any amorphous material containing silicon may be used.
A compound with a silicon atom containing at least one element selected from oxygen is preferable, and a compound containing a-SiC as a main component is particularly preferable.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.

Further, hydrogen atoms and / or
And a halogen atom must be contained,
This is important for compensating for dangling bonds of silicon atoms and improving the layer quality, particularly, the photoconductive properties and the charge retention properties. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, based on the total amount of the constituent atoms.
Atomic%, optimally 40 to 60 atomic% is desirable. The content of fluorine atoms is usually 0.1.
It is desirable that the content be 01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%.

The substance which can serve as a silicon (Si) supply gas used in forming the surface layer includes Si (Si).
H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc.
Alternatively, silicon hydrides (silanes) which can be gasified can be used effectively, and SiH ₄ , Si ₂ H can be used in terms of ease of handling at the time of forming the layer, high Si supply efficiency, and the like.
₆ is preferred. In addition, these S
The raw material gas for supplying i is optionally H ₂ , He, Ar,
It may be used after being diluted with a gas such as Ne.

Examples of the substance that can serve as a carbon supply gas include:
A gaseous hydrocarbon such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ or a gasifiable hydrocarbon can be used effectively. CH ₄ and C ₂ H ₆ are preferred in terms of good supply efficiency and the like. Further, the raw material gas for supplying C may be used after being diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

Substances that can serve as nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ , CO, C
Compounds in a gaseous state or gasifiable such as O ₂ and N ₂ are mentioned as being effectively used. In addition, these nitrogen and oxygen supply source gases may be replaced with H ₂ ,
It may be used after being diluted with a gas such as He, Ar, or Ne.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 503 to be formed, these gases may further be hydrogen gas or silicon compound gas containing hydrogen atoms. Also, it is preferable to form a layer by mixing desired amounts. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

Effective as a source gas for supplying halogen atoms
For example, halogen gas, halide, halogen
, Halogen-substituted silanes containing
Gaseous or gasifiable simple substance or halo such as a derivative
Gen compounds are preferred. In addition,
Gaseous gas containing recon and halogen atoms
Or gasification, silicon hydride containing halogen atoms
Compounds can also be mentioned as effective. In the present invention
As a simple substance or a halogen compound that can be suitably used in
Specifically, specifically, fluorine gas (F_Two), BrF, ClF,
ClF_Three, BrF _Three, BrF_Five, IF_Three, IF₇ Such as haloge
And intermolecular compounds. Contains halogen atoms
Silicon compounds, silanes substituted with so-called halogen atoms
As the derivative, specifically, for example, SiF_Four, Si_TwoF
₆ Can be cited as preferred.
You.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 503, for example, the temperature of the support 501, a raw material used to contain hydrogen atoms and / or halogen atoms The amount to be introduced into the reaction vessel, the discharge power and the like may be controlled.

Carbon atoms and / or oxygen atoms and / or
Alternatively, the nitrogen atoms may be uniformly contained in the surface layer, or there may be a portion having a non-uniform distribution such that the content changes in the thickness direction of the surface layer.

Further, it is preferable that the surface layer 503 contains atoms for controlling conductivity as necessary. The atoms controlling the conductivity may be contained in the surface layer 503 in a state of being distributed uniformly and evenly, or there may be a part contained in the layer thickness direction in a non-uniform state. .

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to Group IIIb of the Periodic Table giving p-type conduction properties (hereinafter abbreviated as "Group IIIb atom") or an atom belonging to Group Vb of the Periodic Table giving n-type conduction properties (hereinafter "Group Vb atom") Abbreviated as ").

Examples of group IIIb atoms include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of atoms for controlling conductivity contained in the surface layer 503 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 1
Desirably, the concentration is 0 ² atomic ppm, most preferably 1 × 10 ^-1 to 1 × 10 ² atomic ppm. Atoms controlling conductivity,
For example, in order to structurally introduce a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a source material for introducing a group Vb atom in a gaseous state in a reaction vessel at the time of forming a layer. What is necessary is just to introduce with another gas for forming the surface layer 503 into it. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is used. Is desirable. As such a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆
H _12, B ₆ H ₁₄ borohydride such as, BF _3, BCl _3, BB
and boron halide such as r ₃ . In addition, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , Tl
Cl _{3 and the} like can also be mentioned.

As a raw material for introducing a group Vb atom, it is effective to use PH ₃ ,
Phosphorus hydride such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl
₃ , phosphorus halides such as PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl
₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr
_{3 and the} like can also be mentioned as effective starting materials for introducing Group Vb atoms.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with a gas such as H ₂ , He, or Ar as necessary.

The thickness of the surface layer 503 is usually 0.0
1 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.
It is desirable that the thickness be 1 to 1 μm. If the thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light receiving member, and if it exceeds 3 μm, the electrophotographic properties such as an increase in residual potential are reduced. .

The surface layer 503 is carefully formed so that the required characteristics are provided as desired. That is, a substance containing Si, C and / or N and / or O, H and / or X as a constituent element takes a form from a crystal to an amorphous depending on the formation conditions, and is electrically conductive. In the present invention, a compound having desired properties according to the purpose is shown, since the properties between the properties from a semiconductive property to an insulating property, and properties from a photoconductive property to a non-photoconductive property are respectively shown. The formation conditions are strictly selected as desired so that is formed.

For example, in order to provide the main purpose of improving the pressure resistance of the surface layer 503, the surface layer 503 is manufactured as a non-single-crystal material having a remarkable electrical insulating property in a use environment. When the surface layer 503 is provided for the main purpose of improving the continuous repetitive use characteristics and the use environment characteristics, the above-described degree of electrical insulation is reduced to some extent, and the non-conductive layer has a certain sensitivity to irradiated light. Formed as a single crystal material. In order to form the surface layer 503 having characteristics capable of achieving the object, it is necessary to appropriately set the temperature of the support 501 and the gas pressure in the reaction vessel.

The optimum range of the temperature (Ts) of the support 501 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable that the temperature be 330 ° C., optimally 250 to 300 ° C. Similarly, the gas pressure in the reaction vessel is appropriately selected in an optimum range according to the layer design.
× 10 ^{-4 to} 10 Torr, more preferably 5 × 10 ^-4 to
Preferably, the pressure is 5 Torr, most preferably 1 × 10 ^{−3 to} 1 Torr.

Desirable numerical ranges of the temperature and gas pressure of the support for forming the surface layer include the above-mentioned ranges. However, the conditions are not usually determined separately and independently, but the light having the desired characteristics is not usually determined. It is desirable to determine the optimum value based on mutual and organic relationships to form the receiving member.

A region in which the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms continuously decreases toward photoconductive layer 502 may be provided between surface layer 503 and photoconductive layer 502. . As a result, the adhesion between the surface layer and the photoconductive layer can be improved, and the influence of interference due to light reflection at the interface can be reduced. At the same time, carrier trapping at the interface can be prevented, and the photoconductor characteristics can be improved. Can be reached.

[Charge Injection Blocking Layer] If necessary, a charge injection blocking layer 504 that functions to block charge injection from the conductive support side may be provided between the conductive support and the photoconductive layer. Good. That is, the charge injection blocking layer 504 has a function of preventing charge from being injected from the support side to the photoconductive layer side when the photoreceptor is subjected to a charging treatment of a fixed polarity on its surface. Such a function is not exhibited when it is subjected to a charging treatment, that is, it has a polarity dependency. In order to provide such a function, the charge injection blocking layer 504 is provided.
Contains relatively more atoms for controlling the conductivity than the photoconductive layer.

The atoms for controlling the conductivity contained in the layer may be distributed evenly and uniformly in the layer, or may be contained evenly in the direction of the thickness of the layer. Some portions may be contained in a state of being uniformly distributed. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

However, in any case, it is necessary to uniformly contain a uniform distribution in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics in the in-plane direction uniform. .

As the atoms for controlling the conductivity contained in the charge injection blocking layer 504, there can be mentioned so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the periodic table that provide p-type conduction characteristics ( Hereafter "Group IIIb atom"
Abbreviation) or V of the periodic table giving n-type conduction characteristics
atom belonging to group b (hereinafter abbreviated as "group Vb atom")
Can be used.

As the Group IIIb atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth). In particular, P and As
Is preferred.

The content of the atoms controlling the conductivity contained in the charge injection blocking layer 504 is appropriately determined as desired, but is preferably 10 to 1 × 10 ⁴ atoms p.
pm, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

Further, by including at least one of carbon atoms, nitrogen atoms and oxygen atoms in the charge injection blocking layer 504, adhesion to another layer provided in direct contact with the charge injection blocking layer 504 is achieved. The performance can be further improved.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be evenly distributed in the layer, or may be contained evenly in the layer thickness direction. Some portions may be contained in a non-uniformly distributed state. However, in any case, it is necessary to be uniformly contained in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics uniform in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer 504 is appropriately determined so that the object of the present invention is effectively achieved. But, in the case of one kind, as quantity
In the case of two or more kinds, preferably 1 × 10
^-3 to 50 at%, more preferably 5 × 10 ⁻³ to 30 at%, and most preferably 1 × 10 ⁻² to 10 at%.

Further, hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer 504 compensate for dangling bonds existing in the layer, and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer 504 is preferably 1 to
50 at%, more preferably 5 to 40 at%, optimally 1
The content is desirably 0 to 30 atomic%.

The thickness of the charge injection blocking layer 504 is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 from the viewpoints of obtaining desired electrophotographic characteristics and economic effects.
μm, optimally 0.5 to 3 μm.

To form the charge injection blocking layer 504, a vacuum deposition method similar to the above-described method for forming the photoconductive layer is employed. As in the case of the photoconductive layer 502, it is necessary to appropriately set the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, and the temperature of the support 501.

The flow rate of the diluent gas H ₂ and / or He is appropriately selected according to the layer design, but H ₂ and / or He may be added to the Si supply gas.
In the normal case, it is desirable to control to a range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
0 ^{-4 to} 10 Torr, preferably 5 × 10 ^{-4 to} 5 Torr
r, and most preferably, 1 × 10 ^{−3 to} 1 Torr.

Desirable numerical ranges of the mixing ratio of the diluent gas, the gas pressure, the discharge power, and the temperature of the support for forming the charge injection blocking layer 504 include the above-mentioned ranges, and the factors for forming these layers are usually independent. However, it is desirable that the optimum value of each layer forming factor be determined based on mutual and organic relationships in order to form layers having desired properties.

For the purpose of further improving the adhesion between the support 501 and the photoconductive layer 502 or the charge injection blocking layer 504, for example, Si ₃ N ₄ , SiO ₂ , SiO, or silicon atoms are used as a base material. , A hydrogen atom and / or a halogen atom, and an amorphous material containing a carbon atom and / or an oxygen atom and / or a nitrogen atom. Further, a light absorbing layer for preventing an interference pattern from being generated by light reflected from the support may be provided.

[0128]

The present invention will be described in more detail with reference to the following Experimental Examples and Examples, which should not be construed as limiting the present invention.

<Experimental Example 1 and Comparative Experimental Example 1> In Experimental Example 1, a high-frequency power supply was mounted on a cylindrical aluminum cylinder 105 having a diameter of 80 mm and a length of 358 mm using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG. The oscillation frequency of 103 is 1
Film formation was performed under the conditions shown in Table 1 at 00 MHz.

[0130]

[Table 1] The high-frequency power introducing means 102 is installed at the center of a film forming space 106 surrounded by a cylindrical aluminum cylinder 105 arranged on the same circumference.
Was set to 125 mm from the central axis of the cylindrical aluminum cylinder 105 to the central axis of the cylindrical aluminum cylinder 105.

The auxiliary member 111 has a thickness of 2 mm outside the SUS304 column having a diameter of 10 mm and a length of 358 mm.
Of alumina. The auxiliary member 111 was fixed on an alumina cylinder having a diameter of 10 mm provided in the reaction vessel 101 so as to be parallel to and at the same height as the cylindrical aluminum cylinder 105. A total of eight auxiliary members 111 were arranged between each cylinder. The distance from the central axis of the high-frequency power introducing means 102 to the central axis of each auxiliary member 111 was 180 mm.

Under these conditions, the film was formed without rotating the motor 109, that is, without rotating the cylinder 105. After the film was formed, the distribution of the number of structural defects of 10 μm or more in the circumferential direction of the cylinder was examined. The thickness of the deposited film to be formed was such that the maximum thickness on the cylinder 105 was 30 μm.

In Comparative Example 1, the auxiliary member 111 was removed from the reaction vessel 101, and the cylinder 105 was similarly operated.
A film was formed thereon, and after the film formation was completed, the distribution of the number of structural defects of 10 μm or more in the circumferential direction of the cylinder was examined.

FIG. 6 shows the results of Experimental Example 1 and Comparative Experimental Example 1. As shown in FIG. 6, an electrically floating auxiliary member containing a conductive material is provided inside the reaction vessel, and the installation position of the auxiliary member is set outside the film formation space from a cylindrical surface passing through the central axes of the plurality of cylindrical substrates. It was confirmed that the occurrence of structural defects around ± 45 to 60 degrees in the circumferential direction of the substrate could be suppressed.

<Experimental Example 2 and Comparative Experimental Example 2> In Experimental Example 2, the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 1 was manufactured in the same manner as in Experimental Example 1 except that the installation position of the auxiliary member 111 was changed to 160 mm. A film was formed on a cylindrical aluminum cylinder 105 having a diameter of 80 mm and a length of 358 mm without rotating the cylinder 105 under the conditions shown in Table 1 above. The circumferential distribution of the cylinder was investigated.

In Comparative Example 2, the auxiliary member 111 was removed from the reaction vessel 101, and the cylinder 105 was similarly operated.
A film was formed thereon, and after the film formation was completed, the distribution of the number of structural defects of 10 μm or more in the circumferential direction of the cylinder was examined.

FIG. 7 shows the results of Experimental Example 2 and Comparative Experimental Example 2. As shown in FIG. 7, an electrically floating auxiliary member including a conductive member is provided inside the reaction vessel, and the position of the auxiliary member is set such that the auxiliary member is positioned outside the film-forming space from the cylindrical surface passing through the central axes of the plurality of cylindrical substrates. It has been confirmed that the occurrence of a structural defect in the vicinity of ± 45 to 60 degrees in the circumferential direction of the substrate can be suppressed by setting the inside of the cylindrical surface so as to be in contact with the surrounding cylindrical surface.
In addition, the effect of suppressing the structural defect was larger than that of Experimental Example 1, and it was confirmed that a larger effect could be obtained by installing the auxiliary member at such a position.

Example 1 A high-frequency power source 1 was placed on a cylindrical aluminum cylinder 105 having a diameter of 80 mm and a length of 358 mm using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
A photoreceptor comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared by the following procedure under the conditions shown in Table 2 with the oscillation frequency of No. 03 set to 450 MHz.

[0139]

[Table 2] First, a cylindrical substrate 105 is placed in a reaction vessel 101,
The inside of the reaction vessel 101 was exhausted through an exhaust pipe 112 by an exhaust device (not shown). Subsequently, the cylindrical body 105 is rotated at a speed of 10 rpm by the motor 109 via the rotating shaft 105, and the heating element 1 is further supplied while supplying 500 sccm of Ar into the reaction vessel by the raw material gas supply means 113.
07, the cylindrical substrate 105 was heated and controlled at 240 ° C., and the state was maintained for 2 hours.

Next, the supply of Ar was stopped, and
After exhausting the inside of 01 through an exhaust pipe 112 by an exhaust device (not shown), a source gas used for forming a charge injection blocking layer shown in Table 2 was introduced through a source gas supply unit 113. After confirming that the flow rate of the raw material gas has reached the set flow rate and that the pressure in the reaction vessel 101 has been stabilized, the output value of the high-frequency power supply 103 is set to the power shown in Table 2, and the high-frequency power is supplied through the matching box 104. By supplying high-frequency power to the power introducing means 102, a charge injection blocking layer was formed on the cylindrical substrate 105. After the formation of the predetermined film thickness, the supply of the high-frequency power was stopped, the supply of the source gas was stopped, and the formation of the charge injection blocking layer was completed. By repeating the same operation a plurality of times, a photoconductive layer and a surface layer were sequentially formed.

The high frequency power introducing means 102 has a diameter of 20 mm
Is formed by covering the outside of a SUS304 column with an alumina material having a thickness of 3 mm, and forming a film forming space 10 surrounded by a cylindrical aluminum cylinder 105 disposed on the same circumference.
6 was set at the center. The distance from the central axis of the high-frequency power introducing means 102 to the central axis of the cylindrical aluminum cylinder 105 was 125 mm.

The auxiliary member 111 is a SUS304 cylinder having a diameter of 10 mm and a length of 358 mm.
The cylindrical aluminum cylinder 105 was fixed on the alumina cylinder having a diameter of 10 mm set in 1 so as to be parallel to and at the same height as the cylindrical aluminum cylinder 105. A total of eight auxiliary members 111 were arranged between each cylinder. High frequency power introduction means 10
The distance from the center axis of No. 2 to the center axis of each auxiliary member 111 was 180 mm.

The thus manufactured a-Si photoreceptor was manufactured by Canon Copier NP-675 modified for this test.
0, and the characteristics of the photoreceptor were evaluated. Evaluation items were "image defect", "charging ability", "sensitivity", "characteristic unevenness",
Each item was evaluated by the following specific evaluation method with five items of “total image characteristics”.

Image Defects: A halftone chart made by Canon (part number FY9-9042) is placed on a platen, and white spots having a diameter of 0.1 mm or more within the same area of a copy image obtained when copying are performed. I counted that number.

Charging ability: A dark part potential at the developing device position when a constant current is applied to the main charging device of the copying machine is measured. Therefore, the higher the dark area potential, the better the charging ability. The charging ability was measured over the entire area of the photoconductor in the generatrix direction, and evaluated based on the lowest dark area potential therein.

Sensitivity: After adjusting the main charger current so that the dark portion potential at the developing device position becomes a constant value, using a predetermined white paper having a reflection density of 0.01 or less for the original, the light portion potential at the developing device position Is evaluated based on the image exposure light amount when the image exposure light amount is adjusted so that is a predetermined value. Therefore, the smaller the image exposure light amount, the better the sensitivity. The sensitivity was measured over the entire area of the photoconductor in the generatrix direction, and evaluated based on the maximum image exposure light amount therein.

Image density unevenness: First, the main charger current was adjusted so that the dark portion potential at the developing device position became a constant value, and then a predetermined white paper having a reflection density of 0.01 or less was used for the original. The image exposure light amount was adjusted so that the bright portion potential became a predetermined value. Next, the Canon halftone chart (part number: F
Y9-9042) was placed on a platen and evaluated by the difference between the maximum value and the minimum value of the reflection density in the entire area on the copy image obtained when copying.

Overall image characteristics: Copy images were comprehensively evaluated, including image deletion, optical memory, and the like.

Table 3 shows the evaluation results.

<Comparative Example 1> The procedure of Example 1 was repeated, except that the auxiliary member 111 was removed.
On a cylindrical aluminum cylinder 105 having a length of 0 mm and a length of 358 mm, a photosensitive member comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared under the conditions shown in Table 2 above.

The manufactured a-Si photoreceptor was used in Example 1 and was modified for this test.
6750, and the characteristics of the photoreceptor were evaluated. The evaluation items were five items of “image defect”, “chargeability”, “sensitivity”, “characteristic unevenness”, and “total image characteristics”, and each item was evaluated by the same specific evaluation method as in Example 1. . Table 3 shows the evaluation results.

[0152]

[Table 3] ：: very good ：: good ：: normal ▲: slightly bad ×: very bad As shown in Table 3, in Example 1, good results were obtained in any of the items. It was confirmed that an a-Si photosensitive member excellent in electrophotographic characteristics including defects, charging ability, sensitivity, and image density unevenness was stably manufactured. On the other hand, in Comparative Example 1, a clear difference was observed between Example 1 in image defects and overall image characteristics.

<Embodiment 2> A high-frequency power source 1 was placed on a cylindrical aluminum cylinder 105 having a diameter of 80 mm and a length of 358 mm using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
03 oscillation frequency of 13.56 MHz, 50 MHz, 1
A photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared in the same procedure as in Example 1 under the conditions shown in Table 4 as four conditions of 00 MHz, 450 MHz, and 900 MHz.

[0154]

[Table 4] The high-frequency power introducing means 102 has a structure in which a nickel cylinder having a diameter of 20 mm is covered with an alumina material having a thickness of 3 mm, and a center of a film forming space 106 surrounded by a cylindrical aluminum cylinder 105 arranged on the same circumference. It was installed in. The distance from the central axis of the high-frequency power introducing means 102 to the central axis of the cylindrical aluminum cylinder 105 is 12
5 mm.

The auxiliary member 111 is a SUS304 cylinder having a diameter of 10 mm and a length of 200 mm.
The cylindrical aluminum cylinder 105 was fixed on an alumina cylinder having a diameter of 10 mm, which was set at 01, so as to be parallel to the cylindrical aluminum cylinder 105 and vertically symmetric with respect to the generatrix direction of the cylindrical aluminum cylinder 105. A total of eight auxiliary members 111 were arranged between each cylinder. The distance from the central axis of the high-frequency power introducing means 102 to the central axis of each auxiliary member 111 was 160 mm.

The thus manufactured a-Si photoreceptor was manufactured by Canon Copier NP-675 modified for this test.
0, and the characteristics of the photoreceptor were evaluated. Evaluation items were "image defect", "charging ability", "sensitivity", "characteristic unevenness",
Each item was evaluated by the same specific evaluation method as in Example 1, with five items of “total image characteristics”. Table 5 shows the evaluation results.
Shown in

<Comparative Example 2> The procedure of Example 2 was repeated except that the auxiliary member 111 was removed, and the diameter was 80 mm and the length was 358.
A photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared on a cylindrical aluminum cylinder 105 having a thickness of 1 mm under the conditions shown in Table 4 above.

The manufactured a-Si photoreceptor was used in Example 2 and was modified for this test.
6750, and the characteristics of the photoreceptor were evaluated. The evaluation items were five items of “image defect”, “chargeability”, “sensitivity”, “characteristic unevenness”, and “total image characteristics”, and each item was evaluated by the same specific evaluation method as in Example 1. . Table 5 shows the evaluation results.

[0159]

[Table 5] ：: very good ：: good ：: normal ：: slightly bad ×: very bad As shown in Table 5, in Example 2, good results were obtained in any of the items. It was confirmed that an a-Si-based photoreceptor excellent in electrophotographic characteristics including image defects, charging ability, sensitivity, and image density unevenness was stably manufactured. In particular, it has been confirmed that the effect of the present invention appears more remarkably when the frequency of the high-frequency power is in the range of 50 MHz to 450 MHz. On the other hand, Comparative Example 2
In Example 2, a remarkable difference was observed between Example 2 in image defects and overall image characteristics.

<Embodiment 3> A high-frequency power supply 1 was placed on a cylindrical aluminum cylinder 105 having a diameter of 80 mm and a length of 358 mm using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
A function-separated a-Si photoreceptor comprising a charge transport layer, a charge generation layer and a surface layer was produced in the same procedure as in Example 1 under the conditions shown in Table 6 with the oscillation frequency of No. 03 being 105 MHz.

[0161]

[Table 6] The high-frequency power introduction means 102 is a SUS30 having a diameter of 20 mm.
The four cylinders were configured such that the outside of the cylinder was covered with an alumina material having a thickness of 3 mm, and was placed at the center of a film forming space 106 surrounded by a cylindrical aluminum cylinder 105 arranged on the same circumference. The distance from the central axis of the high-frequency power introducing means 102 to the central axis of the cylindrical aluminum cylinder 105 is 1
It was 25 mm.

The auxiliary member 111 was formed by laminating a SUS304 disk having a diameter of 10 mm and a thickness of 80 mm with an alumina disk having a diameter of 10 mm and a thickness of 2 mm interposed therebetween, and having a diameter of 10 mm and a length of 408 mm. Auxiliary member 11
1 was fixed on an alumina cylinder having a diameter of 10 mm provided in the reaction vessel 101 so as to be parallel to the cylindrical aluminum cylinder 105 and vertically symmetric with respect to the generatrix direction of the cylindrical aluminum cylinder 105. Auxiliary member 11
No. 1 was arranged between each cylinder, eight pieces in total. From the central axis of the high-frequency power introduction means 102, each auxiliary member 111
The distance to the central axis was 160 mm.

The thus manufactured a-Si photoreceptor was manufactured by Canon Copier NP-675 modified for this test.
0, and the characteristics of the photoreceptor were evaluated. Evaluation items were "image defect", "charging ability", "sensitivity", "characteristic unevenness",
Each item was evaluated by the same specific evaluation method as in Example 1, with five items of “total image characteristics”. Table 7 shows the evaluation results.
Shown in

<Embodiment 4> The auxiliary member 111 has a thickness of 2 mm.
An a-Si-based photoreceptor was produced in the same manner as in Example 3, except that the structure was covered with an alumina cylinder. Created a
The Si photoreceptor was installed in a Canon copier NP-6750 modified for this test, and the characteristics of the photoreceptor were evaluated. The evaluation items were five items of "image defect", "charging ability", "sensitivity", "characteristic unevenness", and "total image characteristics".
Each item was evaluated by the same specific evaluation method as in Example 1. Table 7 shows the evaluation results.

Comparative Example 3 The procedure of Example 3 was repeated except that the auxiliary member 111 was removed, and the diameter was 80 mm and the length was 358.
A function-separated a-Si photoreceptor comprising a charge transport layer, a charge generation layer and a surface layer was prepared on a cylindrical aluminum cylinder 105 mm under the conditions shown in Table 6 above. The produced a-Si photoreceptor was installed in a Canon copier NP-6750 modified for the test used in Example 3,
The characteristics of the photoreceptor were evaluated. The evaluation items were five items of “image defect”, “chargeability”, “sensitivity”, “characteristic unevenness”, and “total image characteristics”, and each item was evaluated by the same specific evaluation method as in Example 1. . Table 7 shows the evaluation results.

[0166]

[Table 7] ：: very good ：: good 普通: normal ▲: slightly bad ×: very bad As shown in Table 7, in Example 3, good results were obtained in any of the items. It was confirmed that an a-Si-based photoreceptor excellent in electrophotographic characteristics including image defects, charging ability, sensitivity, and image density unevenness was stably manufactured.

Also in Example 4, good results were obtained in any of the items. According to the present invention, a- images having excellent electrophotographic characteristics including image defects, charging ability, sensitivity, and image density unevenness were obtained over the entire area. It was confirmed that the Si-based photoconductor was stably manufactured. Further, it was confirmed that, by adopting a configuration in which the auxiliary member 111 was covered with an alumina material, a better result as in Example 3 was obtained with respect to “image defect”.

On the other hand, in Comparative Example 3, a remarkable difference was observed between Examples 3 and 4 in image defects and overall image characteristics, and the effect of the present invention was confirmed.

[0169]

As described above, according to the present invention, it is possible to suppress dust adsorption on a substrate in a region near an adjacent substrate during formation of a deposited film, while suppressing an increase in cost, complexity, and size of the apparatus. For example, it is possible to reduce structural defects in the deposited film of the a-Si photoconductor. As a result, image defects are suppressed, and an a-Si photosensitive member having good other electrophotographic characteristics can be stably formed at low cost.

Further, according to the present invention, the formed a-Si
An unexpected effect was also obtained in that the variation of the system photoreceptor characteristics among lots was suppressed.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of an a-Si-based photoconductor manufacturing apparatus that can be used in the present invention.

FIG. 2 shows a conventional RF plasma C using a frequency in an RF band.
It is a schematic block diagram which showed an example of the manufacturing apparatus of the light receiving member for electrophotography by the VD method.

FIG. 3 shows a conventional MW plasma C using a MW band frequency.
It is a schematic block diagram which showed an example of the manufacturing apparatus of the light receiving member for electrophotography by the VD method.

FIG. 4 is a schematic configuration diagram showing an example of a conventional apparatus for manufacturing an electrophotographic light-receiving member by a VHF plasma CVD method using a frequency in a VHF band.

FIG. 5 is a diagram illustrating an example of a layer configuration of an a-Si photoconductor.

FIG. 6 is a diagram showing evaluation results of Experimental Example 1 and Comparative Experimental Example 1 performed to confirm the effects of the present invention.

FIG. 7 is a diagram showing evaluations of Experimental Example 2 and Comparative Experimental Example 2 performed to confirm the effects of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Reaction container 102 High frequency electric power introduction means 103 High frequency power supply 104 Matching box 105 Cylindrical substrate 106 Film formation space 107 Heating element 108 Rotating shaft 109 Motor 110 Reduction gear 111 Auxiliary member 112 Exhaust pipe 113 Source gas supply means 2100 Deposition device 2111 Reaction container 2112 Cylindrical substrate 2113 Supporting heater 2114 Source gas introduction pipe 2115 Matching box 2116 Source gas pipe 2117 Reaction vessel leak valve 2118 Main exhaust valve 2119 Vacuum gauge 2200 Source gas supply device 2211-2216 Mass flow controller 2221-2226 Source gas cylinder 2231 ２２2236 Raw material gas cylinder valve 2241 to 2246 Gas inflow valve 2251 to 2256 Gas outflow valve 2261 2266 Pressure regulator 301 Reaction vessel 302 Dielectric window 303 Waveguide 304 Exhaust pipe 305 Cylindrical substrate 306 Film formation space 307 Heating element 308 Rotating shaft 309 Motor 310 Reduction gear 351 Source gas introduction pipe 401 Reaction vessel 402 High frequency power introduction means 403 High-frequency power supply 404 Matching box 405 Cylindrical substrate 406 Film formation space 407 Heating element 408 Rotating shaft 409 Motor 410 Reduction gear 411 Auxiliary member 412 Exhaust pipe 413 Source gas supply means 500 Electrophotographic photoconductor 501 Support 502 Photoconductive layer 503 Surface layer 504 Charge injection blocking layer 505 Charge generation layer 506 Charge transport layer

Claims (6)

[Claims] 1. A deposition film forming apparatus by a plasma CVD method having means for arranging a plurality of substrates so as to surround a film formation space in a reaction vessel, wherein at least a part of the reaction vessel is made of a conductive material. A deposited film forming apparatus, wherein an electrically floating auxiliary member is provided. 2. A means for arranging a plurality of cylindrical substrates on the same circumference so as to surround a film-forming space in a vacuum-tight airtight reaction vessel, a source gas supply means, and at least one high-frequency power introduction means. A plasma for generating a glow discharge in the reaction vessel and forming a deposited film on the substrate by introducing high-frequency power from the high-frequency power introduction means to the source gas supplied from the source gas supply means; 2. The deposited film forming apparatus according to claim 1, wherein the apparatus is a CVD method, and an installation position of the auxiliary member is outside a film forming space from a cylindrical surface passing through the central axes of the plurality of cylindrical substrates. 3. The frequency of the high-frequency power is 50 MHz or more.
3. The deposited film forming apparatus according to claim 2, wherein the frequency is 450 MHz. 4. The deposited film forming apparatus according to claim 2, wherein the auxiliary member is provided inside a cylindrical surface surrounding the outer surface of the film-forming space of the plurality of cylindrical substrates so as to be in contact therewith. 5. The deposited film forming apparatus according to claim 2, wherein a surface of said auxiliary member is covered with a ceramic material. 6. A method of forming a deposited film by a plasma CVD method in which a plurality of substrates are arranged in a reaction vessel so as to surround a film forming space, wherein at least a part of the substrate is formed of an electrically conductive material. A method for forming a deposited film, wherein a deposited film is formed in a reaction vessel provided with a floating auxiliary member.