JPH09219372A - Equipment and method for manufacturing amorphous silicon photosensitive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the ununiformity in characteristic on a photosensitive body by supplying material gas from a material gas supplying means through a gas jetting port installed on the surface of a high-frequency power supplying means and scattering the material gas by shields installed outside the gas jetting port. SOLUTION: In a high-frequency electrode 101 which also serves for a material gas supplying means, shields 102 are fixed to the high-frequency electrode 101 by a shield support 103. The size of each shield 102 is such that the radius R of the largest inscribed circle of the shield 102 out of ones having a central axis which passes through the center of the gas jetting port 104 and is vertical to the high-frequency electrode 101 and the radius γ of a circumscribed circle of the gas jetting port 104 may satisfy a formula R>=3γ. Each of the shields 102 is so located as to meet a formula a<=2R, where the radius of the biggest inscribed circle of the shield 2 out of ones having a central axis which pass through the center of the gas jetting port 104 and is vertical to the high-frequency electrode 101 is R and the minimum distance between such an inscribed circle and the gas jetting port 104 is 'a'. Then, material gas is scattered by these shields 2 and thereby the uniform characteristic of a photosensitive body can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for producing an amorphous silicon type photosensitive member using a plasma CVD method, and more particularly to amorphous silicon for electrophotography (hereinafter referred to as a-Si).
Referred to as “) -type photoconductor manufacturing apparatus.

[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. It is required to have characteristics such as having an absorption spectrum, fast photoresponsiveness, having a desired dark resistance value, and being harmless to the human body during use. In particular, 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-polluting property at the time of use is important. Hydrogenated amorphous silicon (hereinafter abbreviated as "a-Si: H") is a photoconductive material exhibiting such excellent properties. For example, Japanese Patent Publication No. Sho 60-35059 discloses an electrophotographic light-emitting material. Application as a receiving member is described. Generally, such an electrophotographic photoreceptor is prepared by heating a conductive support to 50 ° C. to 400 ° C., and performing a vacuum deposition method on the support.
Sputtering method, ion plating method, thermal CVD
A by a film forming method such as a plasma CVD method, a photo CVD method, or the like.
A photoconductive layer made of -Si is formed. 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 element (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 Also, Japanese Patent Application Laid-Open No.
No. 115556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has electrical, optical, photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. Non-photoconductive amorphous material containing silicon and carbon atoms on a photoconductive layer composed of an amorphous material based on silicon atoms in order to improve the environmental characteristics of use and the stability over time. A technique for providing a surface barrier layer composed of Further, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 0-67951 describes a technique for a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. A technique using an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements as a surface layer is described.

On the other hand, Japanese Patent Application Laid-Open No. Sho 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the photoreceptor surface 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. Also, JP-A-61-283116
The publication describes a microwave plasma CVD method (hereinafter abbreviated as "MW-PCVD") suitable for forming an amorphous semiconductor and its apparatus. JP-A-63-14938
In Japanese Patent No. 1 publication, a plurality of cylindrical substrates are installed on concentric circles,
A technique is described in which an amorphous film is formed on a substrate by applying microwave power to a discharge space surrounded by a cylindrical substrate. With these technologies, aS for electrophotography
The electrical, optical and photoconductive characteristics of the i-type photoreceptor and the use environment characteristics have been improved, and the image quality has been improved accordingly.

The manufacturing apparatus and manufacturing method of such an a-Si photosensitive member are as follows. FIG. 3 is a schematic configuration 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 supply. The configuration of the manufacturing apparatus shown in FIG. 3 is as follows.
This apparatus is roughly composed of a deposition apparatus 3100, a source gas supply apparatus 3200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel 3111. A cylindrical support 3 is provided in a reaction vessel 3111 in the deposition apparatus 3100.
112, a support heating heater 3113, and a raw material gas introduction pipe 3114 are installed, and a high frequency matching box 3115 is further connected. Source gas supply device 3200
Is SiH4, GeH4, H2, CH4, B2H6, P
Cylinders 3221 to 326 for source gas such as H3 and valves 3231 to 236, 3241 to 246, 3251 to
3256 and mass flow controller 3211-3
216, and the cylinder of each source gas is a valve 32.
It is connected to the gas introduction pipe 3114 in the reaction container 3111 via 60.

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction container 31
A cylindrical support 3112 is installed in the chamber 11, and the inside of the reaction vessel 3111 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical support 3112 is raised to 200 ° C. to 350 ° C. by the support heating heater 3113.
The temperature is controlled to a predetermined temperature. In order to allow the source gas for forming the deposited film to flow into the reaction vessel 3111, the valves 3231 to 237 of the gas cylinder and the leak valve 3117 of the reaction vessel are used.
The inlet valve 324 is closed.
After confirming that 1 to 3246, outflow valves 3251 to 3256, and auxiliary valve 3260 are open, first open main valve 3118 to exhaust reaction vessel 3111 and gas piping 3116. Next, when the reading of the vacuum gauge 3119 becomes about 5 × 10 ⁻⁶ Torr, the auxiliary valve 32 is read.
60, close outflow valves 3251 to 256. After that, each gas is introduced from the gas cylinders 3221 to 226 by opening the valves 3231 to 236, and is introduced into the pressure regulator 326.
Each gas pressure is adjusted to ² kg / cm ^{2 according} to 1-366. Next, the inflow valves 3241 to 246 are gradually opened, and each gas is supplied to the mass flow controllers 3211 to 32.
16 is introduced.

After the preparation for film formation is completed as described above, each layer is formed in the following procedure. Cylindrical support 31
When 12 reaches a predetermined temperature, the outflow valve 3251
~ 3256 required and auxiliary valve 326
0 is gradually opened, and a predetermined gas is supplied from the gas cylinders 3221 to 326 via the gas introduction pipe 3114 to the reaction vessel 311.
Install within 1. Next, mass flow controller 321
The raw material gases are adjusted so as to have a predetermined flow rate by 1 to 3216. At that time, the pressure in the reaction vessel 3111 is 1
The vacuum gauge 3119 is set to a predetermined pressure equal to or lower than Torr.
While watching, adjust the opening of the main valve 3118. When the internal pressure stabilizes, the RF of frequency 13.56 MHz
A power source (not shown) is set to a desired power, and R is inserted into the reaction vessel 3111 through the high frequency matching box 3115.
F power is introduced to cause glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 3112. After the desired film thickness is formed, the supply of RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, 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. When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is supplied into the reaction vessel 3111 and outflow valve 3251.
Outflow valves 3251 to 3256 to avoid remaining in the piping from
Is closed, the auxiliary valve 3260 is opened, the main valve 3118 is fully opened, and the system is once evacuated to a high vacuum as required. To achieve uniform film formation,
During the formation of the layer, it is also effective to rotate the support 3112 at a predetermined speed by a driving device (not shown). Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

On the other hand, the development of the deposited film forming apparatus shown in FIG. 4 which is capable of forming a plurality of photoconductors at the same time and has a very high productivity is being actively promoted. FIG. 4A is a schematic cross-sectional view, and FIG. 4B is a schematic cross-sectional view along the cutting line BB ′ in FIG. An exhaust pipe 404 is integrally formed on a side surface of the reaction vessel 401, and the other end of the exhaust pipe 404 is connected to an exhaust device (not shown). Waveguides 403 are attached to the upper surface and the lower surface of the reaction vessel 401, respectively.
Is connected to a microwave power supply (not shown). A dielectric window 402 is hermetically sealed at an end of each waveguide 403 on the side of the reaction vessel 401. Six 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. There is a space surrounded by the cylindrical substrate 405 and each dielectric window 402 in the reaction vessel 401, and this space becomes a film formation space 406. In addition, a raw material gas introduction pipe 451 is provided in a gap between two adjacent cylindrical substrates 405. The source gas introduction pipe 351 is used to form the source gas into a film blank 406.
It is supposed to be introduced in.

When manufacturing an electrophotographic photoreceptor using this apparatus, first, the inside of the reaction vessel 401 is set to 10 ^-7 Torr.
The air is evacuated to the following temperature, and then the cylindrical body 405 is heated and maintained at a desired temperature by the heating element 407. Then, the source gas is introduced into the reaction vessel 401 via the source gas introduction pipe 451. Simultaneously with this, a microwave having a frequency of 500 MHz or more, preferably 2.45 GHz, is applied to the waveguide 4.
03. The light enters the reaction vessel 401 through the dielectric window 402. As a result, a glow discharge occurs in the film formation space 406, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 405. At this time, by rotating the motor 409, a deposited film can be formed over the entire circumference of the cylindrical substrate 405.

[0010]

A good a-Si type photoreceptor is formed by the above-mentioned conventional apparatus and method. However, in order to respond to the high demands in the current market, further techniques are required. Improvement is needed. Specific examples include further reduction of image defects, reduction of afterimage phenomenon on an electrophotographic image called optical memory, reduction of cost, and the like. In the optical memory, the latent image formed during the previous copy is not completely erased by the next copy, and the previous copy image is slightly formed on the next copy image.
In order to improve the electrophotographic image characteristics and reduce the cost, further development of a-Si based photoreceptor manufacturing technology, particularly a-Si film forming technology, is indispensable. Regarding the a-Si film forming technique, many innovations and improvements have been made for the purpose of various applications, not limited to the photoconductor, and the technique has been steadily improved every day. For example, one of the things that has been attracting attention in recent years is VH using high frequency power in the VHF band.
There is an F plasma CVD (hereinafter abbreviated as "VHF-PCVD") method. Since the VHF-PCVD method has a high film deposition rate and can obtain a high-quality a-Si film, it is expected that cost reduction and quality improvement of products can be achieved at the same time, and various product manufacturing using this Law development is enthusiastic.

However, when this VHF-PCVD method is used for forming an a-Si type photoreceptor, there is a problem to be solved. When the cost reduction of the a-Si photosensitive member formation by the VHF-PCVD method is considered, the apparatus configuration is the same as that of the MW-PCVD method. For example, a plurality of cylindrical substrates as shown in FIG. A device configuration that is installed above and that applies high-frequency power to the discharge space surrounded by the cylindrical substrate is effective. In such an apparatus configuration, not only is it possible to manufacture a plurality of photoconductors at the same time, but most of the active species decomposed in the film formation space are deposited on the cylindrical substrate, so the raw material gas utilization efficiency is improved. The high cost also contributes to cost reduction of the product. In this device configuration, when an attempt is made to deposit a film of the same quality on all of a plurality of cylindrical substrates, the method of supplying the source gas is to provide a plurality of gas supply means on concentric circles, or to use an electrode installed at the center. A method of supplying the raw material gas from the surface can be considered. In the case of the method of providing a plurality of gas supply means on the concentric circles, if the gas supply means are too close to the high frequency electrode, there arises a problem that the plasma becomes nonuniform and destabilized. On the other hand, in order to suppress such non-uniformity and destabilization of plasma, the gas supply means and the cylindrical substrate come close to each other when they are moved away from the high-frequency electrode. Therefore, they are separated from the surface of the source gas supply means during film deposition. The film easily adheres to the surface of the cylindrical substrate, making it difficult to suppress image defects in the a-Si-based photoreceptor. On the other hand, in the case of the method of supplying the raw material gas from the electrode surface installed in the center, the above-mentioned inhomogeneity and instability of plasma do not occur, and the gas supply section is a cylindrical substrate. Since there is no proximity, the problem of image defects is solved. A configuration similar to this is MW-P
The CVD method is proposed in, for example, Japanese Unexamined Patent Publication No. 3-219081. In this publication, a bias electrode for applying an electric field is provided in the center of the film formation space, and gas is supplied from the surface of the bias electrode.
It is disclosed that an —Si-based photoreceptor can be formed.

The present inventor also conducted a study to achieve high film quality and cost reduction while suppressing image defects by supplying gas from the electrode surface in the VHF-PCVD method as described above. However, as a result, VH
In the F-PCVD method, if the gas is supplied from the gas supply port opened on the electrode surface, the characteristics at the portion corresponding to the position of the gas supply port on the formed a-Si-based photosensitive member will be unsatisfactory. It became clear that it would be sufficient. It is presumed that such a difference from the MW-PCVD method is caused by the difference in the role and action of the electrode. M
In the W-PCVD method, decomposition of raw material gas is performed by microwave energy supplied from a waveguide or the like. The bias electrode installed in the film forming space acts to apply an electric field between the plasma and the substrate, but does not substantially contribute to the decomposition of the source gas. On the other hand, in the VHF-PCVD method, the source gas is decomposed by the high frequency power radiated from the electrodes. That is, in the MW-PCVD method, even when the gas is supplied from the surface of the bias electrode, the source gas decomposition energy supply section and the source gas supply section are separate, whereas in the VHF-PCVD method, the source gas decomposition is performed. The energy supply section and the source gas supply section are the same part. As a result, when gas is supplied from the electrode surface, the decomposition process of the source gas in the vicinity of the electrode, which is both the energy supply source and the source gas supply source in the VHF-PCVD method, becomes completely different locally. ,
It is considered that the characteristics of the deposited film will be greatly changed. Therefore, in the VHF-PCVD method, in order to supply gas from the electrode surface, it is important to find a new electrode configuration considering these points.

Therefore, the present invention solves the problems in the above-mentioned conventional ones, suppresses the non-uniformity of the characteristics on the photoconductor, reduces the optical memory over the entire area, and suppresses the image defects. It is an object of the present invention to provide an apparatus and a method for manufacturing an amorphous silicon-based photosensitive member, which can manufacture the amorphous silicon-based photosensitive member having excellent electrophotographic characteristics at low cost.

[0014]

In order to solve the above problems, the present invention comprises an apparatus and method for manufacturing an amorphous silicon type photosensitive member as follows. That is, the amorphous silicon-based photoreceptor manufacturing apparatus of the present invention has a plurality of cylindrical substrates arranged in a reaction vessel that can be vacuum-tight so as to surround the film formation space, and at least the source gas in the film formation space. A supply means and a high-frequency power introduction means, and by introducing high-frequency power in the VHF band from the high-frequency power introduction means into the raw material gas supplied from the raw material gas supply means, a glow discharge is generated in the film formation space; In the apparatus for manufacturing an amorphous silicon-based photoconductor by a plasma CVD method for forming a deposited film on the substrate, the raw material gas supply means reacts the raw material gas from a gas ejection port provided on the surface of the high frequency power introducing means. It is characterized in that it has a structure for supplying it into the film forming space of the container, and a shield for scattering the source gas is provided outside the gas ejection port. Further, according to the method for producing an amorphous silicon-based photosensitive member of the present invention, the raw material gas supply means supplies the film to the film forming space surrounded by the plurality of cylindrical substrates in the reaction container that can be vacuum-tight. A high frequency power of VHF band is introduced into the source gas by a high frequency power introduction means to cause glow discharge in the film forming space to form a deposited film on the substrate. In the manufacturing method, the raw material gas is supplied from the raw material gas supply means through a gas jet port provided on the surface of the high-frequency power introducing means, and the raw material gas is provided by a shield provided outside the gas jet port. The feature is that it is made to scatter. Further, in the present invention, the shield has an inscribed circle radius of an inscribed circle of the shield whose size passes through the gas ejection port center and has a central axis perpendicular to the high-frequency electrode. It is preferable that the maximum value R of R is set to R ≧ 3r with respect to the circumscribed circle radius r of the gas ejection port. Further, the shield has an inscribed circle having a maximum radius R among the inscribed circles of the shield passing through the center of the gas ejection port and having a central axis perpendicular to the high frequency electrode, and the gas ejection port. Minimum distance a
However, it is preferable to install in the range of a ≦ 2R. Also, the VH
The high frequency power in the F band has a frequency of 20 MHz to 450
MHz, preferably 50 MHz to 45 MHz
More preferably, it is 0 MHz.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention, which has the above-described structure, can achieve high-speed film formation and high film quality, which are features of the VHF-PCVD method, while suppressing image defects. The a-Si electrophotographic photosensitive member having excellent electrophotographic characteristics can be manufactured at low cost to achieve the above-mentioned object of the present invention, which was studied by the present inventors. As a result, if only the structure in which the gas ejection port is provided on the electrode surface is formed,
-Based on the finding that such local deterioration is caused by the sheath formed on the surface of the high-frequency electrode, in view of insufficient characteristics in the portion corresponding to the gas supply port position on the Si-based photosensitive member. Is. The mechanism by which the above-described results are obtained in the present invention is considered to be roughly as follows. In the case of the structure in which the gas ejection port is simply provided on the electrode surface, the characteristics at the portion corresponding to the gas supply port position on the a-Si based photosensitive member formed as described above become insufficient. As a result of various studies on the cause, the present inventor has come to judge that such local deterioration is caused by the sheath formed on the surface of the high frequency electrode. When a plurality of cylindrical substrates are arranged so as to surround the film formation space, the cathode area (high-frequency electrode surface area) becomes smaller than the anode area (area of the cylindrical substrate in contact with plasma). Therefore, a large potential difference occurs in the sheath on the surface of the high frequency electrode. Although the value changes depending on the discharge conditions, a potential difference of about 150 to 250 V was confirmed in the study by the present inventors. Due to such a large potential difference, some of the ions in the plasma are accelerated in the sheath,
While becoming high-energy ions, they enter the cathode surface. The ions that have reached the cathode surface cause secondary electrons to be emitted from the cathode surface by the secondary electron emission effect, and these secondary electrons become high-energy electrons while being accelerated in the sheath toward the plasma. On the other hand, the gas ejected from the gas ejection port has a locally high density near the ejection port, that is, near the sheath. In this situation, there are high-energy ions and high-energy electrons,
Under high gas density conditions, the gas is easily decomposed. In addition, a so-called secondary reaction in which the decomposed active species further react with each other is actively performed. As a result, a reaction different from that in the plasma bulk proceeds in the vicinity of the gas ejection port, and different active species are generated. Therefore, a-Si
Even if the conditions for forming the system photoconductor are optimized, it is difficult to optimize the reaction in the vicinity of the gas ejection port. Therefore, in VHF-CVD, when a plurality of cylindrical substrates are arranged so as to surround the film forming space and gas is supplied from the gas supply port opened on the electrode surface, the formed a- It is considered that the characteristic becomes insufficient in the portion corresponding to the gas supply port position on the Si-based photoconductor.

In the conventional MW-PCVD method, good characteristics of a-Si type photoconductor can be obtained with a similar structure.
In the PCVD method, the source gas is decomposed by microwaves, and the bias electrode is for applying an electric field. Therefore, the applied power is small and the potential difference at the sheath portion formed on the electrode surface is as low as about 10 to 50 V. It is considered to be a thing. In the present invention, since the shielding material for scattering the raw material gas is installed outside the gas ejection port, the gas density is locally high and there is no region where high-energy electrons / ions exist as described above. In the present invention, there is a region where the gas density is high locally until the gas ejected from the gas ejection port reaches the shield, but in this region, the shield prevents the incidence of high-energy ions from the plasma. Since it is prevented, the condition that the gas density is high and the high-energy ions and electrons are present is not satisfied. Further, outside the shield, high energy ions are incident from the plasma, but the gas density is low because the gas is scattered by the shield. As described above, in the present invention, since the gas density is high and there is no region where high-energy ions / electrons are present, the local gas decomposition and the progress of the secondary reaction as described above do not occur, and the entire region is uniform. Film formation is performed.

The contents of the present invention will be described in detail below with reference to the drawings. FIG. 1 (a) shows an example of a high-frequency electrode that also serves as a gas supply means that can be used in the present invention. In the figure, 101 is a high-frequency electrode also serving as a gas supply path, 1
Reference numeral 02 is a shield, 103 is a shield support, and 104 is a gas ejection port. The high frequency electrode 101 may be formed of a conductive material, the surface of an insulating material may be coated with a conductive material, or the surface of a conductive material may be coated with an insulating material. At that time, the coating portion may be provided only on the inner surface, only on the outer surface, or on both sides. In addition, a conductive material and an insulating material may be formed in combination as long as high-frequency power is transmitted. As a typical material, a conductive material is Ti,
Ni, Au, Ag, Pt, Cu, W, Fe, Cr, A
1, SUS, Inconel, and the like, and examples of the insulating material include alumina, boron nitride, silicon carbide, silicon nitride, glass, and the like. The shield 102 may be a conductive material, an insulating material, or a combination thereof. Typical materials are Ti, Ni, Au, Ag, P
t, Cu, W, Fe, Cr, Al, SUS, Inconel, alumina, boron nitride, silicon carbide, silicon nitride,
Glass and combinations thereof. Shield 1
The shape of 02 is not particularly limited, but the gas ejection port 10
4 is shielded from the plasma, and needs to have a size large enough to scatter the gas ejected from the ejection port.

FIG. 1 (b) is a partial schematic view of a high-frequency electrode which also serves as a source gas supply means which can be used in the present invention. In FIG. 1B, the shield 102 is fixed to the high frequency electrode 101 by a shield support (not shown). The size of the shield 102 is such that the largest inscribed circle radius R of the inscribed circles of the shield 102 that passes through the center of the gas ejection port 104 and has a central axis perpendicular to the high-frequency electrode 101 is the gas ejection port 104. It is preferable to set R ≧ 3r for the circumscribed circle radius r. If the maximum value R of the radius of the inscribed circle of the shield 102 is smaller than this condition, the raw material gas ejected from the gas ejection port 104 will not be sufficiently scattered, and the position on the photoconductor corresponding to the gas ejection port 104 will be reduced. The characteristics will not be improved sufficiently. Also, the shield 1
Reference numeral 02 denotes a minimum distance a between the inscribed circle having the maximum radius R and the gas ejection port 104 among the inscribed circles of the shield 102 that passes through the center of the gas ejection port 104 and has a central axis perpendicular to the high frequency electrode. However, it is preferable to install in the range of a ≦ 2R. Gas spout 10
When the distance between 4 and the shield 102 is more than this, plasma circulates between the gas jet 104 and the shield 102, and the characteristic improvement at the position on the photoconductor corresponding to the gas jet 104 cannot be sufficiently performed. I will end up. The size and the number of the gas ejection ports 104 may be any size and number such that the source gas is uniformly supplied into the film formation space. The shield 102 must be provided for each gas ejection port.

The deposition film formation by the a-Si type photoconductor manufacturing apparatus using the present invention can be carried out by the following procedure. FIG. 2 is a schematic view showing an example of an a-Si-based photoconductor manufacturing apparatus that can be used in the present invention. In FIG. 2, 201 is a reaction vessel, 202 is a high-frequency electrode that also serves as a source gas supply means, 204 is an exhaust pipe integrally formed on the side surface of the reaction vessel 201, 205 is a cylindrical substrate, 206 is a film forming space, 207 is a heating element, 208
Is a rotating shaft, 209 is a motor, 210 is a reduction gear, 211
Is a high frequency matching box, and 212 is a high frequency power supply. In FIG. 2, the high-frequency electrode 202 is simply shown as a rod shape, but the configuration is such that the present invention can be achieved as shown in FIG. In the deposited film forming procedure using such an apparatus, first, the inside of the reaction vessel 201 is set to 10 ⁻⁷ T.
The gas is evacuated to or or less, and then the heating element 207 heats and holds the cylindrical substrate 205 at a desired temperature. And
Via the high-frequency electrode 202 which also serves as a source gas supply means,
Source gas is introduced into the reaction vessel 201. After confirming that the flow rate of the raw material gas has reached the set flow rate and the pressure inside the reaction vessel 201 has stabilized, high frequency power is supplied from the high frequency power supply 212 to the high frequency electrode 202 via the matching box 211. Film forming space 206 from the high-frequency electrode 202
The glow discharge is generated in the film formation space 206 by the high frequency power radiated to the source gas, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 205. At this time, by rotating the motor 209, a deposited film can be formed over the entire circumference of the cylindrical substrate 205. The layer structure of the a-Si-based photoconductor that can be produced using the present invention 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. FIG.
The electrophotographic photosensitive member 500 shown in FIG.
And a photoconductive layer 502 made of a-Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 503.
It is composed of The electrophotographic photosensitive member 500 shown in FIG. 5C is obtained by forming a-Si: H, X on the support 501.
And a photoconductive layer 502 having photoconductivity, an amorphous silicon-based surface layer 503, and an amorphous silicon-based charge injection blocking layer 504. FIG.
The electrophotographic photosensitive member 500 shown in FIG.
A photoconductive layer 502 is provided thereon. The photoconductive layer 502 is composed of a charge generation layer 505 made of a-Si: H, X and a charge transport layer 506, and an amorphous silicon based surface layer 503 is provided thereon.

The support for the photoreceptor may be either conductive or electrically insulating. As the conductive support, Al,
Cr, Mo, Au, In, Nb, Te, V, Ti, P
Examples include metals such as t, Pd, and Fe, and alloys thereof, for example, stainless steel. Also, polyester, polyethylene, polycarbonate, cellulose acetate,
Polypropylene, polyvinyl chloride, polystyrene, polyamide or other synthetic resin film or sheet, glass,
A support in which at least the surface on the side on which the light receiving layer is formed of an electrically insulating support such as ceramic is subjected to a conductive treatment can also be used. The shape of the support 501 may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and its thickness is appropriately determined so that the electrophotographic photosensitive member 500 can be formed as desired. , Electrophotographic photoreceptor 5
When flexibility as 00 is required, the support 50
It can be made as thin as possible within the range in which the function of 1 can be sufficiently exhibited. However, the support 501 is usually 1 in terms of production, handling, mechanical strength and the like.
It is set to 0 μm or more.

The photoconductive layer 502 in the present invention is formed on the support 501 by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Photoconductive layer 5
To form 02, basically silicon atoms (Si)
Gas for supplying Si capable of supplying hydrogen and hydrogen atoms (H)
A raw material gas for H supply or / and a raw material gas for X supply capable of supplying a halogen atom (X) are introduced in a desired gas state into a reaction vessel whose inside can be reduced in pressure,
Glow discharge is generated in the reaction container, and aS is placed on a predetermined support 501 which is installed at a predetermined position in advance.
i: A layer composed of H and X is formed. In addition, the photoconductive layer 5
02 must contain a hydrogen atom and / or a halogen atom, in order to compensate the dangling bonds of the silicon atom and improve the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable to.
Therefore, the content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 10 to 40 atom%, more preferably 15 to 25 atom% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. Is desirable. SiH is a substance that can serve as a gas for supplying Si.
4, Si2H6, Si3H8, Si4H10, and other gas-state or gasifiable silicon hydrides (silanes) are mentioned as being effectively used. Further, they are easy to handle during layer formation, and have good Si supply efficiency. In terms of SiH4, S
i2H6 is mentioned as a preferable thing. Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 502, and the introduction ratio of hydrogen atoms is controlled more easily, and in order to obtain good film characteristics, these gases are further added. It is also effective to mix a desired amount of H2 and / or He or a silicon compound gas containing a hydrogen atom to form a layer. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

Further, a material gas for supplying a halogen atom is preferably a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. To 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), BrF, ClF, ClF3, BrF3, BrF
5, interhalogen compounds such as IF3 and IF7 can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, silicon fluoride such as SiF4 or Si2F6 can be specifically mentioned as a preferable example. Photoconductive layer 502
In order to control the amount of hydrogen atoms and / or halogen atoms contained therein, for example, the temperature of the support 501, introduction of the raw material used for containing hydrogen atoms and / or halogen atoms into the reaction vessel The amount of discharge, the discharge power, etc. may be controlled. It is preferable that the photoconductive layer 502 contain atoms for controlling conductivity as necessary. The atoms that control the conductivity may be contained in the photoconductive layer 502 in a uniformly distributed state, or may be contained in the layer thickness direction in a non-uniform distribution state. Is also good.

Examples of the atoms that control 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 characteristics (hereinafter abbreviated as “IIIb group atom”) or an atom belonging to Group Vb of the Periodic Table giving n-type conduction characteristics (hereinafter “V
(abbreviated as “group b atom”) can be used. IIIb
As the group atoms, specifically, boron (B), aluminum (Al), gallium (Ga), indium (In),
There are thallium (Tl) and the like, and B, Al and Ga are particularly preferable. As the group Vb atom, specifically, phosphorus (P),
Arsenic (As), antimony (Sb), bismuth (Bi)
And P and As are particularly preferable. Photoconductive layer 502
As the content of atoms controlling conductivity contained in,
It is preferably 1 × 10 ^-2 to 1 × 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ^-1 to 1 × 10 ³ atomic ppm. Is desirable. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group material for introducing a group Vb atom may be used in forming a layer. The raw material may be introduced in a gaseous state into the reaction vessel together with another gas for forming the photoconductive layer 502.

As a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom,
It is desirable to employ one that is gaseous at normal temperature and normal pressure or that can be easily gasified at least under layer forming conditions. As the raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B2H6, B4H10,
B5H9, B5H11, B6H10, B6H12, B6
Examples thereof include boron hydride such as H14, boron halide such as BF3, BCl3, and BBr3. In addition, AlCl
3, GaCl3, Ga (CH3) 3, InCl3, Tl
Other examples include Cl3 and the like. What is effectively used as a raw material for introducing a Group Vb atom is phosphorus hydride such as PH3, P2H4, PH4I, P for introducing a phosphorus atom.
F3, PF5, PCl3, PCl5, PBr3, PBr
5, phosphorus halides such as PI3 can be mentioned. In addition, A
sH3, AsF3, AsCl3, AsBr3, AsF
5, SbH3, SbF3, SbF5, SbCl3, Sb
Cl5, BiH3, BiCl3, BiBr3, etc. are also Vb
It can be cited as an effective starting material for introducing a group atom. Further, these raw material substances for atom introduction for controlling conductivity may be diluted with H2 and / or He as necessary and used.

Further, it is effective that the photoconductive layer 503 contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 1 with respect to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms.
0 atomic%, more preferably 1 × 10 ⁻⁴ to 8 atomic%, most preferably 1 × 10 ^{−3 to} 5 atomic%. Carbon atoms and / or
Alternatively, oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the photoconductive layer, or may have a non-uniform distribution in which the content changes in the thickness direction of the photoconductive layer. There may be. The layer thickness of the photoconductive layer 502 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and is preferably 1 to 100 μm.
m, more preferably 20-50 μm, optimally 23-4
It is desirable that the thickness be 5 μm. In order to form the photoconductive layer 502 having desired film characteristics, it is necessary to appropriately set the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the support temperature. is there.

The flow rate of H2 and / or He used as the diluent gas is appropriately selected in accordance with the layer design. Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
^{-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 temperature of the support and the gas pressure for forming the photoconductive layer include the above-mentioned ranges, but the conditions are usually not independently determined separately, and the light-receiving member having desired characteristics It is desirable to determine the optimal value based on the mutual and organic relationships to form.

As the surface layer in the present invention, it is preferable to further form an amorphous silicon type surface layer 503 on the photoconductive layer 502 formed on the support 501 as described above. 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-based material. For example, amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) and further containing carbon atoms ( Hereinafter, "a-SiC:
H, X ”), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing an oxygen atom (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 referred to as “a-SiN: H, X”),
Amorphous silicon containing a hydrogen atom (H) and / or 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-SiC”).
ON: H, X ") and the like are preferably used.

The surface layer 503 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions 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 source gas for supplying Si that can supply silicon atoms (Si) and a gas for supplying C that can supply carbon atoms (C) are basically used. A raw material gas and a raw material gas for supplying H that can supply hydrogen atoms (H) or / and a raw material gas for X supply that can supply halogen atoms (X) are placed in a reaction vessel capable of reducing the pressure inside a desired reaction vessel. Introduced in a gaseous state, a glow discharge is generated 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. The material of the surface layer may be any amorphous material containing silicon, but at least one element selected from carbon, nitrogen and oxygen may be used.
A compound with a silicon atom containing at least one
It is preferable to use iC as a main component.

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. In addition, the surface layer 5
It is necessary to contain a hydrogen atom and / or a halogen atom in 03, which compensates for dangling bonds of a silicon atom and improves the layer quality, especially the photoconductive property and the charge retention property. Is important for. In general, the hydrogen content is desirably 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic%, based on the total amount of the constituent atoms. In addition, the content of fluorine atoms is usually 0.01 to 15 atomic%, preferably 0.1 to 15 atomic%.
It is desirable that the content be 1 to 10 atomic%, optimally 0.6 to 4 atomic%.

As a substance which can be a gas for supplying silicon (Si) used in forming the surface layer, SiH is used.
4, Si2H6, Si3H8, Si4H10, and other gas-state or gasifiable silicon hydrides (silanes) are mentioned as being effectively used. Further, they are easy to handle during layer formation, and have good Si supply efficiency. In terms of SiH4, S
i2H6 is mentioned as a preferable thing. In addition, if necessary, H2, He, and
It may be used after being diluted with a gas such as Ar or Ne. CH4 and C2H are substances that can be used as carbon supply gas.
6, C3H8, C4H10, etc. in a gas state or a gasifiable hydrocarbon are effectively used, and CH4 and C2H6 are more preferable in terms of ease of handling during layer formation, good Si supply efficiency and the like. It is mentioned as a preferable one. In addition, these raw material gases for supplying C may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. As substances that can be used as nitrogen or oxygen supply gas, NH3, NO, N2O, NO2, O2, C
A compound in a gas state such as O, CO2, N2 or the like which can be gasified is mentioned as being effectively used. In addition, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. In order to further facilitate the control of the introduction ratio of hydrogen atoms introduced into the surface layer 503 to be formed, a hydrogen gas or a silicon compound gas containing hydrogen atoms is also added to these gases in a desired amount. It is preferable to form a layer by mixing. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

As a source gas for supplying a halogen atom, a gaseous or gasizable halogen compound such as a halogen gas, a halide, an interhalogen compound containing a halogen, a silane derivative substituted with a halogen, or the like is preferably mentioned. . 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 in the present invention include fluorine gas (F2), BrF, ClF, ClF3, BrF3,
There may be mentioned interhalogen compounds such as BrF5, IF3 and IF7. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom,
Specifically, for example, silicon fluoride such as SiF4 and Si2F6 can be mentioned as a preferable example. Surface layer 5
In order to control the amount of hydrogen atoms and / or halogen atoms contained in 03, for example, the temperature of the support 501, into the reaction vessel of the raw material used to contain hydrogen atoms and / or halogen atoms, The amount to be introduced, discharge power, etc. may be controlled. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the surface layer, or may have a non-uniform distribution such that the content changes in the thickness direction of the surface layer. There may be a part.

Further, it is preferable that the surface layer 503 contains atoms for controlling conductivity, if necessary. The atoms for controlling the conductivity may be contained in the surface layer 503 in a state of being uniformly distributed without unevenness, or even if there is a part contained in the layer thickness direction in a non-uniform distribution state. Good. Examples of the atom that controls the conductivity include so-called impurities in the field of semiconductors, and an atom that belongs to Group IIIb of the periodic table that gives p-type conductivity (hereinafter abbreviated as “Group IIIb atom”). Alternatively, an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) which imparts n-type conductivity can be used. Specific examples of the group IIIb atom include boron (B) and aluminum (A
1), gallium (Ga), indium (In), thallium (Tl), and the like, and B, Al, and Ga are particularly preferable. Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, with P and As being particularly preferable. The content of the atoms controlling the conductivity contained in the surface layer 503 is preferably 1 × 10 ⁻³ to 1 × 10 ³ atom ppm, more preferably 1 × 10 ^{−2 to} 5 × 10 ² atom ppm, Optimally 1 x 1
It is desirable that the concentration be 0 ⁻¹ to 1 × 10 ² atomic ppm. To structurally introduce a conductivity controlling atom, for example, a Group IIIb atom or a Group Vb atom, during the layer formation,
A raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom is placed in a gas state in a reaction vessel, and a surface layer 50 is formed.
It may be introduced together with other gas for forming 3. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at ordinary temperature and normal pressure or a substance which can be easily gasified at least under layer forming conditions is employed. It is desirable. As the raw material for introducing such a group IIIb atom, specifically, for introducing a boron atom, B2H6, B4H10, B5H
9, B5H11, B6H10, B6H12, B6H14
And borohydrides such as BF3, BCl3, and BBr3. In addition, AlCl3, Ga
Other examples include Cl3, Ga (CH3) 3, InCl3, TlCl3 and the like.

As a raw material for introducing a group Vb atom, PH3 for introducing a phosphorus atom is effectively used.
Phosphorus hydride such as P2H4, PH4I, PF3, PF5, P
Examples thereof include phosphorus halides such as Cl3, PCl5, PBr3, PBr5 and PI3. In addition, AsH3, AsF
3, AsCl3, AsBr3, AsF5, SbH3, S
bF3, SbF5, SbCl3, SbCl5, BiH
3, BiCl3, BiBr3 and the like can also be mentioned as effective starting materials for introducing a Group Vb atom. In addition, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H2, He, Ar, Ne or the like, if necessary. As the layer thickness of the surface layer 503,
It is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the light receiving member, and the thickness is 3 μm.
If it exceeds m, a decrease in electrophotographic characteristics such as an increase in residual potential is observed.

The surface layer 503 is carefully formed to provide its desired properties as desired. That is,
The material containing Si, C and / or N and / or O, H and / or X as a constituent element takes a form from crystalline to amorphous depending on its forming condition, and from electrical property to semiconductor from electrical property. In the present invention, a compound having desired properties according to the purpose is formed, since the properties between the properties and the insulating properties and the properties between the photoconductive properties and the non-photoconductive properties are shown. As such, the choice of the formation conditions is strictly made as desired. For example, to provide the surface layer 503 mainly for the purpose of improving the pressure resistance,
It is made as a non-single-crystal material with a remarkable electrical insulating behavior in the use environment. When the surface layer 503 is provided for the purpose of mainly improving the continuous repetitive use characteristics and the use environment characteristics, the degree of the above-mentioned electrical insulation is alleviated to some extent, and a certain sensitivity to the irradiated light is obtained. Is formed as a non-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 as desired. The temperature (Ts) of the support 501 is appropriately selected according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 2
It is desirable that the temperature is 30 to 330 ° C, most preferably 250 to 300 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 1 × 10 ^{−4 to} 10 Torr, more preferably 5 ×.
10 ^{-4 to 5} Torr, optimally 1 × 10 ^{-3 to} 1 Torr
It is preferred that The support temperature for forming the surface layer, the above-mentioned range as a desirable numerical range of the gas pressure are mentioned, but the conditions are not usually independently determined separately, and a light-receiving member having desired properties is usually used. It is desirable to determine the optimum value based on the mutual and organic relationships to form. Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms continuously decreases toward the photoconductive layer 502 may be provided between the surface layer 503 and the 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.

In the present invention, if necessary, a charge injection blocking layer 504 having a function of blocking injection of charges from the conductive support side may be provided between the conductive support and the photoconductive layer. . 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 impart such a function, the charge injection blocking layer 504
Contains relatively more atoms for controlling the conductivity than the photoconductive layer. The conductivity-controlling atoms contained in the layer may be evenly distributed in the layer, or may be uniformly distributed in the layer thickness direction but unevenly distributed. There may be a portion contained in the state of being. 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 the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the properties uniform in the in-plane direction.

As the atoms contained in the charge injection blocking layer 504 for controlling the conductivity, there are so-called impurities in the field of semiconductors, and the atoms belonging to Group IIIb of the periodic table which give the p-type conduction characteristics (hereinafter referred to as “atoms”). (Abbreviated as "Group IIIb atom") or Vb of the periodic table giving n-type conduction characteristics
An atom belonging to the group (hereinafter abbreviated as “Group Vb atom”) can be used. Specific examples of Group IIIb atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), and Ta (thallium), and B, Al, and Ga are particularly preferable. is there. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth) and the like.
As is preferred.

The content of the atoms for 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, most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm. Further, the charge injection blocking layer 504 has carbon atoms,
By including at least one of a nitrogen atom and an oxygen atom, it is possible to further improve the adhesion with another layer provided in direct contact with the charge injection blocking layer 504. The carbon atoms, nitrogen atoms, or oxygen atoms contained in the layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the layer thickness direction, but may be unevenly distributed. There may be a portion contained in a distributed state. However, in any case, it is necessary to uniformly contain the particles in the in-plane direction parallel to the surface of the support from the viewpoint of making the properties uniform in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire layer region of the charge injection blocking layer 504 is appropriately determined so that the object of the present invention can be effectively achieved. However, in the case of one kind, the amount thereof, and in the case of two or more kinds, the sum thereof, preferably 1 × 10 ⁻³
-50 at%, more preferably 5 x 10 ^-3 to 30 at%,
Most preferably, it is 1 × 10 ⁻² to 10 atomic%. In addition, 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 film quality. Charge injection blocking layer 5
The content of the hydrogen atom or the halogen atom or the sum of the hydrogen atom and the halogen atom in No. 04 is preferably 1 to 50 atomic%, more preferably 5 to 40 atomic%, and most preferably 10 to 30 atomic%.
It is desirable to set it at atomic%. The thickness of the charge injection blocking layer 504 is preferably 0.1 to 5 μm, more preferably 0.3 to 4 μm, and most preferably 0.5 from the viewpoints of obtaining desired electrophotographic characteristics and economic effects. It is desirable that the thickness be 3 μm. To form the charge injection blocking layer 504, a vacuum deposition method similar to the above-described method of 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 diluting gas H2 and / or He is appropriately selected in accordance with the layer design, but H2 and / or He is 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 gas pressure inside the reaction vessel is appropriately selected in accordance with the layer design, but in the usual case, it is 1 × 10 ^{−4 to} 10 Tor.
r, preferably 5 × 10 ^{−4 to} 5 Torr, optimally 1 ×
It is preferably 10 ^{−3 to 1} Torr. A mixing ratio of a diluent gas for forming the charge injection blocking layer 504, a gas pressure,
Although the above-mentioned ranges are mentioned as desirable numerical ranges of the discharge power and the substrate temperature, these layer forming factors are not usually independently determined separately, but they are mutually dependent to form a surface layer having desired characteristics. It is desirable to determine the optimum value of each layer formation factor based on the physical and organic relationships. 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, Si3N4, SiO2, SiO, or a silicon atom is used as a base material, and a hydrogen atom and / or a halogen atom. An adhesion layer composed of an amorphous material containing atoms and carbon atoms and / or oxygen atoms and / or nitrogen atoms may be provided. Further, a light absorption layer may be provided to prevent the occurrence of an interference pattern due to the reflected light from the support.

[0042]

The present invention will be described in more detail with reference to experimental examples and examples, but the present invention is not limited to these. (Experimental Example 1) Using the electrophotographic photoconductor manufacturing apparatus shown in FIG. 2, the electrode having the structure shown in FIG.
The oscillation frequency of the high frequency power source 212 is set to 1 on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm.
3.56MHz, 20MHz, 50MHz, 100MH
z, 250 MHz, 450 MHz, and 600 MHz were changed to prepare a photoreceptor including a charge injection blocking layer, a photoconductive layer, and a surface layer under the conditions shown in Table 1. However, 14MHz, 2
With respect to 0 MHz, it was impossible to generate a discharge with the internal pressure shown in Table 1, so that the charge injection blocking layer was 150 mTorr,
Photoconductive layer is 200mTorr, surface layer is 300mTorr
r. The electrode is tubular with a total length of 400 mm and has a wall thickness of 1.
It is made of 0 mm SUS304. The radius of 0.
Ten 5 mm gas ejection ports are provided at an interval of 4 cm in the axial direction of the electrode, and these are provided in three rows at intervals of 120 degrees in the circumferential direction. In addition, a cylindrical shield is provided outside the gas ejection port for each gas ejection port. The cylindrical shield is made of SUS304 with a radius of 5.0 mm and a height of 2.0 mm, and is installed so that its central axis passes through the center of the gas ejection port and is orthogonal to the central axis of the high frequency electrode. The cylindrical shield is made of SUS304, and is fixed on the high-frequency electrode by four shield supports having a diameter of 1 mm so that the distance between the gas ejection port and the cylindrical shield is 4.0 mm. The a-Si photoconductor manufactured under these conditions was installed in a Canon copying machine NP-6060 modified for this test, and the "chargeability unevenness", "sensitivity unevenness", and "optical memory unevenness" Three items were evaluated by the following specific evaluation methods. Charging ability unevenness: First, over a whole area in the photoconductor bus direction, the dark area potential at the developing device position when a constant current is applied to the main charger of the copying machine is measured, and the charging ability of each part is determined. . Next, the difference between the maximum value and the minimum value of the obtained charging ability of each part is obtained and evaluated based on the value. Sensitivity unevenness: After adjusting the main charger current so that the dark area potential at the developing device position becomes a constant value, the reflection density of 0.0
Using a predetermined white paper of 1 or less, the image exposure light amount when the image exposure light amount is adjusted so that the bright portion potential at the developing device position becomes a predetermined value is measured over the entire area in the photoreceptor generatrix direction. Evaluation is based on the difference between the value and the minimum value. Optical memory unevenness: After adjusting the current value of the main charger so that the dark area potential at the developing device position becomes a predetermined value, the image is adjusted so that the light area potential when a predetermined white paper is used as a document becomes the predetermined value. Adjust the amount of exposure light. In this state, a Canon ghost test chart (part number FY9-9040) with a black circle having a reflection density of 1.1 and a diameter of 5 mm attached to a document table, and a Canon halftone chart superimposed thereon. In the copied image, the optical memory is measured by measuring the difference between the reflection density of the black circle having a diameter of 5 mm and the reflection density of the halftone portion of the ghost chart recognized on the halftone copy. The optical memory is measured over the entire area in the photoconductor bus direction, and the optical memory unevenness is evaluated based on the difference between the maximum value and the minimum value. The evaluation result is shown in FIG. In the figure, it is shown that the smaller the unevenness in charging ability, the unevenness in sensitivity, and the unevenness in optical memory, the smaller the unevenness and the better. From this result, the frequency of the high frequency power is 20 to 45.
It was found that in the range of 0 MHz, uneven charging ability, uneven sensitivity, and uneven optical memory were improved, and the effects of the present invention were obtained. Particularly, a remarkable effect was confirmed in the range of 50 to 450 MHz.

[0043]

[Table 1] (Experimental Example 2) In the present invention, the following experiment was conducted in order to clarify how the radius of the gas ejection port installed on the electrode surface and the radius of the shield affect the characteristics of the produced photoconductor. . Using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 2, the electrode having the structure shown in FIG.
m, 0.75 mm, and 1.0 mm, and the radius of the SUS304 columnar shield was changed to 1 times, 2 times, 3 times, 5 times, and 10 times the radius of the gas ejection port, and the diameter was 108 mm. Fifteen photoconductors each including a charge injection blocking layer, a photoconductive layer, and a surface layer were formed on a cylindrical aluminum cylinder having a length of 358 mm under the conditions shown in Table 1. The electrode is a SUS3 tube with a total length of 400 mm and a wall thickness of 1.0 mm.
It is made of 04. The height of the cylindrical shield is 2.0 mm,
The center axis of the high-frequency electrode passes through the center of the gas ejection port and is orthogonal to the center axis of the high-frequency electrode. The distance between the columnar shield and the gas ejection port was set to 1 mm, and the number of gas ejection ports was adjusted so as to minimize the uneven charging ability under each condition. The oscillation frequency of the high frequency power source 212 is 100 MH.
z. A copying machine NP-6 made by Canon in which the a-Si photoconductor manufactured under such conditions is modified for this test.
It was installed in No. 060, and three items of "uniform charging ability", "uneven sensitivity" and "uneven optical memory" were evaluated by the same specific evaluation method as in Experimental Example 1. The evaluation result is shown in FIG. In the figure, it is shown that the smaller the unevenness in charging ability, the unevenness in sensitivity, and the unevenness in optical memory, the smaller the unevenness and the better. From this result, it has been clarified that the effect of the present invention is particularly remarkable when the radius of the gas scattering shield is three times or more the radius of the gas ejection port. In addition, the shape of the gas outlet was changed from a circle to a square, and the same experiment was conducted using the circumscribed circle radius of the square as the radius of the gas outlet. It was

(Experimental Example 3) As in Experimental Example 2, the shape of the gas scattering shield was a rectangular parallelepiped as shown in FIG. 8, and the relative position to the gas hole was asymmetrical as shown in FIG. The following experiments were conducted to clarify how the radius of the gas ejection port installed on the electrode surface and the size of the shield affect the characteristics of the produced photoconductor. In FIG. 8, reference numeral 801 is a high frequency electrode, 802 is a raw material gas ejection port,
Reference numeral 03 is a rectangular parallelepiped shield. In FIG. 8, R is a shield 803 that is perpendicular to the high-frequency electrode 801, has its center on a straight line 1 passing through the raw material gas ejection port 802, and is parallel to the high-frequency electrode 801.
Shows the radius of the inscribed circle. The inscribed circle having the radius R is in contact with three of the four surfaces of the rectangular parallelepiped parallel to the straight line l. The height d of the rectangular parallelepiped was 3 mm. Using the electrophotographic photoconductor manufacturing apparatus shown in FIG. 2 and using the electrode having the structure shown in FIG. 1 as the high frequency electrode, the radius of the gas ejection port installed on the electrode surface was 1.0 mm, and a SUS304 rectangular parallelepiped shield was used. Figure 8
The size of the medium radius is 1 time, 2 times, 3 times, 5 times the radius of the gas ejection port.
Double, 10 times, diameter 108mm, length 358
Five photoconductors each including a charge injection blocking layer, a photoconductive layer, and a surface layer were prepared on a cylindrical aluminum cylinder of mm under the conditions shown in Table 1. The electrode is made of SUS304 with a total length of 400 mm and a wall thickness of 1.0 mm. The distance between the rectangular parallelepiped shield and the gas ejection port is 1 mm, and the number of gas ejection ports and the installation position are the gas ejection port diameter of Experimental Example 2 of 1.0 mm.
As in the case of The oscillation frequency of the high frequency power source 212 is 100 MHz. The a-Si photosensitive member manufactured under such conditions was installed in a Canon copier NP-6060 modified for this test in the same manner as in Experimental Example 2, and "charging ability unevenness" and "sensitivity unevenness" were set. , "Optical memory unevenness" were evaluated by the same specific evaluation method as in Experimental Example 2. FIG. 9 shows the evaluation results. In the figure, for comparison, the result of the gas ejection port radius of 1.0 mm in Experimental Example 2 is also shown. In the figure, uneven charging ability,
It is shown that the smaller the value of both the sensitivity unevenness and the optical memory unevenness, the smaller the unevenness and the better. From this result, the maximum value R of the radius of the inscribed circle of the shield which is centered on the straight line perpendicular to the high frequency electrode and passing through the center of the gas ejection port and parallel to the high frequency electrode is three times or more the radius of the gas ejection port. At times, it became clear that the effects of the present invention were particularly remarkable.

(Experimental Example 4) In the present invention, the following experiment was conducted in order to clarify how the distance between the shield and the gas ejection port affects the characteristics of the produced photoconductor. Using the electrophotographic photoconductor manufacturing apparatus shown in FIG. 2, the electrode having the structure shown in FIG. 1 was used as the high frequency electrode, and the radius of the gas ejection port installed on the electrode surface was 0.5 mm.
Radius of 304 cylindrical shield is 2.0mm, 3.0m
m, 4.0 mm, and shields for each
The distance between the gas outlets is set to a cylindrical shield radius of 0.5, 1,
2, 3, 5 times, diameter 108 mm, length 35
1 layer consisting of a charge injection blocking layer, a photoconductive layer and a surface layer on the 8 mm cylindrical aluminum cylinder under the conditions shown in Table 1.
Five photoconductors were produced. The electrode is made of SUS304 with a total length of 400 mm and a wall thickness of 1.0 mm. The height of the cylindrical shield is 2.0 mm, and it is installed so that its central axis passes through the center of the gas ejection port and is orthogonal to the central axis of the high-frequency electrode. The gas outlet is 10 in the axial direction of the high-frequency electrode.
They are provided at intervals of 4 cm, which is 12 in the circumferential direction.
Three rows are provided at 0 degree intervals. In addition, the high frequency power source 21
The oscillation frequency of 2 was 100 MHz. The a-Si photoconductor manufactured under such conditions was installed in a Canon copier NP-6060 modified for this test, and the "chargeability unevenness", "sensitivity unevenness", and "optical memory unevenness" The three items were evaluated by the same specific evaluation method as in Experimental Example 1. The evaluation result is shown in FIG. In the figure, it is shown that the smaller the unevenness in charging ability, the unevenness in sensitivity, and the unevenness in optical memory, the smaller the unevenness and the better. From this result, it has been clarified that the effect of the present invention is remarkably obtained when the distance between the gas scattering shield and the gas ejection port is not more than twice the radius of the shield. In addition, the shape of the gas outlet was changed from a circle to a square, and the same experiment was conducted using the circumscribed circle radius of the square as the radius of the gas outlet. It was

(Experimental Example 5) As in Experimental Example 4, the shape of the gas-scattering shield was a rectangular parallelepiped as shown in FIG. 8, and the relative position to the gas hole was asymmetrical as shown in FIG. The following experiment was conducted in order to clarify how the shield-gas jetting distance affects the characteristics of the produced photoconductor. In FIG. 8, reference numeral 801 denotes a high frequency electrode, 8
Reference numeral 02 is a raw material gas ejection port, and 803 is a rectangular parallelepiped shield. In FIG. 8, R indicates a radius of an inscribed circle of a shield 803 which is perpendicular to the high-frequency electrode 801, has its center on a straight line 1 passing through the raw material gas ejection port 802, and is parallel to the high-frequency electrode 801. The inscribed circle having the radius R is in contact with three of the four surfaces of the rectangular parallelepiped parallel to the straight line l. The height d of the rectangular parallelepiped was 3 mm. Using the electrophotographic photoconductor manufacturing apparatus shown in FIG. 2, the electrode having the structure shown in FIG. 1 was used as the high frequency electrode, and the radius of the gas ejection port installed on the electrode surface was 0.5 mm.
The size of R in Fig. 8 made of 304 rectangular parallelepiped shield is 4.0 m.
m, and the distance between the shield and the gas ejection port is 0.5, 1, 2 of the size of R in FIG. 8 of the rectangular parallelepiped shield made of SUS304.
The diameter is 108mm and the length is 358m.
A photoconductor including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 1 on a cylindrical aluminum cylinder of m. The electrode is made of SUS304 with a total length of 400 mm and a wall thickness of 1.0 mm. There are ten gas ejection ports arranged in the axial direction of the high-frequency electrode at intervals of 4 cm,
This is provided in three rows at 120 ° intervals in the circumferential direction. The oscillation frequency of the high frequency power source 212 is 100 MHz. The a-Si photosensitive member manufactured under the above conditions was installed in a Canon copier NP-6060 modified for this test in the same manner as in Experimental Example 4, and "uneven charging ability" and "uneven sensitivity" were set. , "Optical memory unevenness" were evaluated by the same specific evaluation method as in Experimental Example 4. FIG. 11 shows the evaluation results. For comparison, the results of the cylindrical shield radius of 4.0 mm of Experimental Example 4 are also shown in the figure for comparison. In the figure, it is shown that the smaller the unevenness in charging ability, the unevenness in sensitivity, and the unevenness in optical memory, the smaller the unevenness and the better. From this result, the distance between the shield and the gas outlet is perpendicular to the high-frequency electrode and is centered on a straight line passing through the center of the gas outlet, and the maximum value R of the maximum radius R of the inscribed circle of the shield parallel to the high-frequency electrode is 2 It has been revealed that the effect of the present invention is particularly remarkable when the amount is not more than twice.

[Example 1] Using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 2, an electrode having the structure shown in FIG. 1 was used as a high frequency electrode, and a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm was formed. Under the conditions shown in Table 2, a photoreceptor having a charge injection blocking layer, a photoconductive layer and a surface layer was prepared. The oscillation frequency of the high frequency power supply 212 was 450 MHz. The electrode has a cylindrical shape with a total length of 400 mm and a wall thickness of 1.0 mm
It is made of SUS304. 0.5mm radius on the electrode surface
10 gas ejection ports are provided at intervals of 4 cm, and three gas ejection ports are provided at 120 ° intervals in the circumferential direction. Further, a conical shield is provided outside the gas ejection port for each gas ejection port with its apex facing the gas ejection port side. The conical shield is a SU with a bottom radius of 5.0 mm and a height of 3.0 mm.
It is made of S304. The conical shield is made of SUS304 and is fixed by four shield supports having a diameter of 1 mm so that the central axis of the conical shield passes through the center of the gas ejection port and is orthogonal to the central axis of the high frequency electrode. The distance between the gas ejection port and the bottom surface of the conical shield was 5.0 mm. The a-Si photosensitive member manufactured under such conditions was set in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items were 5 items of "charging ability", "sensitivity", "optical memory", "image defect" and "total image characteristics", and each item was evaluated by the following specific evaluation methods. Charging ability: Measures the dark area potential at the developing device position when a constant current is applied to the main charger of the copying machine. Therefore,
The higher the dark area potential, the better the charging ability.
The charging ability was measured over the entire area of the photoreceptor in the bus line direction, and evaluated by the lowest potential in the dark area. Sensitivity: After adjusting the main charger current so that the dark portion potential at the developing device position becomes a constant value, use a predetermined white paper with a reflection density of 0.01 or less for the original and set the bright portion potential at the developing device position. The evaluation is performed based on the image exposure light amount when the image exposure light amount is adjusted to a predetermined value. Therefore, it is shown that the smaller the amount of image exposure light, 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 in the area. Optical memory: After adjusting the current value of the main charger so that the dark portion potential at the developing device position becomes a predetermined value, image exposure is performed so that the light portion potential when a predetermined white paper is used as a document becomes a predetermined value. Adjust the light intensity. In this state, a Canon ghost test chart (part number: FY9-9040) with a black circle having a reflection density of 1.1 and a diameter of 5 mm attached to a document table, and a Canon halftone chart superimposed thereon. The difference between the reflection density of the black circle having a diameter of 5 mm and the reflection density of the halftone portion of the ghost chart observed on the halftone copy was measured on the copied image. The optical memory measurement was performed over the entire area of the photoconductor in the generatrix direction, and the maximum reflection density difference was evaluated. Image defect ... Canon black chart (part number:
FY9-9073) placed on the platen and copied to obtain a copy image having a diameter of 0.2 mm within the same area.
The above white spots were counted and evaluated. Overall image characteristics: including image deletion, uneven image density, etc.
The copied image was judged comprehensively. Table 3 shows the evaluation results. Good results were obtained in any of the items, and according to the present invention, an a-Si type photoreceptor having excellent electrophotographic image characteristics such as optical memory, charging ability and image defects over the entire area of the electrophotographic image is provided. It was confirmed to be produced.

Comparative Example 1 In the high frequency electrode used in Example 1, the electrophotographic photosensitive member shown in FIG. 2 was prepared in the same manner as in Example 1 except that the conical shield and the shield support were removed. Using the manufacturing apparatus, a photoreceptor including a charge injection blocking layer, a photoconductive layer, and a surface layer was manufactured under the conditions shown in Table 2. VH
The oscillation frequency of the F power supply 212 is 450 M as in the first embodiment.
Hz. The manufactured a-Si photoreceptor used in Example 1 was modified for this test and a Canon copier NP-
It was installed at 6060 and the characteristics of the photoconductor were evaluated. The evaluation items were 5 items of "charging ability", "sensitivity", "optical memory", "image defect", 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. In any of the charging ability, the sensitivity, and the optical memory, a region with insufficient characteristics was generated at the position corresponding to the gas ejection port in the direction of the photoconductor bus, compared to other regions. 4 cm on halftone copy image
Streaky density unevenness occurred at intervals.

[0049]

[Table 2]

[0050]

[Table 3] Example 2 Using the electrophotographic photoconductor manufacturing apparatus shown in FIG. 2 and using the electrode having the structure shown in FIG. 1 as the high frequency electrode,
On a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm, a photoreceptor including a charge injection blocking layer, a photoconductive layer and a surface layer was prepared under the conditions shown in Table 4. The oscillation frequency of the high frequency power source 212 was 50 MHz. The electrode has a total length of 4
It is made of titanium with a tubular shape of 00 mm and a thickness of 1.0 mm. Eight gas outlets having a radius of 0.6 mm are provided at an interval of 5 cm on the electrode surface in the axial direction of the electrode, and three gas outlets are provided at intervals of 120 degrees in the circumferential direction. A columnar shield is provided outside the gas ejection port for each gas ejection port. The cylindrical shield has a bottom radius of 3.0 mm and a height of 1.0
mm made of Inconel. The cylindrical shield is made of Inconel and is fixed on the high-frequency electrode so that the central axis of the cylindrical shield passes through the center of the gas ejection port and is orthogonal to the high-frequency electrode central axis by four shield supports with a diameter of 1 mm. There is. The distance between the gas ejection port and the cylindrical shield was 3.0 mm. The a-Si photosensitive member manufactured under such conditions was set in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items were 5 items of "charging ability", "sensitivity", "optical memory", "image defect" 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. Good results were obtained in any of the items, and according to the present invention, an optical memory over the entire area of the electrophotographic image,
It was confirmed that an a-Si-based photoreceptor having excellent electrophotographic image characteristics such as chargeability and image defects was produced.

[Embodiment 3] The charge injection blocking layer was formed under the conditions shown in Table 4 in the same manner as in Embodiment 2 except that the distance between the gas ejection port and the cylindrical shield was 7.5 mm. A photoconductor including a photoconductive layer and a surface layer was prepared. The produced a-Si photoconductor was installed in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photoconductor were evaluated. Evaluation items are "chargeability", "sensitivity",
5 of "optical memory", "image defect", and "total image characteristics"
Each item was evaluated by the same specific evaluation method as in Example 1 as an item. Table 5 shows the evaluation results. Good results were obtained in all of the items, and the effect of the present invention was confirmed, but the effect of Example 2 was not obtained.

Comparative Example 2 In the high frequency electrode used in Example 2, the electrophotographic photosensitive member shown in FIG. 2 was prepared in the same manner as in Example 2 except that the cylindrical shield and the shield support were removed. Using the manufacturing apparatus, a photoreceptor including a charge injection blocking layer, a photoconductive layer and a surface layer was prepared under the conditions shown in Table 4. The produced a-Si photoconductor was installed in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photoconductor were evaluated. Evaluation items are "chargeability", "sensitivity",
5 of "optical memory", "image defect", and "total image characteristics"
Each item was evaluated by the same specific evaluation method as in Example 1 as an item. Table 5 shows the evaluation results. In any of the charging ability, the sensitivity, and the optical memory, a region with insufficient characteristics was generated at the position corresponding to the gas ejection port in the direction of the photoconductor bus, compared to other regions. Further, on the halftone copy image, streak-like density unevenness occurred at 5 cm intervals.

[0053]

[Table 4]

[0054]

[Table 5] [Embodiment 4] Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 2, the electrode having the structure shown in FIG.
On a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm, a photoreceptor including a charge transport layer, a charge generation layer and a surface layer was prepared under the conditions shown in Table 6. High frequency power supply 2
The oscillation frequency of 12 was 100 MHz. The electrode has a total length of 4
It is made of nickel with a tubular shape of 20 mm and a thickness of 1.0 mm. There are 6c gas outlets with a radius of 0.75mm on the electrode surface.
Seven pieces are provided at m intervals, and three rows are provided at 120 degree intervals in the circumferential direction. In addition, a hemispherical shield is provided outside the gas ejection port for each gas ejection port with the flat portion facing the film formation space side (the side opposite to the gas ejection port). The hemispherical shield is made of alumina with a bottom radius of 3.0 mm. The hemispherical shield is made of SUS304, so that the distance between the gas ejection port and the flat surface of the hemispherical shield is 4.0 mm by the four shield supports with a diameter of 1 mm, and the center of the flat surface of the hemispherical shield Is fixed on the high-frequency electrode so that a straight line connecting the center of the gas ejection port and the center of the gas ejection port is orthogonal to the central axis of the high-frequency electrode. The a-Si photosensitive member manufactured under such conditions was set in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items were 5 items of "charging ability", "sensitivity", "optical memory", "image defect" 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. Good results were obtained in any of the items, and according to the present invention, an optical memory over the entire area of the electrophotographic image,
It was confirmed that an a-Si-based photoreceptor having excellent electrophotographic image characteristics such as chargeability and image defects was produced.

[Embodiment 5] In the same manner as in Embodiment 4, except that the bottom radius of the hemispherical shield is 2.0 mm, the charge transport layer, the charge generation layer, and the charge transport layer are formed under the conditions shown in Table 6.
A photoconductor having a surface layer was prepared. Fabricated a-Si
Canon copier N with photoconductor modified for this test
It was installed in P-6060, and the characteristics of the photoconductor were evaluated. The evaluation items are 5 items of "chargeability", "sensitivity", "optical memory", "image defect", and "total image characteristics".
Each item was evaluated by the same specific evaluation method as in Example 1. Table 7 shows the evaluation results. Good results were obtained in all items, and the effect of the present invention was confirmed, but the effect of Example 4 was not obtained.

Comparative Example 3 The electrophotographic photoreceptor shown in FIG. 2 was prepared in the same manner as in Example 4 except that the hemispherical shield and the shield support were removed from the high frequency electrode used in Example 4. Using the manufacturing apparatus, a photoreceptor having a charge transport layer, a charge generation layer and a surface layer was prepared under the conditions shown in Table 6. The produced a-Si photoconductor was installed in a Canon copying machine NP-6060 modified for this test, and the characteristics of the photoconductor were evaluated. The evaluation items were 5 items of "charging ability", "sensitivity", "optical memory", "image defect" 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. In any of the charging ability, the sensitivity, and the optical memory, a region with insufficient characteristics was generated at the position corresponding to the gas ejection port in the direction of the photoconductor bus, compared to other regions. Further, streak-like density unevenness occurred at 6 cm intervals on the halftone copy image.

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

As described above, according to the present invention, the raw material gas is supplied from the raw material gas supply means through the gas jet port provided on the surface of the high frequency power introducing means, and the gas jet port is provided outside the gas jet port. By scattering the raw material gas by the shielding material provided in, the non-uniformity of characteristics on the photoconductor is suppressed, the optical memory is reduced over the entire area, image defects are suppressed, and other electrophotographic characteristics are also suppressed. A good amorphous silicon-based photoconductor can be manufactured at low cost. Further, in the present invention, it is possible to suppress the characteristic variation between the manufacturing lots of the formed amorphous silicon-based photosensitive member, and further improve the uniformity of the characteristic of the amorphous silicon-based photosensitive member. Can be planned.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a high-frequency power supply electrode that can be used in an a-Si-based photoconductor manufacturing apparatus of the present invention.

FIG. 2 is a diagram showing an example of the configuration of an a-Si-based photoconductor manufacturing apparatus that can be used in the present invention.

FIG. 3 shows a conventional RF plasma C using an RF 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 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. 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 an experimental example performed to confirm the effects of the present invention.

FIG. 7 is a diagram showing evaluation results of an experimental example performed to confirm the effect of the present invention.

FIG. 8 is a diagram showing an example of a positional relationship between a shield and a gas ejection port used in an experimental example.

FIG. 9 is a diagram showing evaluation results of an experimental example performed to confirm the effects of the present invention.

FIG. 10 is a diagram showing evaluation results of an experimental example performed to confirm the effects of the present invention.

FIG. 11 is a diagram showing evaluation results of experimental examples conducted to confirm the effect of the present invention.

[Explanation of reference numerals] 101: high frequency electrode 102: shield 103: shield support 104: gas ejection port 201: reaction vessel 202: high frequency electrode also serving as a source gas supply means 204: exhaust pipe 205: cylindrical substrate 206: Film-forming space 207: Heating element 208: Rotating shaft 209: Motor 210: Reduction gear 211: High frequency matching box 212: High frequency power supply 451: Raw material gas introduction pipe 301: Reaction vessel 302: VHF electrode 304: Exhaust pipe 305: Cylindrical substrate 306: Film forming space 307: Heating element 308: Rotating shaft 309: Motor 310: Reduction gear 311: High frequency matching box 312: High frequency power supply 351: Raw material gas introduction pipe 3100: Deposition apparatus 3111: Reaction vessel 3112: Cylindrical substrate 3113: Support heating heater 3114: Raw material gas introduction pipe 3 115: Matching Box 3116: Raw Material Gas Pipe 3117: Reaction Vessel Leak Valve 3118: Main Exhaust Valve 3119: Vacuum Gauge 3200: Raw Material Gas Supply Device 3211 to 3216: Mass Flow Controller 3221 to 326: Raw Material Gas Cylinder 3231 to 236: Raw Material Gas Cylinder Valve 3241 ˜3246: Gas inflow valve 3251 to 2566: Gas outflow valve 3261 to 3266: Pressure regulator 401: Reaction vessel 402: Dielectric window 403: Waveguide 404: Exhaust pipe 405: Cylindrical substrate 406: Film forming space 407: Heating element 408: Rotating shaft 409: Motor 410: Reduction gear 451: Raw material gas introduction pipe 500: Electrophotographic photosensitive member 501: Support 502: Photoconductive layer 503: Surface layer 504: Charge injection blocking layer 505: Charge generation layer 5 6: The charge transport layer 801: high-frequency electrode 802: gas port 803: shield

Claims (9)

[Claims] 1. A plurality of cylindrical substrates are arranged in a vacuum-tight reaction container so as to surround a film forming space, and at least a source gas supply means and a high frequency power introducing means are provided in the film forming space. A plasma CVD method in which glow discharge is generated in the film forming space by introducing high frequency power in the VHF band from the high frequency power introducing means to the source gas supplied from the gas supply means to form a deposited film on the substrate. In the apparatus for producing an amorphous silicon-based photosensitive member according to the above, the raw material gas supply means has a structure for supplying the raw material gas into the film forming space of the reaction container from a gas ejection port provided on the surface of the high frequency power introduction means. An apparatus for producing an amorphous silicon-based photosensitive member, characterized in that a shield for scattering the raw material gas is provided outside the gas ejection port. 2. The shield has a maximum radius of an inscribed circle among the inscribed circles of the shield whose size passes through the center of the gas ejection port and has a central axis perpendicular to the high frequency electrode. Value R
2. The apparatus for producing an amorphous silicon-based photoconductor according to claim 1, wherein R ≧ 3r with respect to a radius r of the circumscribed circle of the gas ejection port. 3. The shield is an inscribed circle having a maximum radius R among the inscribed circles of the shield passing through the center of the gas ejection port and having a central axis perpendicular to the high frequency electrode, and a gas. The minimum distance a to the jet outlet is set in a range of a ≦ 2R.
The amorphous silicon-based photoconductor manufacturing apparatus described in 1. 4. The production of an amorphous silicon-based photoconductor according to claim 1, wherein the high frequency power in the VHF band has a frequency of 20 MHz to 450 MHz. apparatus. 5. The production of an amorphous silicon-based photoconductor according to claim 1, wherein the high frequency power in the VHF band has a frequency of 50 MHz to 450 MHz. apparatus. 6. A high-frequency wave in a VHF band from a high-frequency power introduction means to a raw material gas supplied from a raw material gas supply means in a film forming space formed by surrounding a plurality of cylindrical substrates in a vacuum-tight reaction container. In the method for producing an amorphous silicon-based photoconductor by plasma CVD in which electric power is introduced to cause glow discharge in the film formation space to form a deposited film on the substrate, the raw material from the raw material gas supply means is used. The gas is supplied from a gas outlet provided on the surface of the high-frequency power introducing means, and the raw material gas is scattered by a shield provided outside the gas outlet. Method for producing crystalline silicon-based photoreceptor. 7. The shield has a maximum inscribed circle radius among the inscribed circles of the shield having a central axis perpendicular to the high frequency electrode and passing through the center of the gas ejection port. Value R
The method according to claim 6, wherein R ≧ 3r 2 with respect to the circumscribed circle radius r of the gas ejection port. 8. The shield is an inscribed circle having a maximum radius R among the inscribed circles of the shield passing through the center of the gas outlet and having a central axis perpendicular to the high frequency electrode, and a gas. 7. The minimum distance a to the ejection port is set in a range of a ≦ 2R.
8. A method for manufacturing an amorphous silicon-based photoconductor according to item 1. 9. The production of an amorphous silicon-based photoconductor according to claim 6, wherein the high frequency power in the VHF band has a frequency of 20 MHz to 450 MHz. Method. 10. The method for producing an amorphous silicon-based photoconductor according to claim 6, wherein the high frequency power in the VHF band has a frequency of 50 MHz to 450 MHz. .