JPH0619172A - Photoreceptive member and its production - Google Patents

Abstract

PURPOSE:To obtain a method capable of stably producing an electrophotographic sensitive body which has no cloud on the surface of a photosensitive body and is excellent in potential characteristic eveness such as eveness of the electrostatic chargeability and halftone, and has tolerance to environmental changes and high durability. CONSTITUTION:In the producing method of the electrophotographic sensitive body, a cut conductive base body 101 is washed by water 122 and is, thereafter, subjected to a process 131 being in contact with the pure water and then, a photoconductive layer consisting of a nonsingle crystal SiC in which carbon atom content distribution is high at a lower part is formed thereon by a plasma CVD method and further, a surface layer consisting of silicon atoms, hydrogen atoms, carbon atoms, oxygen atoms and nitrogen atoms is formed thereon.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptive member such as an electrophotographic photoreceptor having a photoreceptive layer having a base material of silicon formed on a conductive substrate, and a method for producing the same. The present invention relates to a method for producing an electrophotographic photoconductor that can be widely used in electrophotographic application fields such as an electrophotographic copying machine, a laser beam printer, an LED printer, a liquid crystal printer, and a laser plate making machine.

[0002]

2. Description of the Related Art Conventionally, non-single-crystal deposited films, for example, amorphous deposited films such as amorphous silicon compensated by hydrogen and / or halogen (eg, fluorine, chlorine) have been proposed for use in electrophotographic photoreceptors. , Some of which are put to practical use. Conventionally, as a method of forming such a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (optical CVD method), a method of decomposing a source gas by plasma (plasma A large number of methods such as the CVD method) are known. Among them, the plasma CVD method, that is, the method of decomposing the raw material gas by direct current, high frequency or microwave glow discharge or the like to form a thin film deposition film on the substrate is
It is most suitable for the method of forming an amorphous silicon deposited film for electrophotography, and is now very practically used. Such an example is described in, for example, JP-A-54-86341. This amorphous silicon photoconductor is non-polluting, and has the characteristics of high image quality and high durability, and the amorphous silicon photoconductor currently put into practical use sufficiently shows its characteristics. However, in order for the amorphous silicon photoconductor to become more and more popular in the future, further cost reduction, further improvement of electrical characteristics,
Higher durability is desired. Further, in recent years, global-scale environmental pollution has become a problem, and it is urgently necessary to improve not only substances that lead to environmental pollution but also use in the manufacturing stage. Although the amorphous silicon photoconductor itself is non-polluting, it is necessary to reconsider from the viewpoint of cleaning the cylinder, which is the base portion of the photoconductor, to packaging after the production at the stage of manufacturing the photoconductor.

It has been conventionally known that care must be taken when cleaning an amorphous silicon photoconductor before cleaning a substrate before forming a film. As a substrate for depositing the amorphous silicon photoconductor, a metal is used in order to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to keep high positional accuracy so as not to deteriorate image quality. Many. for that reason,
In particular, aluminum alloys, which are excellent in workability and dimensional stability, are widely adopted. Generally, when processing these substrates, lathe processing is performed using an oil-based substance such as cutting oil. Therefore, after processing, there is always a residue of an oil-based substance on the substrate, and further cutting powder during processing, dust in the air, etc. are attached. If these residues remain due to insufficient cleaning, a defect-free uniform deposited film cannot be formed or sufficient electrical characteristics cannot be obtained, causing image defects especially when used for a long time. The point is known. Therefore,
When manufacturing an electrophotographic photosensitive member, it is necessary to wash the substrate thoroughly with great care. Under these circumstances,
For example, Japanese Unexamined Patent Publication No. 61-171798 discloses a technique relating to a method for processing a substrate of an electrophotographic photosensitive member.
The publication discloses a technique for obtaining an electrophotographic photoreceptor of good quality such as amorphous silicon by cutting a substrate by using a cutting oil having a specific component. Further, the publication describes that after cutting, the substrate is washed with triethane (trichloroethane: C ₂ H ₃ Cl ₃ ). The photoconductor prepared by using the substrate washed by such a method has some characteristics, and is now widely used without any particular problems. However, an organic solvent such as trichloroethane is Its use has to be avoided as it not only affects the human body but also the local environment.

In order to solve this problem, in recent years, several methods of cleaning the substrate with an aqueous system have been proposed instead of the aforementioned cleaning. For example, Japanese Patent Laid-Open No. 63-264764 discloses a technique of roughening the surface of a substrate with a water jet. Further, Japanese Patent Application Laid-Open No. 1-130159 discloses a technique of cleaning a substrate for electrophotography with a water jet. The publication mentions selenium and an organic photoconductor as well as amorphous silicon as an example of a photoconductor, and it is suggested that the present technology can be applied to an amorphous silicon photoconductor. However, it is the fact that this publication does not mention at all the problems when actually performed, particularly the problems peculiar to the plasma CVD method. On the other hand, the study of improving the quality of amorphous silicon photoconductors has been steadily progressing by studying the layer structure. JP-A-54-145540
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that by using amorphous silicon containing 0.1 to 30 atomic% of carbon as a chemical modifier as a photoconductive layer of an electrophotographic photosensitive member, high dark resistance and excellent photosensitivity are obtained. It has been shown to exhibit properties. Further, JP-A-57-119357 discloses that an electrophotographic photoreceptor having excellent characteristics can be obtained by distributing a large number of carbon atoms in the amorphous silicon on the substrate side. The performance of the electrophotographic photosensitive member has been improved by such techniques, but there is still room for improvement.

Under these circumstances, the following problems are listed up from the viewpoints of high image quality, high durability and no pollution. First of all, reduction of black dot or white dot image defects called spots is one of the most desired problems. At present, there is a growing demand for high image quality to reduce the size of microscopic dots, which has not been a problem in the past. Analysis of the cause of this problem is progressing day by day, and some knowledge has been obtained. Most of the causes of the spots are due to abnormal growth called spherical protrusions, which are caused by dust and the like generated when depositing the amorphous silicon film. In addition to this, there is also a durability pot that increases as the durability continues, which is caused by toner scattering and paper dust mixed in the separation charger. In order to reduce image defects caused by some of these causes, as a manufacturer of photoconductors, it is necessary to improve the cleanliness in the deposited film forming apparatus and suppress the generation of spherical protrusion nuclei that cause image defects. Needless to say, it is necessary to take measures such as improving the method for forming a deposited film and increasing the withstand voltage of the amorphous silicon photoconductor from the manufacturing aspect. Further, it has been known that when the electrophotographic photosensitive member rubs against a transfer paper or a cleaning blade, a comparatively large spherical projection is lost during repeated copying to cause spots on an image. This reduction of the porosity improves the electrical withstand voltage of the photoconductor at the same time as the reduction of the spherical projections and makes it difficult to cause the dielectric breakdown, which is effective for preventing the leakage porosity.

Furthermore, in recent years, the use of recycled paper has increased in the field of electrophotography as part of the protection of the global environment. However, recycled paper causes the generation of additives and paper dust during the papermaking process.
Compared with conventional new paper. For example, rosin, which is used as an additive (surface treatment agent) such as white clay used as a bleaching agent for old newspapers, may adhere to the surface of the photoconductor to easily cause toner fusion and image deletion. The problem is becoming recognized. Therefore, the quality of the recycled paper has been improved, and further improvement of the surface of the electrophotographic photoreceptor has been demanded. Further, in recent years, electrophotographic copying machines are required to have higher image quality and higher functions, so that it is essential to be able to faithfully reproduce originals including halftones such as photographs. Therefore, reduction in unevenness in halftone is particularly desired for the electrophotographic photosensitive member.
In particular, in a full-color copying machine which has been widely used in recent years, this unevenness causes subtle unevenness in color and becomes visually apparent, which is a serious problem. Furthermore, it is desired that the electrophotographic photosensitive member maintain high image quality and high sensitivity and greatly improve durability performance under all environments. Amorphous silicon photoconductors are best suited for this durability because they do not need to be replaced until the life of the copier body is reached. , The possibility of being released from maintenance such as photoconductor replacement is beginning to be seen. Therefore, further new products are required to have durability equal to or higher than that of the main body of the copying machine, and it is desired to further enhance durability. Amid such requirements, it has been difficult to achieve both high charging ability and prevention of image deletion at a high level, and it is difficult to significantly extend durability in any environment, which is still insufficient.

In addition, maintaining high electrical characteristics, image characteristics, etc.,
There is still a need for improvement in producing a photosensitive body continuously with good reproducibility. A technique from this point of view is disclosed in, for example, Japanese Patent Laid-Open No. 2-197574. The publication discloses a container for introducing a substrate into a vacuum atmosphere for continuously producing an amorphous silicon photosensitive member by a microwave plasma CVD method, and a reaction container for manufacturing a photosensitive member by a microwave plasma CVD method. There is disclosed a system for continuous production of a photoreceptor, which comprises a cooling container for slowly cooling the resulting photoreceptor in a vacuum. Using such a system, it has become possible to repeatedly manufacture a photoreceptor, but as it is manufactured many times in succession, a deposited film gradually adheres to the reaction container, which causes image defects. It becomes easy to generate dust. Therefore, it is necessary to periodically return the reaction vessel to the atmosphere to remove the deposited film, for example, every several months. After cleaning the reaction vessel by exposing it to the atmosphere, residual air, moisture, etc. remain and the content of oxygen atoms and nitrogen atoms as impurities increases immediately after the formation of the deposited film, which affects the characteristics. There was also a problem that was not stable. Under the current circumstances, it is necessary to review all of these various problems from the step of cleaning the conductive substrate to the step of manufacturing the electrophotographic photosensitive member, and to make a comprehensive study of image characteristics and stable manufacturing. Further, conventionally, as a method of recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light receiving member with a laser beam modulated according to the digital image information, and then the electrostatic latent image is formed. A method is known in which an image is recorded by developing the image or further performing processing such as transfer and fixing, if necessary. Among them, in the image forming method by electrophotography, He--N which is small and inexpensive as a laser is used.
e laser or semiconductor laser (usually 650-8
It is common to perform image recording using (having an emission wavelength of 20 nm).

However, when a semiconductor laser is used in the electrophotographic process, there have been problems as will be described later. As the light receiving member for electrophotography, Se photoconductor, O
PCs (organic photoconductors), CdS photoconductors, ZnO photoconductors, etc. have been put into practical use. However, as a photoreceptive member for electrophotography suitable when a semiconductor laser is used, the photosensitivity region matching is other than that. In addition to being excellent in comparison with various types of light receiving members, it has been evaluated in terms of high Vickers hardness and less problem of pollution. For example, JP-A-54-86.
No. 341 or JP-A-56-83746, an amorphous material containing silicon atoms as a base material (hereinafter,
It is abbreviated as "a-Si". The light receiving member composed of (1) is attracting attention. However, regarding the light receiving member, if the light receiving layer is a single-layer a-Si layer, it is required for electrophotography while maintaining its high photosensitivity.
^{In order} to secure a dark resistance of ¹² Ωcm or more, hydrogen atoms, halogen atoms, or in addition to these, atoms capable of controlling the conductivity of the photoreceptive layer, such as boron atoms and phosphorus atoms, should be added in a specified amount range. It must be contained in a controlled manner with structural bonds. For this reason, there are considerable restrictions on the tolerance of the design of the light receiving member, such as strict control of various conditions in forming the layer. On the other hand, it has been proposed to improve such a design tolerance by making effective use of the high photosensitivity even if the dark resistance is somewhat low. That is, for example, JP-A-54-121743, JP-A-57-4053, and JP-A-57-41.
As disclosed in JP-A-72, each of the light-receiving layers has a layer structure of two or more layers in which layers having different conductivity are laminated to form a depletion layer inside the light-receiving layer, or JP-A-57-57. -52178, JP-A-57-52179, JP-A-57-52180, and JP-A-57-5.
As disclosed in JP-A-8159, JP-A-57-58160 and JP-A-57-58161, a barrier is provided between the support and the light receiving layer and / or on the upper surface of the light receiving layer. There has been proposed a light-receiving member having a higher apparent dark resistance, such as a multilayer structure having layers.

However, in such a light receiving member having a multilayer structure of the light receiving layer, the layer thickness of each layer varies, and when laser recording is performed using this, the laser light is coherent monochromatic light. , The free surface of the light-receiving layer on the laser light irradiation side, each layer constituting the light-receiving layer and the layer interface between the support and the light-receiving layer (hereinafter referred to as "interface" in the sense of combining both the free surface and the layer interface) Often, each of the reflected lights reflected from the (. This interference phenomenon is
It appears as an interference fringe pattern, which causes a defective image. Particularly, when a halftone image having high gradation is formed, a rough image having markedly inferior discrimination is provided. It is also important to note that as the wavelength region of the semiconductor laser light used becomes longer, the absorption of the semiconductor laser light in the light-receiving layer decreases, so that the reflection at the interface increases, resulting in the interference. There is a problem that the phenomenon becomes remarkable. That is, for example, in a structure of two or more layers (multilayer), an interference phenomenon occurs in each of these layers, and the respective interferences act synergistically to form an interference fringe pattern, which remains as it is. There is a problem that the transfer member is affected, and interference fringes corresponding to the interference fringe pattern are transferred and fixed on the transfer member to appear in a visible image, resulting in a defective image.
The following methods have been proposed as measures to solve such problems. (1) A method of forming a light-scattering surface by diamond cutting the surface of a support to form irregularities of ± 500 to ± 10,000 on the surface of the support (for example, JP-A-58).
-162975). (2) A method of providing a light absorbing layer by subjecting the surface of an aluminum support to black alumite treatment or by dispersing carbon, a coloring pigment and a dye in a resin (for example, JP-A-57-165845). (3) A method of providing a light-scattering / anti-reflection layer on the surface of an aluminum support by subjecting the surface of the aluminum support to a matte finish alumite treatment or providing fine irregularities in the form of grain by sandblasting (for example, JP-A-57-16554). Issue).

Although these proposed methods have some tentative results, they are not sufficient to completely eliminate the interference fringe pattern appearing on the image. That is, in the above method (1), a large number of irregularities having a specific roughness are provided on the surface of the support, and although the appearance of an interference fringe pattern due to the light scattering effect is suppressed for some time, Since the specular reflection light component still remains as the scattering, in addition to the interference fringe pattern due to the specular reflection light remains, due to the light scattering effect on the support surface, the irradiation spot of the laser light spreads, It causes a substantial reduction in resolution.
Regarding the method (2), the black alumite treatment cannot completely absorb the light, and the reflected light on the surface of the support remains. In addition, when the color pigment dispersed resin layer is provided, since the substrate needs to be heated when the a-Si layer is formed, the degassing phenomenon occurs from the resin layer, and the layer quality of the formed light receiving part layer is improved. Remarkably lowering, the resin layer is damaged by the plasma at the time of forming the a-Si layer, the original absorption function is reduced, and the subsequent deterioration of the surface state adversely affects the formation of the a-Si layer. There are problems such as. With regard to the method (3), for example, regarding incident light, a part of the incident light is reflected on the surface of the light-receiving layer to be reflected light, and the rest enters the light-receiving layer to be transmitted light. The transmitted light is at the surface of the support,
Part of the light is scattered and becomes diffused light, and the rest is specularly reflected and becomes reflected light, and part of it becomes emitted light and goes out, but the emitted light is a component that interferes with the reflected light. hand,
In any case, the interference fringe pattern does not completely disappear because it remains.

Incidentally, in order to prevent interference, in addition to the above methods (1) to (3), an attempt is made to increase the diffusivity of the surface of the support so as not to cause multiple reflection inside the light-receiving layer. However, in such a case, the light diffuses in the light-receiving layer to cause halation, which eventually reduces the resolution. Particularly, in the light receiving member having a multi-layered structure, even if the surface of the support is irregularly roughened in order to enhance the diffusivity, the reflected light at the surface layer and the reflected light at the interface between the first layer and the second layer After that, the reflected light at each interface and the specularly reflected light at the surface of the support interfere with each other to form an interference fringe pattern according to each layer thickness of the light receiving member. Therefore, in the light receiving member having a multilayer structure, it is impossible to completely prevent interference fringes by irregularly roughening the surface of the support. For example, when the surface of the support is irregularly roughened by a method such as sandblasting, the roughness varies widely among lots, and even within the same lot, the roughness is uneven, which is a problem in manufacturing control. There is. Furthermore, relatively large protrusions are often formed randomly, and these large protrusions cause local breakdown of the photoreceptor layer. On the other hand, when the surface is simply and regularly roughened, the photoreceptive layer is usually deposited along the irregular shape of the surface of the support. The sloping surface of the unevenness is parallel to the area where the incident light causes bright and dark areas, and the light-receiving layer has a non-uniform thickness of the light-receiving layer. Will appear. Therefore, the occurrence of the interference fringe pattern cannot be completely prevented only by regularly roughening the surface of the support.

Further, even when a multi-layered light receiving layer is deposited on a support whose surface is regularly roughened, specular reflection light on the support surface and reflection light on the light reception layer surface are obtained. In addition to the above interference, the interference due to the reflected light at the interface between the layers is added, so that the degree of occurrence of the interference fringe pattern is more complicated than that of the light receiving member having a further structure. One of the means for solving these problems is JP-A-62-135661 and JP-A-62-69.
No. 272 and JP-A No. 62-69273, respectively. The technique disclosed in each of these publications is generally described by dropping a rigid sphere having substantially the same diameter from a certain height onto a surface of a support to form a plurality of spherical spheres having substantially the same width and curvature on the surface of the support. By providing the depressions (hereinafter referred to as “dimples”), interference fringes generated by the interference of the reflected light of the light incident on the surface of the support are provided in the respective dimples, and a souring corresponding to a so-called Newton ring phenomenon is provided. By generating and dispersing the interference fringes generated in the entire light receiving member, the generation of the interference fringes in the light receiving member is prevented. As a result, the problem of interference fringes is almost solved, and even when laser light, which is coherent monochromatic light, is used as a light source, the appearance of interference fringe patterns in the formed image due to the interference phenomenon is significantly prevented. It became possible to form a very high quality visible image. However, JP 61-231561, JP 62-69272, and JP 62-69273.
In the light receiving member disclosed in each of the publications, considering further improvement in performance, cost reduction during mass production, and so-called ecological problems (that is, environmental problems), the following problems to be solved still remain. Remains.

First, the standards required for electrophotographic light-receiving members are becoming stricter year by year, making it difficult to satisfy the image quality such as uniformity and high definition in the current standards. It's starting. In order to further improve the resolution of the image, when the toner used is made into fine particles, or when the diameter and thickness of the support are changed, and when the wavelength of the laser used is changed, the conditions are Since the optimum width and radius of curvature of the dimples are different, it is necessary to change the diameter or hardness of the rigid sphere to be used, which is difficult to cope with with the conventional technique, and the cost is increased. Secondly, when the hard spheres forming the dimples are made of metal, chips may be generated when the hard spheres and the support collide with each other, thereby impairing the surface property of the support. In particular, if the ball is repeatedly used for a long time during mass production, the quality of the hard sphere deteriorates, so that the above problem becomes more prominent as the usage time elapses. Thirdly, in order to fully exhibit the characteristics of amorphous silicon, it is essential that the surface of the support is treated cleanly. Therefore, during mass production, the support should be supported before and after the step of forming the spherical depressions on the surface of the support. A body cutting process or a cleaning process is essential. Therefore, such a large number of pretreatments before forming the a-Si photoreceptive layer on the support increases the manufacturing cost. Further, in the above-mentioned cutting step, cutting oil is used to improve its lubricity, but in order to remove this cutting oil from the surface of the support, an organic solvent is mainly used in the conventional washing step. . However, the use of this organic solvent causes environmental pollution, and its solution is urgently desired.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points and has an electrophotographic photoreceptor having a conventional light-receiving layer composed of a material having a silicon atom as a base as described above. SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems, to provide a photoconductor having excellent electric characteristics and greatly reducing image defects at a low cost with a high yield. That is, the main object of the present invention is not to use an organic solvent in the manufacturing process, it is excellent in environmental protection, and further significantly improves the yield in the appearance defect of the manufactured electrophotographic photosensitive member, image defects, such as halftone unevenness. It is intended to provide a method for producing a photoconductor having excellent characteristics, which can be used in any environment, at low cost. Another object of the present invention is to provide a material having a uniform and high-quality silicon atom as a base material, which has excellent adhesion between the layer provided on the conductive substrate and the conductive substrate or between the layers of the laminated layers. An object of the present invention is to provide an electrophotographic photoreceptor having a structured light receiving layer. Still another object of the present invention is that, when applied as an electrophotographic photoreceptor, it has sufficient charge retention ability during charging processing for electrostatic image formation, produces a clear halftone, and has a high resolution. An electrophotography having a photoreceptive layer composed of a material having a silicon atom as a base material, which can easily obtain a high-quality image and exhibits excellent electrophotographic characteristics to which an ordinary electrophotographic method can be applied very effectively. It is to provide a method of manufacturing a photoreceptor. Also,
An object of the present invention is to overcome various problems in the conventional light receiving member as described above, and to satisfy various requirements for a light receiving member having a light receiving layer mainly composed of a-Si. That is, the electrical, optical, and photoconductive properties are practically always stable with little dependence on the operating environment, have excellent light fatigue resistance, and do not cause a deterioration phenomenon during repeated use, durability, It has excellent moisture resistance, no or little residual potential is observed, the manufacturing process can be simplified, and the preparation conditions can be easily adjusted.
It is an object of the present invention to provide a light-receiving member having a light-receiving layer composed of a-Si, which is effective for the problem of environmental pollution, and a method for producing the same.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support or between the layers to be laminated, to be strict and stable in terms of structural arrangement, A high-quality light-receiving member having a light-receiving layer composed of a-Si, and a method for producing the same. Still another object of the present invention is suitable for image formation using coherent monochromatic light, and even in repeated use for a long period of time, there is no appearance of interference fringe patterns and color unevenness at the time of reversal phenomenon, and image defects and image defects and Photoreceptive member having a photoreceptive layer composed of a-Si capable of obtaining a high-quality image having no image blur, high density, clear halftone, and high resolution, and method for producing the same To provide.

[0016]

The inventors of the present invention have made earnest studies from the standpoints of productivity and cost reduction and environmental protection in order to overcome the above-mentioned problems in the conventional deposited film forming method. As a result, it was achieved. The present invention has been completed on the basis of the above-mentioned findings. To describe the gist of the invention, the first invention is to perform a step of cutting the surface of a conductive substrate with a predetermined accuracy and a substrate surface after cutting. A step of washing with water, a step of bringing the surface of the conductive substrate into contact with pure water, and a photoconductive layer and a surface layer composed of a non-single-crystal material having silicon atoms as a matrix on the conductive substrate. A method for producing an electrophotographic photosensitive member, which comprises a step of forming a light receiving layer, wherein the surface layer contains carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms, and Containing carbon atoms and hydrogen atoms across the layer, the content of the carbon atoms is unevenly distributed in the film thickness direction,
Further, the light receiving layer highly distributed on the side of the conductive substrate is formed on the conductive substrate by a plasma CVD method such as microwave plasma or high frequency plasma. A second invention is a step of cutting the surface of the conductive substrate with a predetermined accuracy, a step of cleaning the surface of the substrate after cutting with water, a step of bringing the surface of the conductive substrate into contact with pure water, and the conductive A method for manufacturing an electrophotographic photosensitive member, comprising the step of forming, on a substrate, a photoreceptive layer composed of a photoconductive layer composed of a non-single-crystal material having a silicon atom as a matrix and a surface layer, the method comprising: The conductive layer contains carbon atoms, hydrogen atoms, halogen atoms, and oxygen atoms throughout the layer, and the content of the carbon atoms is unevenly distributed in the film thickness direction, and is high on the side of the conductive substrate. It is characterized in that a light receiving layer which is distributed and contains carbon atoms and hydrogen atoms in the surface layer is formed on a conductive substrate by a plasma CVD method.

A third invention is a step of cutting the surface of the conductive substrate with a predetermined accuracy, a step of cleaning the surface of the substrate after cutting with water, a step of bringing the surface of the conductive substrate into contact with pure water, and A method for producing an electrophotographic photosensitive member, comprising the step of forming a photoreceptive layer composed of a photoconductive layer composed of a non-single-crystal material having silicon atoms as a matrix and a surface layer on the conductive substrate. , The surface layer contains carbon atoms, hydrogen atoms and Group III elements of the periodic table, and the photoconductive layer contains carbon atoms and hydrogen atoms throughout the layer, and the content of the carbon atoms is Is formed on the conductive substrate by a plasma CVD method using, for example, microwave plasma or high-frequency plasma. It has a feature. A fourth invention is a step of cutting the surface of the conductive substrate with a predetermined accuracy, a step of cleaning the substrate surface after cutting with water, and a step of cleaning the substrate surface by bringing the cleaned substrate surface into contact with pure water. , The cleaned substrate surface contains carbon atoms and hydrogen atoms, and the content of the carbon atoms is nonuniform in the layer thickness direction and highly distributed on the side of the conductive substrate. A step of forming a first photoconductive layer made of a non-single-crystal material by a plasma CVD method, and a plasma CVD method of forming a second photoconductive layer containing silicon atoms as a base material on the formed first photoconductive layer. And a step of forming a surface layer containing silicon atoms as a matrix and containing carbon atoms, hydrogen atoms and Group III elements of the periodic table on the formed second photoconductive layer by a plasma CVD method. This It is characterized by. A fifth invention is a step of cutting the surface of the conductive substrate with a predetermined accuracy, a step of cleaning the substrate surface after cutting with water, and a step of bringing the cleaned substrate surface into contact with pure water to clean the substrate surface. , The cleaned substrate surface contains carbon atoms and hydrogen atoms, and the content of the carbon atoms is nonuniform in the layer thickness direction and highly distributed on the side of the conductive substrate. A step of forming a first photoconductive layer made of a non-single-crystal material by a plasma CVD method, and a plasma CVD method of forming a second photoconductive layer containing silicon atoms as a base material on the formed first photoconductive layer. And a step of forming a surface layer containing silicon atoms as a matrix and containing carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms on the formed second photoconductive layer by a plasma CVD method. It is characterized by a door.

The light receiving member of the sixth invention comprises a support and a light receiving layer having a multi-layered structure formed on the support, and the surface of the support naturally comprises a plurality of spherical ice particles. It has an unevenness due to a plurality of trace depressions obtained by dropping or pressurizing and spraying the plurality of spherical ice particles on the surface of the support. Here, the irregularities due to the plurality of trace depressions may be irregularities due to the spherical trace depressions having substantially the same radius of curvature. The unevenness due to the plurality of trace dimples may be unevenness due to spherical trace dimples having substantially the same radius of curvature and substantially the same width. Concavities and convexities due to the plurality of trace depressions cause a plurality of spherical ice particles of approximately the same size to spontaneously fall from approximately the same height or to be pressure-injected at approximately the same pressure, so that the plurality of spherical ice particles are It may be obtained by colliding with the surface of the support. The plurality of spherical ice particles may be produced by atomizing pure water in a gas phase and freezing the dispersed pure water by a cooling means. The width of the trace recess may be 500 μm or less. The diameter of the spherical ice particles is 10 μm
It may be -10 mm. The support may be a metal body. A method for producing a light-receiving member according to a seventh aspect of the present invention is a method for producing a light-receiving member including a support and a light-receiving layer having a multi-layered structure formed on the support. The particles of natural fall or pressure injection, the plurality of spherical ice particles to collide with the surface of the support, to form a concavo-convex by the plurality of trace depressions on the surface of the support, And a step of forming the light receiving layer on the support.

Here, in the unevenness forming step, a plurality of spherical ice particles having substantially the same size are spontaneously dropped from substantially the same height or pressure-injected with approximately the same pressure, and the plurality of spherical ice particles are sprayed. Particles may be allowed to collide with the surface of the support.
The concavo-convex forming step includes an ice making step in which pure water is dispersed in a gas phase in a mist state and then the dispersed pure water is frozen by a cooling means to produce the plurality of spherical ice particles. But it's okay. The fall distance or the pressure of pressure injection of the plurality of spherical ice particles may be set so that the width of the trace dent is 500 μm or less. The unevenness forming step may double as a support washing step of washing the support. The spherical ice particles have a diameter of 10 μm to 10 μm.
It may be mm. The support may be a metal body. Hereinafter, the present invention will be described in detail. (First Invention) The procedure for actually forming an electrophotographic photosensitive member by the method for manufacturing an electrophotographic photosensitive member of the first present invention shown in FIG. 5 (a) using an aluminum alloy cylinder as a conductive substrate is described below. One example is a pretreatment device for a conductive substrate shown in FIG. 1 and a microwave C shown in FIGS. 2 (a) and 2 (b).
An explanation will be given using a deposited film forming apparatus by the VD method. Lathe with air damper for precision cutting (PNEUMO PRECL
SION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle, and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed rate was 0.01 mm. Under the condition of / R, mirror cutting is performed so that the outer shape becomes 108 mm. With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG.
2 and the substrate transfer mechanism 103. Processing unit 102
The substrate loading table 111, the substrate cleaning tank 121, the pure water contact tank 131, the drying tank 141, and the substrate unloading table 151. Both the cleaning tank 121 and the pure water contact tank 131 are equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 161, and the transfer arm 161 includes a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the conductive substrate 101, and a chucking mechanism 16.
It is composed of an air cylinder 164 for moving up and down 3. After cutting, the conductive substrate 101 placed on the input table 111 is transported to the cleaning tank 121 by the transport mechanism 103. The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution 122 in the cleaning tank 121. Next, the conductive substrate 101
Is transported to the pure water contact tank 131 by the transport mechanism 103,
Pure water having a resistivity of 17.5 MΩ-cm maintained at a temperature of 25 ° C. is sprayed from the nozzle 132 at a pressure of 50 kg · f / cm ² . Conductive substrate 10 after the pure water contact step
1 is moved to the drying tank 141 by the transfer mechanism 103, and is dried by blowing high-temperature high-pressure air from the nozzle 142. The conductive substrate 101 after the drying process is carried to the carry-out table 151 by the carrying mechanism 103.

Next, an amorphous film is formed on the surface of the electroconductive substrate after the cutting and pretreatment by the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b). A deposited film mainly composed of silicon is formed. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 2.
01 is a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics, or the like) that can efficiently penetrate into 01 and maintain vacuum tightness. 20
Reference numeral 3 denotes a waveguide for transmitting microwave power, which is composed of a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. Waveguide 2
03 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212, and is electrically connected to the electrode 212. The electrophotographic photoreceptor is manufactured using such a deposited film forming apparatus as follows. First, the reaction container 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction container 201 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the heater 207 heats and holds the temperature of the substrate 205 at a predetermined temperature. Therefore, a raw material gas such as a silane gas as a raw material gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluent gas is introduced into the reaction vessel 201 through a gas introduction means (not shown). At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz, and the dielectric window 20 passes through the waveguide 203.
It is introduced into the reaction vessel 201 via the No. Further, a DC power source 211 electrically connected to the bias electrode 212 in the discharge space 206 applies a DC voltage to the bias electrode 212 with respect to the substrate 205. Thus, the conductive substrate 205
In the discharge space 206 surrounded by, the source gas is excited by the energy of microwaves and dissociates, and the electric field between the bias electrode 212 and the base 205 constantly causes ion bombardment on the conductive base 205. While the base 2
05 A deposited film is formed on the surface. At this time, the conductive substrate 2
The rotating shaft 209 on which No. 05 is installed is rotated by the motor 210, and the conductive substrate 205 is rotated around the central axis in the substrate generatrix direction to form a deposited film layer uniformly over the entire circumference of the conductive substrate 205. .

With such a manufacturing apparatus, a light receiving member comprising a photoconductive layer and a surface layer, which is an essential requirement of the present invention, can be manufactured under the conditions shown in Table 2, for example. According to such a procedure, the electrophotographic photosensitive member can be continuously and efficiently produced. In the present invention, the cleaning liquid used in the cleaning step is preferably water or water containing a surfactant added. The water quality can be any. The surfactant used in the washing step may be any of anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added. If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C.
C. or higher and 55.degree. C. or lower are suitable for the present invention. In the present invention, the use of ultrasonic waves in the cleaning step is important for obtaining the full effect of the present invention. The ultrasonic frequency is preferably 100 Hz or higher and 10 MHz or lower, more preferably 1 kHz or higher and 5 MHz or lower, and optimally 10 kHz or higher and 100 kHz or lower. The output of ultrasonic waves is preferably 10 W or more and 100 kW or less, more preferably 100 W or more and 10 kW or less.

Water of water used in the pure water contact step of the present invention
Quality is very important, and semiconductor grade pure water, especially ultra
LSI grade ultrapure water is preferred. Specifically, the water temperature
As low efficiency at 25 ° C, 1 MΩ-cm or more is preferable.
4 MΩ-cm or more, optimally 10 MΩ-cm or more
Suitable for the present invention. The amount of fine particles is 0.2 μm
The above is less than 100,000 pieces per milliliter, preferably
Ku or 10,000 or less, optimally 1000 or less
Suitable for light. The total number of viable bacteria is 1 mi
1000 or less, preferably 100 or less
Below, optimally 10 or less are suitable for the present invention. Organic
The physical quantity (TOC) is 100 mg or less per liter,
10 mg or less, optimally 2 mg or less is suitable for the present invention.
Is suitable. As a method of obtaining water of the above water quality,
Charcoal method, distillation method, ion exchange method, filter filtration method, reverse
Penetration method, ultraviolet sterilization method, etc. are available.
It is hoped that they will be used in combination to raise the required water quality.
Good When bringing pure water into contact with the conductive substrate surface,
It is desirable to apply pressure and spray. When spraying
If the water pressure is too weak, the effect of the present invention will be small.
If it is too strong, on the image of the obtained electrophotographic photoreceptor, especially
A pear-like pattern appears on the halftone image.
U Therefore, the pressure of water is 2 kgf / cm ² Since
Upper, 300kgf / cm² Below, preferably 10kg
・ F / cm² Above, 200kgf / cm² Below, optimal
20kgf / cm² Above 150kgf / cm
² The following are suitable for the present invention. However, in the present invention
Pressure unit kg ・ f / cm² Is the gravity kilogram per square centimeter
1 m · f / cm² Is 9806
Equal to 6.5 Pa. In the method of spraying pure water of the present invention
Sprays high pressure water from a nozzle
Method or pumping water with high pressure air and nose
Method before mixing and spraying with air pressure
Etc.

The flow rate of the pure water of the present invention is 1 liter / mi per conductive substrate in view of the effect of the invention and the economical efficiency.
n or more and 200 liters / min or less, preferably 2 liters / min or more and 100 liters / min or less, optimally 5 liters / min or more, 50 liters / min
The following are suitable for the present invention. The temperature of pure water of the present invention is
If it is too high, an oxide film is generated on the conductive substrate, which may cause peeling of the deposited film and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of pure water is 5 ° C or higher and 90 ° C or lower, preferably 10 ° C or higher and 55 ° C or lower,
Optimally, the temperature of 15 ° C or higher and 40 ° C or lower is suitable for the present invention. If the treatment time of the water contact treatment is too long, an oxide film is generated on the conductive substrate, and if it is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or longer and 30 minutes or shorter, preferably 20 minutes.
Seconds or more and 20 minutes or less, optimally 30 seconds or more and 10 minutes or less are suitable for the present invention. In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film. If the time from cutting to water contact treatment is too long, an oxide film will be generated again on the surface of the substrate, and if it is too short, the process will not be stable, so 1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours. Below, optimally 3 minutes or more, 4
Times below are suitable for the present invention. If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable. Therefore, the time is 1 minute or more and 8 hours or less, preferably 2 minutes or more. Four
It is suitable for the present invention that the time is less than or equal to the time, optimally 3 minutes or more and less than or equal to 2 hours.

As the conductive substrate used in the present invention,
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, or an electrically insulating conductive substrate such as glass or ceramics, on which at least the light receiving layer is formed is formed. A substrate whose surface is subjected to a conductive treatment can be used, but a metal is preferable from the viewpoint of mechanical strength and the like. In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive substrate in order to eliminate an image defect due to an interference fringe pattern that appears in a visible image. The unevenness provided on the surface of the conductive substrate is described in JP-A-60-168156 and JP-A-6-168156.
It is produced by a known method described in, for example, 0-178457 and 60-225854. Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. Unevenness due to a plurality of spherical trace depressions provided on the surface of the conductive substrate is disclosed in Japanese Patent Application Laid-Open No. 61-61.
It is produced by a known method described in Japanese Patent Publication No. 231561.

The photoconductive layer in the present invention is a non-single crystal silicon carbide (hereinafter referred to as nc-Si) containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements from the side of the conductive substrate.
C: Abbreviated as H. And a desired photoconductive property, in particular, a charge retention property, a charge generation property, and a charge transport property. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in the planes parallel to the surface of the conductive substrate, and non-uniform in the thickness direction of the layer. At each point in the film thickness direction, the content on the side of the conductive substrate is high, and the content on the side of the surface layer is low. If the content of carbon atoms is 0.5 or less on the surface on the side where the conductive substrate is provided or in the vicinity of the surface, the function of improving the adhesion with the conductive substrate and preventing the injection of electric charges is deteriorated. In addition, the effect of improving the charging ability due to the decrease in electrostatic capacity is lost. If it is 50% or more, a residual potential will be generated. Therefore, practically 0.5 to 50
Atomic%, preferably 1 to 40 atomic%, optimally 1
It is preferably about 30 atomic%. Further, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for making it happen. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the carbon content. Therefore,
The content of hydrogen atoms on the surface of the conductive substrate is preferably 1 to 4
0 atom%, more preferably 5 to 35 atom%, optimally 1
It is preferably 0 to 30 atom%.

In the present invention, the photoconductive layer is formed by the vacuum deposition film forming method, by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, it can be formed by a glow discharge method (AC discharge CVD method such as low frequency CVD method, high frequency CVD method or microwave CVD method, or DC discharge CVD method). Among them, the microwave glow discharge method and the high-frequency glow discharge method are industrially most suitable. In order to form the nc-SiC: H photoconductive layer by the glow discharge method, basically, a raw material gas for supplying silicon that can supply silicon atoms (Si) and a C supply that can supply carbon atoms (C). A raw material gas for supplying hydrogen and a raw material gas for supplying H capable of supplying hydrogen atoms (H) are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and glow discharge is performed in the reaction vessel. A layer made of nc-SiC: H may be formed on the surface of a predetermined conductive substrate that has been caused to occur and is installed at a predetermined position in advance. Materials that can be used as a gas for supplying silicon in the present invention include SiH ₄ , Si ₂ H ₆ , and S.
Hydrogenated silicon hydrides (silanes) in a gas state such as i ₃ H ₈ and Si ₄ H ₁₀ which can be gasified are mentioned as being effectively used, and further, they are easy to handle at the time of layer formation, and silicon supply efficiency is high. SiH ₄ and Si ₂ H ₆ are preferable in terms of goodness and the like. In addition, these raw material gases for supplying silicon atoms are supplied with H ₂ , He, and A as needed.
It may be diluted with a gas such as r or Ne before use. In the present invention, it is desirable to employ, as a material that can be a raw material for introducing carbon atoms, a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions.

Can be a source gas for introducing carbon atoms (C)
The starting materials effectively used as materials are C and H.
A constituent atom, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
C2-C4 ethylene hydrocarbons, C2-C3 hydrocarbons
Cetylene hydrocarbons and the like can be mentioned. Specifically, saturation
As hydrocarbons, methane (CH_Four ), Ethane (C₂H₆
 ), Propane (C₃ H₈ ), N-butane (n-C_Four H
_Ten), Pentane (C_FiveH₁₂), As an ethylene hydrocarbon
For ethylene (C₂ H_Four ), Propylene (C ₃ H
₆ ), Butene-1 (C_Four H₈ ), Butene-2 (C_Four H
₈ ), Isobutylene (C_Four H₈ ), Penten (C_Five 
H_Ten), As acetylene hydrocarbons, acetylene
(C₂ H₂ ), Methylacetylene (C₃ H_Four ), Butin
(C_Four H₆ ) And the like. Moreover, Si and C are formed.
As the source gas used as atoms, Si (CH₃ )_Four , Si
(C₂ H_Five )_Four Can include alkyl silicides such as
It To structurally introduce hydrogen atoms into the photoconductive layer,
H₂ , Or SiH_Four , Si₂ H₆ , Si₃ 
H₈ , Si_Four H_TenSilicon hydride and silicon atoms such as
Reacts with silicon or silicon compounds to supply
It can also be done by causing the discharge to coexist in the container.
You can Controls the amount of hydrogen atoms contained in the photoconductive layer.
To control, for example, the temperature of the conductive substrate, containing hydrogen atoms
Introduce the raw material used to
The amount of discharge, the discharge power, etc. may be controlled. Light in the present invention
It is particularly effective that the conductive layer contains halogen atoms.
It Halogen atom contained in the photoconductive layer in the present invention
Suppresses the aggregation of carbon and hydrogen atoms,
Ghosts to reduce localized level density in
And it is effective in improving the uniformity of layer quality. halogen
If the number of atoms is less than 1 atom ppm, it is due to halogen atoms
The effect of improving ghost is not fully exerted, and 95 atom p
On the other hand, if it exceeds pm, the film quality will deteriorate and a ghost phenomenon will occur.
It becomes like this. Therefore, the inclusion of halogen atoms
The content is practically 1 to 95 atomic ppm, more preferably
3-80 atom ppm, optimally 5-50 atom ppm
Preferably. Especially for the photoconductive layer within the above range.
Content of halogen atoms when carbon atoms are included
By setting to within the above range,
Experiments show that the image characteristics and durability are significantly improved.
I was confirmed.

In addition, it is effective for the present invention to distribute the contained halogen atoms so as to gradually increase from the vicinity of the substrate toward the upper portion of the photoconductive layer. In order to alleviate the change in internal stress generated between the substrate side and the surface layer side as the content of carbon atoms changes in the layer thickness direction by unevenly distributing the halogen atoms in the layer thickness direction, The defects in the deposited film are reduced and the film quality is improved. As a result, it is possible to improve the so-called temperature characteristic, in which the characteristics of the light receiving member change according to the temperature change of the usage environment of the light receiving member, and the electrophotographic characteristics such as charging ability and image density unevenness between copies are improved. It Examples of such a halogen atom include fluorine, chlorine, bromine, and iodine, preferably fluorine and chlorine, more preferably fluorine. Effective as a supply gas for containing such a fluorine atom in the layer is a gaseous or gasifiable fluorine compound such as a fluorine gas, a fluoride, a halogen compound containing fluorine, or a silane derivative substituted with fluorine. Preferred examples include: Furthermore, a gaseous or gasifiable silicon hydride compound containing a fluorine atom, which contains silicon atoms and fluorine atoms as constituent elements, can also be cited as an effective one. Specific examples of the fluorine compound which can be preferably used in the present invention include F ₂ , BrF, ClF, ClF ₃ , BrF ₃ and BrF.
Examples thereof include halogen compounds such as ₅ , IF ₃ , and IF ₇ . As a silicon compound containing a fluorine atom, a so-called fluorine atom-substituted silane derivative, specifically, silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be given as preferable examples. When forming the characteristic electrophotographic light-receiving member of the present invention by glow discharge or the like using such a silicon compound containing a fluorine atom, it is not necessary to use a silicon hydride gas as a gas for supplying silicon. Even if it is possible to form a photoconductive layer made of non-single crystal silicon containing a fluorine atom on a predetermined support, it is possible to further control the introduction ratio of hydrogen atoms introduced into the formed photoconductive layer. In order to facilitate the formation, it is preferable that a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio. In the present invention, the above-mentioned fluorides or fluorine-containing silicon compounds are effectively used as the fluorine atom supply gas.
Fluorine-substituted silicon hydrides such as F, SiH ₃ F, SiH ₂ F ₂ , and SiHF _{3, and the} like in a gas state or a gasifiable substance can also be cited as effective raw material for forming the photoconductive layer. Among these substances, fluorinated compounds containing hydrogen atoms are introduced with hydrogen atoms, which are extremely effective for controlling electrical or photoelectric properties, at the same time as the introduction of fluorine atoms into the layer during formation of the photoconductive layer. In the present invention, it is used as a suitable gas for supplying fluorine atoms.

In the present invention, it is also effective that the photoconductive layer contains oxygen atoms in addition to halogen atoms. In this case, the synergistic action with the halogen atom relaxes the internal stress of the deposited film and suppresses the structural defect of the film. This improves the mobility of carriers in the photoconductive layer and reduces the potential shift. The content of such oxygen atoms is 10 to 5,000 atom pp within the above range of halogen atom content.
A range of m is preferred. Further, for the present invention, it is preferable to distribute the oxygen atoms contained in the photoconductive layer so as to increase from the substrate side toward the surface layer side.
At this time, the internal stress in the deposited film is effectively relieved and the structural defects of the film are suppressed, so that the mobility of carriers in the photoconductive layer is improved and the surface potential characteristics such as potential shift are further improved. In the present invention, as a raw material gas for containing oxygen atoms in the photoconductive layer, oxygen (O ₂ ) and carbon monoxide (C
O), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen oxide (N ₂ O) in small amounts are effectively added to the source gas. Further, in the present invention, it is preferable that the photoconductive layer contains an atom (M) for controlling conductivity, if necessary.
Atoms for controlling conductivity may be contained in the photoconductive layer in a uniformly distributed state, or even in a portion having a nonuniformly distributed state in the layer thickness direction. Good. Examples of the atom (M) for controlling the conductivity include so-called impurities in the semiconductor field,
Atoms belonging to Group III of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as "Group III atoms") or atoms belonging to Group V of the Periodic Table giving n-type conduction characteristics (hereinafter "Group V atoms")
Abbreviated) can be used.

The group III atom is, specifically,
Element (B), aluminum (Al), gallium (Ga),
There are Isodium (In), Thallium (Tl), etc., especially
B, Al and Ga are preferred. As a Group V atom,
Physically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., with P and As being particularly preferred
Is. Atoms contained in the photoconductive layer that control conductivity
The content of (M) is preferably 1 × 10^-3~ 5x
10^Four Atomic ppm, more preferably 1 × 10^-2~ 1 x 1
0 ^Four Atomic ppm, optimally 1 x 10^-1~ 5 x 10³ atom
It is desirable to set it to ppm. Especially in the photoconductive layer
The content of carbon atoms (C) is 1 × 10³ Atomic ppm or less
In this case, the content of atoms (M) contained in the photoconductive layer
Preferably 1 × 10^-3~ 1 x 10³ Atomic ppm
It is desirable that the content of carbon atoms (C) be 1 × 10
³ If it exceeds atomic ppm, the content of atom (M) shall be considered.
Preferably 1 × 10^-1~ 5 x 10^Four Atomic ppm and
It is desirable to be done. Control conductivity in the photoconductive layer
An atom, for example a Group III atom or a Group V atom,
To introduce artificially, introduce a Group III atom during layer formation.
Gas source material or group V atom introduction source material
In order to form a photoconductive layer in the reaction vessel
It can be introduced with gas. For introduction of group III atoms
Or a raw material for introducing a Group V atom
What you get is that it is gaseous or less at normal temperature and pressure.
Both of them are those that can be easily gasified under layer forming conditions.
Is desirable. Raw materials for introducing such group III atoms
Specifically as a substance, for introducing a boron atom, B
₂ H₆ , B_Four H_Ten, B_Five H₉ , B_Five H₁₁, B₆ H _Ten, B
₆ H₁₂, B₆ H₁₄Borohydride, BF, etc.₃ , BCl
₃ , BBr₃ And the like. This
Other than AlCl₃ , GaCl₃ , Ga (CH ₃ )₃ , I
nCl₃ , TlCl₃ Etc. can also be mentioned.

In the present invention, a raw material for introducing a group V atom is effectively used. For introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ , etc., PH ₄ I, PF
₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr
₅ , and phosphorus halides such as PI ₃ are included. Besides this, A
sH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , S
bCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ etc. are also V
It can be cited as an effective starting material for introducing a group atom. Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary. Further, the photoconductive layer of the light receiving member of the present invention comprises a group Ia, a group IIa,
You may contain at least 1 sort (s) of element selected from VIa group and VIII group. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there. Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and specific examples of the group IIa atom include beryllium (Be), magnesium (Mg) and calcium. (Ca), strontium (Sr), barium (Ba)
Etc. can be mentioned.

Further, as the group VIa atom, specifically,
Chromium (Cr), molybdenum (Mo), tungsten (W) can be mentioned, and as the Group VIII atom, iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned. In the present invention, the layer thickness of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the photoconductive layer is preferably 5 to 50 μm, and more preferably 10
˜40 μm, optimally 20 to 30 μm. Nc-S having characteristics capable of achieving the object of the present invention
In order to form a photoconductive layer made of iC (H), it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction container as desired. The temperature (Ts) of the conductive substrate is
The optimum range is appropriately selected according to the layer design, but in the usual case, preferably 20 to 500 ° C., more preferably 5
It is desirable that the temperature is 0 to 480 ° C, optimally 100 to 450 ° C. The surface layer in the present invention is composed of a non-single-crystal material containing silicon atoms and carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms as constituent elements. The surface layer in the present invention does not substantially contain a substance that controls the conductivity as contained in the photoconductive layer. The carbon atoms contained in the surface layer may be uniformly distributed in the layer, or the carbon atoms may be contained in the layer thickness direction but not in a uniformly distributed state. There may be a part. However, in any case, it is necessary that the content be evenly distributed in the in-plane direction parallel to the surface of the conductive substrate in order to achieve uniform properties in the in-plane direction. .

The carbon atoms, oxygen atoms, and nitrogen atoms contained in the entire surface layer region of the present invention have effects such as high dark resistance and high hardness. The total content of the three atoms contained in the surface layer is (carbon atom + oxygen atom + nitrogen atom) / (silicon atom + carbon atom + oxygen atom +
The value of (nitrogen atom) is preferably 40 to 90 atom%, more preferably 45 to 85 atom%, and most preferably 50 to 80 atom%. In order to further exert the effect of the present invention, the content of oxygen atoms and nitrogen atoms is preferably 10 atom% or less. Further, the hydrogen atom, oxygen atom and nitrogen atom contained in the surface layer in the present invention are n
It compensates for the dangling bonds existing in c-SiC: H, has the effect of improving the film quality, and reduces the carriers trapped at the interface between the photoconductive layer and the surface layer, thus improving the image deletion.
In addition, the inclusion of oxygen atoms and nitrogen atoms in the surface layer improves the adhesiveness at the interface between the surface layer and the photoconductive layer, and it becomes possible to change the structure of the surface layer itself. The surface properties of the body, the pressure resistance, the protection function of the photoconductive layer and the aluminum cylinder that is the conductive substrate are improved, and the durability of the electrophotographic photoreceptor can be dramatically improved while maintaining excellent electrical characteristics. it can. That is, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the durability against high voltage is improved due to the decrease in the dielectric constant, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur.

Further, it is effective that the surface layer of the present invention further contains a halogen atom. Since the halogen atom contained in the surface layer improves the water repellency, the high humidity flow due to the adsorption of water vapor is also reduced, and the electric characteristics of the electrophotographic photosensitive member are further improved. The halogen atom contained in the surface layer is 20 atom% or less, and the sum of the content of hydrogen atom and halogen atom is preferably 30 to 70 atom%, more preferably 35 to 65 atom%, most preferably It is desirable that the content be 40 to 60 atomic%. In the present invention, to form the surface layer composed of nc-SiC: H, the same vacuum deposition method as the method for forming the photoconductive layer described above is adopted. In the present invention, as the silicon supply gas and the raw material gas for introducing carbon atoms (C) used in forming the surface layer, the same ones as those used in forming the photoconductive layer can be used. Is. In the present invention, the introduced gas for containing oxygen atoms and nitrogen atoms in the surface layer,
Oxygen (O ₂ ) and carbon monoxide (C
O), carbon dioxide (CO ₂ ), nitrogen (N ₂ ), ammonia (NH ₃ ) and the like for the nitrogen atom. Nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen oxide (N ₂ O) are preferable as those containing oxygen and nitrogen atoms at the same time. Further, in the present invention, the surface layer is provided with Ia group, IIa group, VIa group, VIII group of the periodic table.
It may contain at least one element selected from the group. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there.

Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and specific examples of the group IIa atom include beryllium (Be) and magnesium (Mg). ), Calcium (C
a), strontium (Sr), barium (Ba), etc. can be mentioned. Specific examples of Group VIa atoms include chromium (Cr), molybdenum (Mo), and tungsten (W), and Group VIII atoms include iron (Fe) and cobalt (Co). , Nickel (N
i) etc. can be mentioned. In the present invention, the layer thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, most preferably 0. 1-1
It is preferably set to 0 μm. When forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The temperature of the conductive substrate is appropriately selected in an optimum range, but is preferably 20 to 500 ° C, more preferably 50 to 500 ° C.
It is desirable that the temperature is 480 ° C., optimally 100 to 450 ° C. The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to 3} Torr, most preferably 1 × 10 ⁻⁴ to 1.
Torr is preferable. In the present invention, the ranges described above are mentioned as desirable numerical ranges of the conductive substrate temperature and the gas pressure for forming the surface layer, but these layer preparation factors are not usually independently determined separately. It is desirable to determine the optimum value of each layer production factor based on mutual and organic relations so as to form a surface layer having desired characteristics.

In the light receiving member of the present invention, a layer region whose composition is continuously changed may be provided between the photoconductive layer and the surface layer. By providing the layer region, the adhesion between the layers can be further improved. Further, in the light receiving member of the present invention, the photoconductive layer has a layer region containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction on the side of the conductive substrate. Is desirable. In the present invention, the energy for generating plasma may be DC, high frequency, microwave, or the like, but the effect of the present invention is more remarkable particularly when microwave or high frequency is used as the energy for generating plasma. Will be things. In the present invention, when microwaves are used for plasma generation, microwave power may be any as long as discharge can be generated, but 100 W or more and 10 kW or less,
Preferably, 500 W or more and 4 kW or less are suitable for carrying out the present invention. Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. <Example 1 and Comparative Example 1> Example 1 Diameter 108 m made of aluminum having a purity of 99.5%
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for manufacturing an electrophotographic photosensitive member according to the present invention described above, and 15 minutes after the completion of the cutting step, as shown in FIG. The surface treatment apparatus shown in Table 1 pretreated the surface of the substrate under the conditions shown in Table 1. However, in this example, as the surfactant, polyethylene glycol nonylphenyl ether was used as a 1 wt% aqueous solution. On the aluminum cylinder thus pretreated, according to the procedure detailed above, the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 was used, and electrophotography was carried out by the high frequency glow discharge method under the manufacturing conditions shown in Table 2. A photoconductor was prepared. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. 7, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly. At this time, the carbon content at the interface of the photoconductive layer with the substrate was set to about 10 atomic%. The carbon content was measured by elemental analysis by Rutherford backscattering method.

The surface layer of the electrophotographic photosensitive member thus prepared was visually evaluated, and then the copying machine NP-755 manufactured by Canon was used.
0 was installed in an electrophotographic device modified for experiments,
The following evaluation was carried out for electrophotographic characteristics such as sensitivity and residual potential and image characteristics after endurance. Surface Haze The produced electrophotographic photosensitive member was visually inspected for the degree of surface haze. ◎: No clouding ○: Partially cloudy △: Partially cloudy at several places and ×: Cloudy on the entire surface. Charging ability / sensitivity / residual potential Charging ability: An electrophotographic photoreceptor is installed in an experimental device, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential meter measures the dark surface potential of the electrophotographic photoreceptor. To do. Sensitivity: The electrophotographic photoreceptor is charged to a constant dark surface potential. Then, the light image is immediately irradiated. The light image is emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. The exposure amount is adjusted so that the light portion surface potential becomes a predetermined potential, and the exposure amount at this time is taken as the sensitivity. Residual potential: The electrophotographic photoreceptor is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. White spots / halftone unevenness ... Put the electrophotographic photoconductor in a copier, which is a Canon copier NP-7550 modified for experiment, and transfer it by a normal electrophotographic process to form an image on a paper surface. Images were evaluated by the procedure.

White Pochi ... A diameter 0.2 within the same area of a copy image obtained when a full black chart made by Canon (part number: FY9-9073) is placed on a platen and copied.
The number of white spots having a size of mm or less was counted. Halftone unevenness ... Image density of 100 points with a circular area of 0.05 mm in diameter as one unit on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on the platen and copied. Was measured and the variation in the image density was evaluated. For each of these, ◎ is “excellently good” ○ is “good” Δ is “no problem in practical use” × is “problem in practical use” Image characteristics after endurance ... Was installed in an electrophotographic apparatus modified for experiments, and an accelerated durability test equivalent to 3.5 million sheets was performed. Then, the image characteristics were evaluated as follows. Image deletion: A Canon test chart (part number: FY9-9058) consisting of all letters on a white background is placed on a document table, and an exposure amount twice the normal exposure amount is applied to make a copy. The obtained copy image was observed, and it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown.

⊚ is good ○ is partly discontinued Δ is many discontinuities but can be recognized as characters and has no practical problem Black spots ... Within the same area of the copy image obtained when a blank sheet is placed on the platen and copied. The number of black image defects having a diameter of 0.2 mm or less was counted. For each of these, ⊚ is “excellently good”, ○ is “good”, Δ is “no problem in practical use”, and “is a problem in practical use”. Comparative Example 1 A conductive substrate similar to that of Example 1 was cut in the same procedure, and the conductive substrate after cutting was subjected to the conventional conductive substrate cleaning apparatus shown in FIG. Was processed. The conductive substrate cleaning apparatus shown in FIG. 3 includes a processing tank 302 and a substrate transfer mechanism 303. Processing tank 3
Reference numeral 02 includes a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361. The transfer arm 361 includes a moving mechanism 362 that moves on the rail 365, a chucking mechanism 363 that holds the substrate 301, and the chucking mechanism 36.
It is composed of an air cylinder 364 for moving up and down 3.

After cutting, the substrate 3 placed on the input table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichloroethane (trade name: ETERNA VG manufactured by Asahi Kasei Kogyo Co., Ltd.) 322 in the cleaning tank 321 performs cleaning for removing cutting oil and chips adhering to the surface. After cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. In the same manner as in Example 1, the substrate thus pretreated in the conventional manner was subjected to the so-called function separation of the three-layer structure of the substrate, the charge transport layer, the charge generation layer and the surface layer under the conditions shown in Table 5. A type electrophotographic photosensitive member was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1, and the results of Example 1 are shown in Table 3. As is clear from Table 3, according to the method of the present invention, the sensitivity is improved,
Moreover, the residual potential is kept low. It can be seen that particularly excellent characteristics are exhibited with respect to haze on the surface of the photoconductor and uneven halftone. Furthermore, according to the present invention, it can be seen that there is no problem on the image even after the endurance of 3.5 million sheets. <Example 2 and Comparative Example 2> Example 2 FIGS. 2 (a) and 2 (b) were formed on a substrate obtained by pretreating the same substrate as in Example 1 by the substrate surface treatment apparatus shown in FIG.
An electrophotographic photosensitive member was manufactured under the conditions shown in Table 6 by the microwave glow discharge method using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. As a result, the same result as in Example 1 was obtained. Comparative Example 2 FIGS. 2A and 2 are formed on a conductive substrate obtained by pretreating the same substrate as in Comparative Example 1 by the substrate surface treatment apparatus shown in FIG.
A so-called function-separated type having a three-layer structure of a substrate, a charge transport layer, a charge generation layer, and a surface layer under the conditions shown in Table 7 by the microwave glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in (b). An electrophotographic photoreceptor was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 2. as a result,
The same result as in Comparative Example 2 was obtained. <Example 3 and Comparative Example 3> Example 3 On the substrate pretreated in the same manner as in Example 1 by the substrate surface treatment apparatus shown in FIG. 1, the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured by the high-frequency glow discharge method under the manufacturing conditions shown in Table 8 according to the procedure detailed above. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 8 and 9, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed to obtain two types of carbon. A photoconductor was prepared. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer is
It was set to about 10 atom%. For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the signal intensity by Auger spectroscopy.

The cloudiness of the surface of the produced electrophotographic photosensitive member is visually checked.
Judgment made visually and experimented with Canon copier NP-7550
Installed in a modified electrophotographic device for sensitivity, residual potential,
For white spots and halftone unevenness, those similar to those in Example 1
Evaluated by law. After that, 350
Evaluate about 10,000 sheets and evaluate image deletion and black spots
The results are shown in Table 9 as in Example 1. Comparative Example 3 Example 3 was carried out on a substrate pretreated in the same manner as Comparative Example 1.
Similarly, the carbon content pattern shown in FIGS.
To produce an electrophotographic photosensitive member, and evaluate in the same manner as in Example 3.
I did. The results are shown in Table 9 and the evaluation results of Example 3 are shown.
Shown with fruits. From Table 9, carbon of the photoconductive layer of the present invention
In the quantity change pattern, compared with the result of Comparative Example 3, initial characteristics,
Good results have been obtained for all image characteristics after endurance
I understand. <Example 4 and Comparative Example 4> Example 4 Using the substrate surface treatment apparatus shown in FIG.
2 (a) and 2 (b) on the pretreated substrate
Microwave glow using an electrophotographic photoconductor manufacturing device.
Table 10 shows the same procedure as in Example 3 except that the discharge method was used.
An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown. In this example
Shows the change pattern of carbon content in the photoconductive layer.
Introduced during the formation of the photoconductive layer in order to change like
CH _Four Was changed. Which pattern
However, the carbon content on the substrate side surface of the photoconductive layer is about 10
It was made to be atomic%. In addition, for the measurement of carbon content
It was performed by elemental analysis by Rutherford backscattering method. Product
The electrophotographic photosensitive member produced had the same results as in Example 3.
was gotten. Comparative Example 4 By using the substrate surface treatment apparatus shown in FIG.
On the pretreated substrate, as in Example 4,
10, electrophotographic photosensitive with carbon content pattern shown in FIG.
The body was made. The obtained electrophotographic photosensitive member was the same as in Example 4.
The same evaluation as in Comparative Example 3 was performed.
Results were obtained. <Embodiment 5> Using the substrate surface treatment apparatus shown in FIG.
On the substrate pretreated in the same manner as in Example 1, the electrode shown in FIG.
Using the manufacturing device for the sub-photoreceptor, follow the procedure detailed above.
Therefore, the fabrication shown in Table 2 by the high frequency glow discharge method.
An electrophotographic photosensitive member was produced under the conditions. In this embodiment,
The change pattern of carbon content in the electrode layer is shown in FIG.
CH to introduce the carbon content of the side surface during the formation of the photoconductive layer
_Four It was changed by changing the flow rate of. And photoconductive
The carbon content at the substrate side surface of the layer is
It was identified by random elemental analysis.

Haze and surface of the produced electrophotographic photosensitive member
And the number of spherical protrusions, and Canon copier NP-75
The 50 is installed in an electrophotographic device modified for experiments and charged.
Performance, sensitivity, residual potential, white spots, halftone unevenness, etc.
Evaluation of sub-photographic characteristics and image quality after durability of 3.5 million sheets
Valuable. Each item was evaluated by the following methods. Surface Haze Evaluation was carried out in the same manner as in Example 1. The number of spherical protrusions The entire surface of the electrophotographic photosensitive member produced is observed with an optical microscope.
And 100 cm² With a diameter of 20 μm or more within the area of
The number of protrusions was examined. Results for each electrophotographic photoreceptor
The highest number of spherical protrusions is 100%
I made a relative comparison. The results are classified as follows. ⊚ is less than 60% ◯ is 80 to 60% Δ is 100 to 80% Residual potential Evaluation was performed in the same manner as in Example 1. White spots / halftone unevenness White spots / halftone unevenness ... Assessed in the same manner as in Example 1.
did. The results thus obtained are summarized in Table 11.
From this result, as the amount of carbon on the substrate side surface of the photoconductive layer,
Is seen to improve the characteristics at 0.5 to 50 atomic%.
Very good results have been obtained at 1 to 30 atom%. <Embodiment 6> An embodiment using the substrate surface treatment apparatus shown in FIG.
2 (a) and 2 on the substrate which has been pretreated in the same manner as in FIG.
Using the electrophotographic photoreceptor manufacturing apparatus shown in (b),
Follow the procedure detailed in the microwave glow discharge method.
From the above, an electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 6.
It was In this example, the variation pattern of the carbon content in the photoconductive layer was used.
As shown in FIG. 7, the carbon content on the surface of the substrate is adjusted to the photoconductive layer.
CH introduced when forming _Four Change the flow rate of each photoconductor
It changed by doing.

As a result of evaluation in the same manner as in Example 5, the same results as in Table 11 were obtained. <Example 7> A substrate subjected to the same pretreatment as in Example 1 was used and the electrophotographic photosensitive member manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in.
In this example, in order to change the fluorine content in the photoconductive layer as shown in FIG. 13, the flow rate of SiF ₄ introduced at the time of forming the photoconductive layer was changed. And the fluorine content in the photoconductive layer is SIMS (CAMECA IMS-3).
Elemental analysis by F) showed 3a near the substrate.
t. ppm, 40 at. It was ppm. (I) Canon electrophotographic copying machine NP
-7550 was installed in the electrophotographic device modified for experiments,
White spots, halftone spots before the accelerated durability test,
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Example 1 and Example 5. The ghost was evaluated as follows. Ghost: A Canon ghost test chart (part number: FY9-9040) with a black circle with a reflection density of 1.1 and ¢ 5 mm is placed on the front edge of the image on the platen, and a Canon halftone chart is placed on it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion of the ghost chart observed on the halftone copy in the copied images when they were overlapped was measured. In each case, ◎ means "especially good", ○ means "good", Δ means "no problem in practical use", and × means "problem in practical use".

The results are summarized in Table 13. (II) Next, the produced electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-7550 for an experiment, and an accelerated durability test equivalent to 3.5 million sheets was conducted. Then, electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The results are shown in Table 1.
It shows collectively in 4. From the results shown in Tables 13 and 14, it is possible to produce an electrophotographic photosensitive member having very excellent image characteristics and durability by setting the fluorine content in the photoconductive layer in the range of 95 atomic ppm or less. Was shown. <Embodiment 8> By using the substrate surface treating apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 15 in the same manner as in Example 7. Then, the produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 7. The results were exactly the same as in Table 13 and Table 14. <Embodiment 9> A substrate subjected to the same pretreatment as in Embodiment 1 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions of 16. In this experiment, the flow rate of CH ₄ introduced at the time of forming the surface layer was changed so that the amount of carbon contained in the surface layer was changed.

The produced electrophotographic photosensitive member was set in an electrophotographic apparatus which was modified from Canon copier NP-7550 for experiment, and the charging ability, residual potential, image evaluation before endurance, accelerated endurance test equivalent to 3.5 million sheets were carried out. The subsequent image evaluation was performed by the method described below. Charging ability: Performed in the same manner as in Example 1. Residual potential ... The same operation as in Example 1 was performed. Image evaluation after endurance: Limit samples of 5 grades were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 grades. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 17. As is clear from the table, when the carbon content is 40 to 90 atom%, a remarkable improvement in charging ability and durability is observed. <Embodiment 10> The substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), a microwave glow discharge method was performed as in Example 9.
Electrophotographic photoreceptors were produced under the production conditions shown in Table 18. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer.
The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 9. As a result, the same results as in Table 17 were obtained. <Embodiment 11> A substrate subjected to the same pretreatment as that of Embodiment 1 by the substrate surface treatment apparatus shown in FIG. 1 was subjected to a high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions of 19.
In this experiment, the flow rates of H ₂ and / or SiF ₄ introduced at the time of forming the surface layer were changed so as to change the amounts of hydrogen atoms and fluorine atoms contained in the surface layer.

The produced electrophotographic photosensitive member was placed in an electrophotographic apparatus modified from Canon Copier NP-7550 for experiments, and the three items of residual potential, sensitivity and image deletion were evaluated. Residual potential ... The same operation as in Example 1 was performed. Sensitivity ... The same as in Example 1. The results obtained are shown in Table 20. As is clear from Table 20, the sum of hydrogen content and fluorine content in the surface layer is 30
When the content of fluorine is within the range of up to 70 atomic% and the content of fluorine is within the range of 20 atomic% or less, good results can be obtained for both the residual potential and the sensitivity, and the image deletion under strong exposure can be significantly suppressed. all right. <Embodiment 12> By using the substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 21 in the same manner as in Example 10. The He flow rate is 2000s including the H ₂ flow rate.
The internal pressure was kept constant by changing the pressure to be constant at ccm. The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 10. As a result, the same results as in Table 20 were obtained. <Example 13> Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 1 by the substrate surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 22. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 23 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this example, the value of SiF ₄ / SiH ₄ was 10 to 10 so that the content of fluorine in the photoconductive layer could be distributed as shown in FIGS.
The flow rate was smoothly changed within the range of 50 ppm to prepare four types of electrophotographic photosensitive members. An electrophotographic photosensitive member was also produced under the same conditions except that it did not contain fluorine. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, chargeability, sensitivity, residual potential, white spots, halftone unevenness, ghost ... Evaluation similar to that of Example 1 Temperature characteristics ... Put it in a copier modified for experiments, change the surface temperature of the electrophotographic photosensitive member to 30 to 45 ° C, apply a high voltage of +6 kV to the charger, perform corona charging, and use the surface electrometer to measure the surface potential of the dark area. To measure. The change in the surface temperature of the dark portion with respect to the surface temperature of the photoconductor is approximated by a straight line, and the slope is defined as "temperature characteristic", which is expressed in units of [V / deg]. ⊚ is extremely excellent. ○ is excellent. △ is practically no problem. × It is not practical. The above results are shown in Table 24. From the table, it is understood that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, electrophotographic characteristics including ghost and temperature characteristics are improved. <Example 14> The substrates shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 1 by the substrate surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 22. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 25 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this example, the content of fluorine in the photoconductive layer was kept constant, and the content of oxygen was adjusted so as to have a distribution form shown in FIGS.
The flow rate was changed smoothly within the range of O ₂ / SiH ₄ value of 10 to 50 ppm to prepare four types of electrophotographic photosensitive members. An electrophotographic photosensitive member was also produced under the same conditions except that oxygen was not contained. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface fog, chargeability, sensitivity, residual potential, white spots, halftone unevenness, ghost ... Evaluation similar to that in Example 13 Potential shift ... Electrophotographic photoreceptor was set in experimental apparatus and +6 kV was applied to the charger. A high voltage is applied, corona charging is performed, and the surface potential of the dark portion of the electrophotographic photosensitive member is measured by a surface potential meter. At this time, the dark surface potential immediately after the voltage is applied to the charger is V _d0 and the dark surface potential after 2 minutes is V _d . Then, the difference between V _d0 and V _d is the amount of potential shift. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 26. From the table, when the photoconductive layer contains fluorine, and further contains oxygen atoms,
It can be seen that the electrophotographic characteristics including the temperature characteristics and the potential shift are improved.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

[Table 8]

[0057]

[Table 9]

[0058]

[Table 10]

[0059]

[Table 11]

[0060]

[Table 12]

[0061]

[Table 13]

[0062]

[Table 14]

[0063]

[Table 15]

[0064]

[Table 16]

[0065]

[Table 17]

[0066]

[Table 18]

[0067]

[Table 19]

[0068]

[Table 20]

[0069]

[Table 21]

[0070]

[Table 22]

[0071]

[Table 23]

[0072]

[Table 24]

[0073]

[Table 25]

[0074]

[Table 26] (Second invention) An electrophotographic photosensitive member having a structure shown in FIGS. 5 (a) and 5 (b) is manufactured by the method for manufacturing an electrophotographic photosensitive member of the second invention, using an aluminum alloy cylinder as a conductive substrate. An example of the procedure for actually forming will be described using the pretreatment apparatus for the conductive substrate shown in FIG. 1 and the deposited film forming apparatus by the microwave CVD method shown in FIGS. 2A and 2B.

In FIG. 1, a lathe equipped with an air damper for precision cutting (PNEUMO PRECLSION INC.
A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. next,
The rotating flange of this lathe was vacuum chucked to the substrate, white kerosene was sprayed from the attached nozzle, and cutting powder was sucked from the vacuum nozzle also attached, while the peripheral speed was 1000 m / m.
The outer shape is 108 under the condition of in and feed rate of 0.01 mm / R.
Mirror cutting is performed so that it becomes mm. With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. Figure 1
The substrate pretreatment apparatus shown in (1) comprises a processing section 102 and a substrate transfer mechanism 103. The processing unit 102 is a substrate loading table 1
11, substrate cleaning tank 121, pure water contact tank 131, drying tank 1
41 and a substrate unloading table 151. Cleaning tank 12
1. The pure water layer contact tank 131 is also equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. Transport mechanism 1
Reference numeral 03 denotes a transfer rail 165 and a transfer arm 161. The transfer arm 161 includes a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the conductive substrate 101, and an air for moving the chucking mechanism 163 up and down. It consists of a cylinder 164. After cutting, the conductive substrate 101 placed on the input table 111 is transported to the cleaning tank 121 by the transport mechanism 103. The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution 122 in the cleaning tank 121. Next, the conductive substrate 101 is transferred to the transport mechanism 1
No. 03 was carried to the pure water contact tank 131, and pure water having a resistivity of 17.5 MΩ-cm kept at a temperature of 25 ° C. was supplied to the nozzle 13.
It is sprayed at a pressure of 2 to 50 kg · f / cm ² .
The conductive substrate 101 after the pure water contact step is transferred to the transport mechanism 1.
It is moved to the drying tank 141 by 03, and high-temperature high-pressure air is blown from the nozzle 142 to be dried. The conductive substrate 101 after the drying process is carried to the carry-out table 151 by the carrying mechanism 103.

Next, an amorphous film was formed on the surface of the conductive substrate after the cutting and pretreatment by the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b). A deposited film mainly composed of silicon is formed. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 20.
Material that can efficiently permeate into 1 and maintain vacuum tightness (eg quartz glass, alumina ceramics, etc.)
It is a microwave introduction dielectric window formed by. Reference numeral 203 denotes a waveguide for transmitting microwave power, which includes a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. Waveguide 203
Is connected to a microwave power supply (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212,
It is electrically connected to the electrode 212. The electrophotographic photoreceptor is manufactured using such a deposited film forming apparatus as follows. First, the reaction container 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the reaction container 2
The pressure in 01 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the heater 207 heats and holds the temperature of the substrate 205 at a predetermined temperature. Therefore, a raw material gas such as a silane gas as a raw material gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluting gas is supplied to the reaction vessel 20 through a gas introduction means (not shown).
Introduced in 1. At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz and introduces it into the reaction vessel 201 through the waveguide 203 and the dielectric window 202. Further, the discharge space 206
A DC power supply 211 electrically connected to the bias electrode 212 therein applies a DC voltage to the bias electrode 212 with respect to the substrate 205. Thus, in the discharge space 206 surrounded by the conductive substrate 205, the source gas is excited and dissociated by the energy of microwaves, and the electric field between the bias electrode 212 and the substrate 205 causes the source gas to steadily stay on the conductive substrate 205. A deposited film is formed on the surface of the substrate 205 while being subjected to ion bombardment. At this time, the rotating shaft 209 on which the conductive base 205 is installed is rotated by the motor 210, and the conductive base 205 is rotated around the central axis in the base generatrix direction, so that the conductive base 205 is evenly distributed over the entire circumference. Form a deposited film layer.

With such a manufacturing apparatus, for example, under the conditions shown in Table 6, it is possible to manufacture a light receiving member comprising a photoconductive layer and a surface layer, which are essential requirements of the present invention. According to such a procedure, the electrophotographic photosensitive member can be continuously and efficiently produced. In the present invention, the cleaning liquid used in the cleaning step is preferably water or water containing a surfactant added. The water quality can be any. The surfactant used in the washing step may be any of anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added. If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C.
C. or higher and 55.degree. C. or lower are suitable for the present invention. In the present invention, the use of ultrasonic waves in the cleaning step is important for obtaining the full effect of the present invention. The ultrasonic frequency is preferably 100 Hz or higher and 10 MHz or lower, more preferably 1 kHz or higher and 5 MHz or lower, and optimally 10 kHz or higher and 100 kHz or lower. The ultrasonic output is preferably 10 W or more and 100 kW or less, more preferably 100 W or more and 10 kW or less.

Water of water used in the pure water contact step of the present invention
Quality is very important, and semiconductor grade pure water, especially ultra
LSI grade ultrapure water is preferred. Specifically, the water temperature
As the resistivity at 25 ° C, 1 MΩ-cm or more is preferable.
4 MΩ-cm or more, optimally 10 MΩ-cm or more
Suitable for the present invention. The amount of fine particles is 0.2 μm
The above is less than 100,000 pieces per milliliter, preferably
Ku or 10,000 or less, optimally 1000 or less
Suitable for light. The total number of viable bacteria is 1 mi
1000 or less, preferably 100 or less
Below, optimally 10 or less are suitable for the present invention. Organic
The physical quantity (TOC) is 100 mg or less per liter,
10 mg or less, optimally 2 mg or less is suitable for the present invention.
Is suitable. As a method of obtaining water of the above water quality,
Charcoal method, distillation method, ion exchange method, filter filtration method, reverse
Penetration method, ultraviolet sterilization method, etc. are available.
It is hoped that they will be used in combination to raise the required water quality.
Good When bringing pure water into contact with the conductive substrate surface,
It is desirable to apply pressure and spray. When spraying
If the water pressure is too weak, the effect of the present invention will be small.
If it is too strong, on the image of the obtained electrophotographic photoreceptor, especially
A pear-like pattern appears on the halftone image.
U Therefore, the pressure of water is 2 kgf / cm ² Since
Upper, 300kgf / cm² Below, preferably 10kg
・ F / cm² Above, 200kgf / cm² Below, optimal
20kgf / cm² Above 150kgf / cm
² The following are suitable for the present invention. However, in the present invention
Pressure unit kg ・ f / cm² Is the gravity kilogram per square centimeter
1 m · f / cm² Is 9806
Equal to 6.5 Pa. In the method of spraying pure water of the present invention
Sprays high pressure water from a nozzle
Method or pumping water with high pressure air and nose
Method before mixing and spraying with air pressure
Etc.

The flow rate of the pure water of the present invention is 1 liter / mi per conductive substrate in view of the effect of the invention and economical efficiency.
n or more and 200 liters / min or less, preferably 2 liters / min or more and 100 liters / min or less, optimally 5 liters / min or more, 50 liters / min
The following are suitable for the present invention. The temperature of pure water of the present invention is
If it is too high, an oxide film will be formed on the conductive substrate, causing the deposited film to peel off, etc., and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of pure water is 5 ° C or higher, 90 ° C.
C. or less, preferably 10.degree. C. or more and 55.degree. C. or less, optimally 15.degree. C. or more and 40.degree. C. or less are suitable for the present invention. If the treatment time of the water contact treatment is too long, an oxide film is generated on the conductive substrate, and if it is too short, the effect of the present invention is small, so 10 seconds or longer, 30 minutes or shorter, preferably 20 seconds or longer, 20 minutes or less, optimally 30 seconds or more and 10 minutes or less are suitable for the present invention. In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film. If the time from cutting to water contact treatment is too long, an oxide film will be formed again on the substrate surface, and if it is too short, the process will not be stable. Therefore, the time is preferably 1 minute or more and 16 hours or less, more preferably 2 minutes or more. 8 hours or less, optimally 3
Minutes or more and 4 hours or less are suitable for the present invention. If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable. Therefore, preferably 1 minute or more and 8 hours or less,
More preferably, 2 minutes or more and 4 hours or less, most preferably 3 minutes or more and 2 hours or less are suitable for the present invention.

As the conductive substrate used in the present invention,
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, or an electrically insulating conductive substrate such as glass or ceramics, on which at least the light receiving layer is formed is formed. A substrate whose surface is subjected to a conductive treatment can be used, but a metal is preferable from the viewpoint of mechanical strength and the like. In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive substrate in order to eliminate an image defect due to an interference fringe pattern that appears in a visible image. The unevenness provided on the surface of the conductive substrate is described in JP-A-60-168156 and JP-A-6-168156.
It is produced by a known method described in, for example, 0-178457 and 60-225854. Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. Unevenness due to a plurality of spherical trace depressions provided on the surface of the conductive substrate is disclosed in Japanese Patent Application Laid-Open No. 61-61.
It is produced by a known method described in Japanese Patent Publication No. 231561.

The photoconductive layer in the present invention is composed of a photoconductive layer composed of nc-SiC (H) containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements from the side of the conductive substrate, and has desired photoconductive characteristics. In particular, it has charge retention properties, charge generation properties, and charge transport properties. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in the planes parallel to the surface of the conductive substrate, and non-uniform in the thickness direction of the layer. At each point in the film thickness direction, the content on the side of the conductive substrate is high, and the content on the side of the surface layer is low. The content of carbon atoms is 0.5 at the surface on the side where the conductive substrate is provided or near the surface.
% Or less, the adhesion with the conductive substrate is improved and
The function of preventing the injection of charges deteriorates, and the effect of improving the charging ability due to the decrease in electrostatic capacity disappears. If it is 50% or more, a residual potential will be generated. Therefore, it is practically 0.5 to 50 atomic%, preferably 1 to 40 atomic%, and optimally 1 to 30 atomic%. Further, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for making it happen. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the content of carbon atoms. Therefore, the content of hydrogen atoms on the surface of the conductive substrate is preferably 1 to 40 atom%, more preferably 5 to 3
It is desirable that the content is 5 atomic%, optimally 10 to 30 atomic%. In the present invention, the halogen atom contained in the photoconductive layer includes fluorine, chlorine bromine, iodine and the like,
Fluorine is preferable. The halogen atom contained in the present invention suppresses the agglomeration of carbon atoms and hydrogen atoms contained in the photoconductive layer and reduces the local level density in the band gap, thus improving the ghost and improving the quality uniformity. Exerts the effect of improving. Content of halogen atom is 1 atom ppm
If the amount is less, the effect of improving the ghost by the fluorine atom is not sufficient, and if it exceeds 95 atom ppm, the film quality is deteriorated and the ghost phenomenon occurs. Therefore,
The halogen atom contained in the photoconductive layer is practically 1 to
95 atomic ppm, more preferably 3 to 80 atomic ppm,
Optimally, it is desired to be 5 to 50 atomic ppm. Experiments have shown that when carbon atoms are contained in the photoconductive layer in the above-mentioned range, by setting the content of halogen atoms in the above range, the photoconductive characteristics, image characteristics, and durability characteristics are significantly improved. Confirmed by.

In addition, in the present invention, the halogen atoms contained in the photoconductive layer are nonuniform in the layer thickness direction,
And by distributing so as to increase on the substrate side,
It is preferable because it has a function of relaxing internal stress generated as the content of carbon atoms changes in the layer thickness direction. Further, the inclusion of oxygen atoms, which is an essential condition of the present invention, more effectively relieves the internal stress in the photoconductive layer by the synergistic effect with the halogen atom and improves the mobility of carriers in the photoconductive layer. Characteristics such as ghost, and potential shift are also greatly improved. The content of oxygen atoms in the photoconductive layer of the present invention has a delicate synergistic effect with carbon atoms and halogen atoms, and is preferably 10 to 5000 atom ppm. When the content of oxygen atoms is less than 10 atomic ppm, it is not possible to sufficiently improve the adhesion of the film and suppress the occurrence of abnormal growth, resulting in increased image defects. The content of oxygen atoms is 5000 atom ppm
If it exceeds the above range, the electrical characteristics will not be sufficient to sufficiently cope with the speeding up of electrophotography. Furthermore, in the present invention, at least the oxygen atoms contained in the nc-SiC photoconductive layer are nonuniformly distributed in the layer thickness direction, whereby the internal stress of the deposited film can be more effectively relieved, and the structural defects of the film can be reduced. Can be greatly suppressed. Therefore, in particular, since deterioration of the photoconductive layer due to continuous use for a long period of time is suppressed, deterioration of electrophotographic properties such as sensitivity, residual potential and potential shift after long-term durability can be significantly reduced. In the present invention,
The photoconductive layer is formed by a vacuum deposition film forming method with appropriate numerical conditions of film forming parameters set so as to obtain desired characteristics. Specifically, the glow discharge method (low frequency CVD method) is used. AC discharge CVD method such as high-frequency CVD method or microwave CVD method, or DC discharge CV
Method D) is preferable. By glow discharge method nc-SiC:
In order to form the H photoconductive layer, basically, a source gas for supplying Si, which can supply silicon atoms (Si), a source gas for supplying C, which can supply carbon atoms (C), and hydrogen atoms. A raw material gas for supplying H capable of supplying (H) is introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and a glow discharge is caused in the reaction vessel to preliminarily set a predetermined position. Nc- on the surface of a predetermined conductive substrate installed
A layer made of SiC: H may be formed.

Si supply gas used in the present invention
Possible substances include SiH_Four, Si₂ H₆ , Si₃
 H₈ , Si_Four H_TenEtc. in a gas state, or can be gasified
Silicon hydride (silanes) shall be used effectively.
In addition, ease of handling during layer preparation, Si supply effect
SiH in terms of good rate_Four , Si₂ H₆ Is preferred
As. In addition, the raw material gas for supplying these Si
H as needed₂, He, Ar, Ne and other gases
You may use it after diluting it. In the present invention, a carbon atom
As a raw material for introduction, at normal temperature and pressure
Gaseous or easily gasses at least under layer-forming conditions
It is desirable that a material that can be made into be adopted. Carbon atom
(C) Effectively used as a source gas for introduction
The starting material used has C and H as constituent atoms, for example,
For example, saturated hydrocarbons with 1 to 5 carbon atoms, ethylen with 2 to 4 carbon atoms
Hydrocarbons, acetylene hydrocarbons with 2 to 3 carbon atoms, etc.
Is mentioned. Specifically, as a saturated hydrocarbon,
Tan (CH_Four ), Ethane (C₂ H₆ ), Propane (C₃ 
H₈ ), N-butane (n-C_Four H_Ten), Pentane (C_Five 
H₁₂), Ethylene-based hydrocarbons include ethylene (C₂ 
H_Four ), Propylene (C₃ H₆), Butene-1 (C_Four H₈
 ), Butene-2 (C_Four H₈ ), Isobutylene (C_Four H ₈
 ), Penten (C_Five H_Ten), With acetylene hydrocarbons
Then, acetylene (C ₂ H₂ ), Methyl acetylene
(C₃ H_Four ), Butin (C_Four H₆ ) And the like.

In addition, a raw material gas containing Si and C as constituent atoms
For example, Si (CH₃ )_Four , Si (C₂ H_Five )_Four etc
Alkyl silicides of can be mentioned. Light hydrogen atom
In addition to the above, H can be introduced structurally into the conductive layer.₂ ,Ah
Ruiha SiH_Four , Si₂ H₆ , Si₃ H₈ , Si_Four H_Ten
For supplying silicon hydride and Si, such as
Electric discharge is generated by coexisting with silicon compound in the reaction vessel.
You can also do it by Used in the present invention
Halogen atoms used include fluorine, chlorine, bromine, and iodine.
Fluorine is preferable, although there is an element such as iodine. In the present invention
Specific examples of the fluorine atom supply gas that can be preferably used
HF, F₂ , BrF, ClF, ClF₃ , BrF
₃ , BrF_Five , IF₃ , IF₇ Halogen compounds such as
You can get it. In addition, a silicon compound containing a fluorine atom
As a silane derivative substituted with a so-called fluorine atom
Specifically, SiF_Four , Si₂ F₆ Fluorinated silica
Elemental elements can be mentioned as preferable ones, and Si
H₃ F, SiH₂ F₂ , SiHF_Four Fluorine-substituted hydrogen such as
Silicon carbide can also be mentioned as an effective source gas. light
To control the amount of hydrogen atoms contained in the conductive layer,
In addition to the selection of the source gas as described above, for example, the conductive substrate
Temperature, raw material used to contain hydrogen atoms
Control the amount to be introduced into the reaction vessel, the discharge power, etc.
Yes. Further, in the present invention, the photoconductive layer may be added as necessary.
It is preferable to include an atom (M) that controls conductivity by
Good Atoms that control conductivity are well distributed in the photoconductive layer.
It may be contained in a uniformly distributed state, or in a layer
In the thickness direction, there are parts that contain non-uniform distribution.
May be.

As the atom for controlling the above-mentioned conductivity,
So-called impurities in the conductor field can be mentioned.
Atoms belonging to Group III of the periodic table that give p-type conduction characteristics
(Hereinafter abbreviated as "Group III atom") or n-type conduction characteristics
Atoms belonging to Group V of the Periodic Table that give properties (hereinafter referred to as “Group V
Abbreviated as "child") can be used. Group III atom
Specifically, boron (B), aluminum (A
l), gallium (Ga), indium (In), tariu
(Tl), etc., and B, Al, and Ga are particularly preferable.
It Specific examples of the group V atom include phosphorus (P) and arsenic
(As), antimony (Sb), bismuth (Bi), etc.
Yes, P and As are particularly preferable. Contained in the photoconductive layer
The content of atoms (M) that control conductivity is
It is 1 × 10^-3~ 5 x 10^Four Atomic ppm, more preferred
Kuha 1 × 10^-2~ 1 x 10 ^Four Atomic ppm, optimally 1x
10^-1~ 5 x 10³ It is desirable to set it to atomic ppm.
In particular, the content of carbon atoms (C) in the photoconductive layer is 1 ×
10³ If it is less than atomic ppm, it is contained in the photoconductive layer.
The content of atoms (M) is preferably 1 × 10^-3~ 1
× 10³ Atomic ppm is desirable, carbon atom
The content of (C) is 1 × 10³ When exceeding atomic ppm
Is preferably 1 x 10 as the content of atoms (M).
^-1~ 5 x 10^Four It is desirable to set it to atomic ppm. Light
An atom that controls conductivity, such as a group III source,
To structurally introduce a child or group V atom, a layer is formed.
In the case of
The raw material for atom introduction is introduced into the reaction vessel in a gas state,
If it is introduced together with other gas for forming the electric layer,
Good. Raw material for introducing Group III atoms or Group V source
At room temperature and atmospheric pressure, the raw materials for introducing the child can be
Gas, or at least easily under layering conditions.
It is desirable to adopt a material that can be converted into a product. like that
As a raw material for introducing a Group III atom, specifically, boron is used.
For atom introduction, B₂ H₆ , B_Four H_Ten, B_Five H₉ ，
B_Five H₁₁, B₆ H_Ten, B₆ H₁₂, B₆ H₁₄Borohydride, etc.
Elementary, BF₃ , BCl₃ , BBr₃ Boron halide, etc.
Is mentioned. In addition, AlCl₃ , GaCl₃ , Ga
(CH₃ )₃ , InCl₃ , TlCl₃ And so on
You can

In the present invention, a raw material for introducing a Group V atom is effectively used. For introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ , etc., PH ₄ I, PF
₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr
₅ , and phosphorus halides such as PI ₃ are included. Besides this, A
sH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , S
bCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ etc. are also V
It can be cited as an effective starting material for introducing a group atom. Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary. Further, the photoconductive layer of the light receiving member of the present invention comprises a group Ia, a group IIa,
You may contain at least 1 sort (s) of element selected from VIa group and VIII group. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there. Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and specific examples of the group IIa atom include beryllium (Be), magnesium (Mg) and calcium. (Ca), strontium (Sr), barium (Ba)
Etc. can be mentioned.

Further, as the group VIa atom, specifically,
Chromium (Cr), molybdenum (Mo), tungsten (W), etc. can be mentioned, and as the Group VIII atom,
Iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned. In the present invention, the layer thickness of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the photoconductive layer is preferably 5 to 50 μm, and more preferably 10
˜40 μm, optimally 20 to 30 μm. Nc-S having characteristics capable of achieving the object of the present invention
In order to form a photoconductive layer made of iC (H), it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction container as desired. In the present invention, between the photoconductive layer and the surface layer, a second photoconductive layer having a silicon atom as a base and composed of hydrogen atoms and / or halogen atoms and having substantially 0 atomic% carbon atoms is provided. In this case, the present invention is particularly effective. The second photoconductive layer is intended to enhance absorption of long-wavelength light and improve sensitivity, and to reduce ghosts because the mobility of carriers having a polarity opposite to the charging polarity is better than that of the above photoconductive layer. It is provided for. In the present invention, the second photoconductive layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of the film forming parameters so that desired characteristics can be obtained. Specifically, glow discharge method (low frequency CVD method, high frequency CVD method or microwave C
AC discharge CVD method such as VD method, or DC discharge CVD method
Method). In order to form the nc-Si: H photoconductive layer by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and an H supply that can supply hydrogen atoms (H). A raw material gas for use in a reaction vessel whose inside can be decompressed in a desired gas state to cause glow discharge in the reaction vessel, and a predetermined conductive substrate installed in a predetermined position in advance. A layer of nc-Si: H may be formed on the surface. In the present invention, the layer thickness of the second photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects.
Preferably 0.5 to 15 μm, more preferably 1 to 10
[mu] m, optimally 1 to 5 [mu] m is desirable.

The temperature (Ts) during film deposition of the conductive substrate used in the present invention is appropriately selected according to the layer design, but in the usual case, it is preferably 20 to 500.
° C, more preferably 50-480 ° C, optimally 100-
The temperature is preferably 450 ° C. In the light receiving member of the present invention, a layer region whose composition is continuously changed may be provided between the photoconductive layer and the surface layer. By providing the layer region, the adhesion between the layers can be further improved. Further, in the light receiving member of the present invention, the photoconductive layer has a layer region containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction on the side of the conductive substrate. Is desirable. The surface layer in the present invention is composed of a non-single-crystal material containing silicon atoms, carbon atoms, hydrogen atoms and halogen atoms as constituent elements. The surface layer is substantially free of conductivity controlling substances such as those contained in the photoconductive layer. The carbon atoms contained in the surface layer may be uniformly distributed in the layer, or may be contained in the layer thickness direction in a uniform manner but contained in a non-uniformly distributed state. There may be a part that does. However,
In either case, it is necessary that the content be evenly distributed in the in-plane direction parallel to the surface of the conductive substrate in order to obtain uniform properties in the in-plane direction.
The carbon atoms contained in the entire surface area of the surface layer in the present invention have effects such as high dark resistance and high hardness. The content of carbon atoms contained in the surface layer is preferably 40 to 90.
Atomic%, more preferably 45-85 atomic%, optimally 50
It is desirable to be set to -80 atom%.

The hydrogen atoms and halogen atoms contained in the surface layer in the present invention are nc-SiC (H, X).
Compensating for dangling bonds existing in the film has the effect of improving the film quality, and reduces the carriers trapped at the interface between the photoconductive layer and the surface layer, thus improving the image deletion. Further, since the halogen atom improves the water repellency of the surface layer, it also reduces the high humidity flow due to the adsorption of water vapor. The content of halogen atoms in the surface layer is 20 atomic% or less, and the sum of the content of hydrogen atoms and halogen atoms is preferably 30 to 70 atomic%, more preferably 35 to 65 atomic%, optimally Is 40 ~
It is desirable to set it to 60 atom%. Further, in the present invention, the surface layer may contain at least one element selected from Group Ia, Group IIa, Group VIa and Group VIII of the Periodic Table.
The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, the content is evenly distributed with no uneven distribution.
It is also necessary in order to make the characteristics uniform in the in-plane direction. Specific examples of the group Ia atom include lithium (L
i), sodium (Na), potassium (K), and the group IIa atom includes beryllium (B).
e), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like. Further, as the group VIa atom, specifically,
Chromium (Cr), molybdenum (Mo), tungsten (W), etc. can be mentioned, and as the Group VIII atom,
Iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned.

In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.0, from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness is 5 to 20 μm, optimally 0.1 to 10 μm. In the present invention, in order to form the surface layer composed of nc-SiC (H, X), a vacuum deposition method similar to the above-mentioned method of forming the photoconductive layer is adopted. When forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The temperature of the conductive substrate is appropriately selected in an optimum range, but is preferably 20 to 500 ° C, more preferably 50 to 480 ° C, and most preferably 100 to 450 ° C. The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Tor.
r, more preferably 5 × 10 ^{−5 to 3} Torr, most preferably 1 × 10 ^{−4 to} 1 Torr. In the present invention, the ranges described above are mentioned as desirable numerical ranges of the conductive substrate temperature and the gas pressure for forming the surface layer, but these layer preparation factors are not usually independently determined separately. It is desirable to determine the optimum value of each layer production factor based on mutual and organic relations so as to form a surface layer having desired characteristics. In the present invention, the energy for generating plasma may be DC, high frequency, microwave, or the like. In particular, when microwave is used as the energy for generating plasma,
Microwaves are absorbed by the adsorbed water and the change in the interface becomes more prominent, so that the effect of the present invention becomes more prominent.

In the present invention, when microwave is used for plasma generation, any microwave power may be used as long as it can generate discharge, but 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW or less is the main power. It is suitable for carrying out the invention. The present invention is
Although it can be applied to any electrophotographic photoreceptor manufacturing method, in particular, a base film is provided so as to surround the discharge space, and a microwave is introduced from at least one end side of the base material to form a deposited film. If you do it has a great effect. Hereinafter, the effects of the present invention will be specifically described using examples, but the present invention is not limited to these. <Example 15, Example 16 and Comparative Example 5> Example 15 Diameter 108 m made of aluminum having a purity of 99.5%
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for manufacturing an electrophotographic photosensitive member according to the present invention described above, and 15 minutes after the completion of the cutting step, as shown in FIG. The surface of the substrate was pretreated under the conditions shown in Table 27 by the surface treatment apparatus shown in FIG. However, in this example, as the surfactant, polyethylene glycol nonylphenyl ether was used as a 1 wt% aqueous solution. On the aluminum cylinder thus pretreated, according to the procedure detailed above, using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. An electrophotographic photosensitive member having the layer structure shown in (a) was produced. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. 20, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly. At this time, the carbon content at the interface of the photoconductive layer with the substrate was set to about 30 atom%. For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the ratio of signal intensity by Auger spectroscopy.

The surface layer of the produced electrophotographic photosensitive member was visually evaluated, and then the copying machine NP6650 manufactured by Canon was used.
Was installed in an electrophotographic apparatus modified for experiments, and the following items were evaluated for electrophotographic characteristics. Surface Haze The produced electrophotographic photosensitive member was visually inspected for the degree of surface haze. ◎: No clouding ○: Partially cloudy △: Partially cloudy at several places and ×: Cloudy on the entire surface. Charging ability / sensitivity / residual potential / potential shift Charging ability: An electrophotographic photoconductor is installed in the experimental device, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential meter is used to measure the dark surface of the electrophotographic photoconductor. Measure the potential. Sensitivity: The electrophotographic photoreceptor is charged to a constant dark surface potential. Then, the light image is immediately irradiated. The light image is emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. The exposure amount is adjusted so that the light portion surface potential becomes a predetermined potential, and the exposure amount at this time is taken as the sensitivity. Residual potential: The electrophotographic photoreceptor is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter.

Potential shift: The electrophotographic photosensitive member is installed in an experimental apparatus, a high voltage of +6 kV is applied to the charger, corona charging is performed, and the surface potential of the dark portion of the electrophotographic photosensitive member is measured by a surface potential meter. At this time, the dark surface potential immediately after the voltage is applied to the charger is V _d0 and the dark surface potential after 2 minutes is V _d . Then, the difference between V _d0 and V _d is the amount of potential shift. White spots, halftone unevenness, ghosts ... Put the electrophotographic photoconductor in a copying machine that was modified from Canon Copier NP6650 for experiments, and transfer it by a normal electrophotographic process to form an image on the paper surface. The images were evaluated by. White Poti ... Canon made black chart (Part number: FY9
The number of white spots having a diameter of 0.2 mm or less in the same area of the copy image obtained by placing −9073) on the platen was counted. Halftone unevenness ... Image density of 100 points with a circular area of 0.05 mm in diameter as one unit on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on the platen and copied. Was measured and the variation in the image density was evaluated. Ghost: A Canon ghost test chart (Part number: FY9-9040) with a reflection density of 1.1 and a black circle of ¢ 5 mm attached to it is placed on the front edge of the image on the platen, and a Canon halftone chart is overlaid on it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion of the ghost chart observed on the halftone copy in the copy image when left was measured.

In each case, ⊚ is “excellently good”, ◯ is “good”, Δ is “no practical problem”, and “is practically problematic”. Example 16 Table 30 was prepared by the high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 on a substrate which had been pretreated in the same manner as in Example 15 by the substrate surface treating apparatus shown in FIG.
An electrophotographic photosensitive member having the layer structure shown in FIG. 5B was manufactured under the manufacturing conditions shown in FIG. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. 20, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly to change the electrophotographic photosensitive member. Was produced. The initial flow rate of CH ₄ was adjusted so that the carbon content on the substrate-side surface of the photoconductive layer was about 30 atom%. For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the signal intensity by Auger spectroscopy. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 15. The results are shown in Table 29 together with the result of Example 15. Comparative Example 5 A conductive substrate similar to that of Example 15 was cut in the same procedure, and the cut conductive substrate was subjected to a conventional conductive substrate cleaning apparatus shown in FIG. Was processed. The conductive substrate cleaning apparatus shown in FIG. 3 includes a processing tank 302 and a substrate transfer mechanism 303. The processing tank 302 includes a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361, and the transfer arm 361 includes a rail 365.
A moving mechanism 362 that moves up, a chucking mechanism 363 that holds the base 301, and the chucking mechanism 36.
It is composed of an air cylinder 364 for moving up and down 3.

After cutting, the substrate 3 placed on the input table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. A cleaning process for removing cutting oil and chips adhering to the surface is performed by trichloroethane (trade name: ETERNA VG manufactured by Asahi Kasei Co., Ltd.) 322 in the cleaning tank 321. After cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. In the same manner as in Example 15, the conventional substrate pretreatment was performed under the conditions shown in Table 32, ie, the substrate, the charge transport layer, the charge generation layer, and the surface layer.
A so-called function-separated type electrophotographic photosensitive member having a layer structure was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 15, and together with the results of Examples 15 and 16, the results are shown in Table 2.
9 shows. As is clear from Table 29, according to the method of the present invention, the sensitivity is improved and the residual potential is kept low. More particularly, fog on the surface of the photoconductor, potential shift,
It can be seen that the halftone unevenness and the ghost have excellent characteristics. Further, it is understood from Examples 15 and 16 that the sensitivity is improved by providing the second photoconductive layer without impairing other characteristics. <Example 17, Example 18 and Comparative Example 6> Example 17 FIGS. 2 (a) and 2 are formed on a substrate obtained by pretreating the same substrate as in Example 15 by the substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 33. The produced electrophotographic photosensitive member is Example 1
The same evaluation was performed. As a result, exactly the same results as in Example 15 were obtained. Example 18 A substrate obtained by pretreating the same substrate as in Example 15 by the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 34. The produced electrophotographic photosensitive member is Example 1
The same evaluation as in 5 was performed. As a result, exactly the same results as in Example 16 were obtained. Comparative Example 6 FIGS. 2 (a) and 2 (b) are formed on a substrate obtained by pretreating the same substrate as in Comparative Example 5 by the substrate surface treatment apparatus shown in FIG.
Using the apparatus for producing an electrophotographic photosensitive member shown in FIG. 1, a so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate, a charge transport layer, a charge generating layer and a surface layer under the conditions shown in Table 35 by a microwave glow discharge method. The body was made. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 16. As a result, the same result as in Comparative Example 5 was obtained. <Example 19 and Comparative Example 7> Example 19 The electrophotographic photosensitive member manufacturing apparatus shown in FIG. 4 was used on a substrate which was pretreated in the same manner as in Example 15 by the substrate surface treating apparatus shown in FIG. An electrophotographic photosensitive member was manufactured by the high-frequency glow discharge method under the manufacturing conditions shown in Table 36 according to the procedure detailed above. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 21 and 22, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer was changed to obtain two types of carbon. A photoconductor was prepared. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to about 30 atom%. The carbon atom content was determined in the same manner as in Example 15.

The surface of the produced electrophotographic photosensitive member was clouded, and the Canon copying machine NP6650 was installed in an electrophotographic apparatus modified for experiments. evaluated. The results are shown in Table 3.
7 shows. Comparative Example 7 Example 19 was carried out on a substrate pretreated in the same manner as Comparative Example 5.
In the same manner as in, an electrophotographic photosensitive member was produced with the carbon content patterns shown in FIGS. 23 and 24, and the same evaluation as in Example 19 was performed. The results are shown in Table 37 and shown in Example 19
The evaluation results are also shown. It can be seen that, in the carbon content variation pattern of the photoconductive layer according to the present invention, particularly good results are obtained in comparison with the result of Comparative Example 7 regarding surface haze, sensitivity, and residual potential halftone unevenness. Example 20 and Comparative Example 8 Example 20 Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate that had been subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. Table 38 is carried out in the same manner as in Example 19 except that a microwave glow discharge method is used by using an apparatus for producing a photographic photoreceptor.
An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in. In this example, the change pattern of the carbon content in the photoconductive layer is shown in FIG.
The flow rate of CH ₄ introduced at the time of forming the photoconductive layer was changed in order to change it as shown in Nos. 1 and 22. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer is
It was set to about 30 atom%. The electrophotographic photoconductor thus produced gave the same results as in Example 19. Comparative Example 8 The same procedure as in Example 20 was carried out on a substrate pretreated in the same manner as in Comparative Example 5 by the substrate surface treatment apparatus shown in FIG.
An electrophotographic photosensitive member was produced with the carbon content pattern shown in FIGS. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 20, the same results as in Comparative Example 7 were obtained. Example 21 A substrate pretreated in the same manner as in Example 15 with the substrate surface treatment apparatus shown in FIG. 1 was used, and the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 was used, according to the procedure detailed above.
Electrophotographic photoreceptors were produced by the high-frequency glow discharge method under the production conditions shown in Table 30. In this example, the carbon content change pattern in the photoconductive layer was changed by changing the flow rate of CH ₄ introduced at the time of forming the photoconductive layer by using FIG. The carbon content on the substrate-side surface of the photoconductive layer was identified by elemental analysis by Rutherford backscattering method.

The number of occurrences of cloudiness and spherical protrusions on the surface of the electrophotographic photosensitive member produced, and further, Canon copier NP6650
Was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, halftone unevenness, and ghost, and image quality were evaluated. Each item was evaluated by the following methods. Surface haze Evaluation was performed in the same manner as in Example 15. Number of Spherical Protrusions The entire surface of the produced electrophotographic photosensitive member was observed with an optical microscope to check the number of spherical protrusions having a diameter of 20 μm or more within an area of 100 cm ² . Results were obtained for each electrophotographic photosensitive member, and the one having the largest number of spherical projections was set as 100% for relative comparison. The results are classified as follows. ⊚ is less than 60% ◯ is 80 to 60% Δ is 100 to 80% Chargeability / sensitivity / residual potential / potential shift Evaluation was made in the same manner as in Example 1. White spot / halftone unevenness / ghost Evaluation was performed in the same manner as in Example 1. The results thus obtained are summarized in Table 39. From these results, the amount of carbon on the substrate-side surface of the photoconductive layer was 0.5 to 50% by raw material.
The improvement in the characteristics was observed, and extremely good results were obtained at 1 to 30 atom%. <Embodiment 22> A substrate surface-treated as shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), the electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 34 by the microwave glow discharge method according to the procedure detailed above. . In this example, the change pattern of the carbon content in the photoconductive layer is shown in FIG. 20, and the carbon content of the surface on the substrate side is changed by changing the flow rate of CH ₄ introduced during the formation of the photoconductive layer for each photoconductor. Was changed by. Then, as a result of evaluation in the same manner as in Example 21, the same results as in Table 26 were obtained. <Example 23 and Example 24> Example 23 Table 40 is shown by a high-frequency glow discharge method on a substrate pretreated in the same manner as in Example 15 using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photoreceptor was produced under the production conditions. In this example, the oxygen content in the photoconductive layer was kept constant, and the content of fluorine atoms was changed to the distribution shown in FIG. 25.
The charge amount of ₄ was changed. The content of fluorine atoms in the photoconductive layer of the electrophotographic photoreceptor thus formed is determined by SIMS (CAMEC
A IMS-3F). Oxygen atom content is about 50pp when the same measurement is performed.
It was constant at m. (I) Canon electrophotographic copying machine NP
The 6650 was installed in an electrophotographic apparatus modified for experiments, the potential shift was first measured in the same manner as in Example 15, and white spots, halftone spots, ghosts, etc. before the accelerated durability test were performed as images. The electrophotographic characteristics of No. 1 were evaluated in the same manner as in Example 15. The results are summarized in Table 41. (II) Next, the manufactured electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from Canon Copier NP6650 for experiments, and an accelerated durability test equivalent to 3 million sheets was performed. And
The electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The results are summarized in Table 42.

From the results shown in Tables 41 and 42, by setting the content of fluorine atoms in the photoconductive layer in the range of 95 atom ppm or less, an electrophotographic photoreceptor having excellent image characteristics and durability was obtained. It has been shown that it can be made. <Example 24> An electrophotographic photosensitive member was prepared on the substrate pretreated in the same manner as in Example 15 using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 4 by the high frequency glow discharge method under the manufacturing conditions shown in Table 43. Was produced. In this example, the content of fluorine atoms in the photoconductive layer was kept constant, and the amount of CO ₂ as a raw material gas charged was changed so that the content of oxygen atoms was changed. The content of oxygen atoms in the photoconductive layer of the electrophotographic photosensitive member thus formed is SIMS (CAMECA IMS-3).
It was conducted by elemental analysis according to F). When the same measurement was performed, the content of fluorine atoms was constant at about 20 ppm in any electrophotographic photosensitive member. (I) Canon electrophotographic copying machine NP
The 6650 was installed in an electrophotographic apparatus modified for experiments, the potential shift was first measured in the same manner as in Example 15, and white spots, halftone spots, ghosts, etc. before the accelerated durability test were performed as images. The electrophotographic characteristics of No. 1 were evaluated in the same manner as in Example 15. The results are summarized in Table 44. (II) Next, the manufactured electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from Canon Copier NP6650 for experiments, and an accelerated durability test equivalent to 3 million sheets was performed. And
The electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The results are summarized in Table 45.

From the results shown in Tables 44 and 45, when the content of oxygen atoms in the photoconductive layer was set in the range of 5000 atomic ppm or less, the electrophotography was excellent in terms of potential shift, image characteristics and durability. It has been shown that it is possible to make photoreceptors. Further, from the results of Example 23 and Example 24, it is also possible that the fluorine atom and the oxygen atom in the photoconductive layer fall within a specific content range, whereby the potential shift is significantly improved without impairing other characteristics. It was revealed. <Example 25 and Example 26> Example 25 The substrates shown in FIGS. 2 (a) and 2 (b) were formed on the substrate pretreated in the same manner as in Example 15 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 46 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. Then, the produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 23. The results were exactly the same as in Table 41 and Table 42. Example 26 The electrophotographic photoreceptor manufacturing apparatus shown in FIGS. 2 (a) and 2 (b) was used on a substrate pretreated in the same manner as in Example 1 by the substrate surface treating apparatus shown in FIG. By the microwave glow discharge method, various electrophotographic photosensitive members were produced under the production conditions shown in Table 47, except that only the flow rate of CO ₂ was changed. Then, the produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 24. Further, the content of oxygen atoms in the photoconductive layer of the electrophotographic photosensitive member was measured by SIMS. The results were exactly the same as in Tables 44 and 45.

From Example 25 and Example 26, it was found that the microwave discharge CVD method provided the same results as the high frequency discharge CVD method. <Example 27> By using the substrate surface treatment apparatus shown in FIG.
An electrophotographic photosensitive member was manufactured on the substrate pretreated in the same manner as in Example 15 by the high frequency glow discharge method under the manufacturing conditions shown in Table 48 using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. In this experiment, the flow rate of CH ₄ introduced at the time of forming the surface layer was changed so that the amount of carbon contained in the surface layer was changed. The produced electrophotographic photosensitive member is a copy machine N manufactured by Canon.
The P6650 was installed in the electrophotographic device modified for the experiment,
Chargeability, residual potential, image evaluation before endurance, and image evaluation after accelerated endurance test equivalent to 3 million sheets were performed by the following methods. Charging ability: Performed in the same manner as in Example 15. Residual potential ... The same operation as in Example 15 was carried out. Image evaluation after endurance: Limit samples of 5 grades were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 grades. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 49. As is clear from the table, when the carbon content is 40 to 90 atom%, a remarkable improvement in charging ability and durability is observed. <Example 28> The substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), using the microwave glow discharge method, as in Example 27,
Electrophotographic photoreceptors were produced under the production conditions shown in Table 50. In this experiment, the C ₂ H ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer.

The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 27. As a result, the same result as in Table 49 was obtained. <Example 29> A substrate subjected to the same pretreatment as that of Example 15 by the substrate surface treatment apparatus shown in FIG. 1 was subjected to a high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions of 51. In this experiment, the flow rates of H ₂ and / or SiF ₄ introduced at the time of forming the surface layer were changed so as to change the amounts of hydrogen atoms and fluorine atoms contained in the surface layer.
The produced electrophotographic photoconductor is a Canon copier NP665.
No. 0 was installed in an electrophotographic apparatus modified for experiments, and three items of residual potential, sensitivity, and image deletion were evaluated. Residual potential ... The same operation as in Example 15 was carried out. Sensitivity ... The same as in Example 15. Image deletion: A Canon test chart (part number: FY9-9058) consisting of all letters on a white background is placed on a document table, and an exposure amount twice the normal exposure amount is applied to make a copy. The obtained copy image was observed, and it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown. ∘: Good ○: Partially discontinued Δ: Many discontinuities were recognized as characters, and there was no practical problem. The results obtained are shown in Table 52. As is clear from Table 52, the sum of the hydrogen content and the fluorine content in the surface layer is 30
When the content of fluorine is within the range of up to 70 atomic% and the content of fluorine is within the range of 20 atomic% or less, good results can be obtained for both the residual potential and the sensitivity, and the image deletion under strong exposure can be significantly suppressed. all right. <Embodiment 30> Using the substrate surface treating apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 53 in the same manner as in Example 24. The He flow rate is 2000s including the H ₂ flow rate.
The internal pressure was kept constant by changing the pressure to be constant at ccm. The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 29. As a result, the same results as in Table 54 were obtained. <Example 31> Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 15 by the substrate surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 54. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 54 by the microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this embodiment, the value of SiF ₄ / SiH ₄ is 10 so that the content of fluorine in the photoconductive layer becomes the distribution shown in FIGS.
Smoothly change the flow rate within the range of ~ 50ppm, 4
A variety of electrophotographic photoreceptors were made. An electrophotographic photosensitive member was also produced under the same conditions except that it did not contain fluorine.
In addition, the content of oxygen atoms is about 45 for all five electrophotosensitive materials.
It was constant at 0 atomic ppm. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface fog, chargeability, sensitivity, residual potential, potential shift, white spots, halftone unevenness, ghost ... Evaluation similar to that of Example 1 Temperature characteristics ... The produced electrophotographic photosensitive member was a copying machine NP6650 manufactured by Canon Inc. In a copying machine modified for experiment, changing the surface temperature of the electrophotographic photosensitive member to 30 to 45 ° C., applying a high voltage of +6 kV to the charger to perform corona charging,
The surface potential of the dark area is measured with a surface potential meter. The change in the surface temperature of the dark portion with respect to the surface temperature of the photoconductor is approximated by a straight line, and the slope is defined as "temperature characteristic", which is expressed in units of [V / deg]. ◎ Very good. ○ Excellent. △ No problem in practical use. × It is not practical. The above results are shown in Table 56. From the table, it is understood that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, all electrophotographic characteristics including ghost and temperature characteristics are improved. <Example 32> Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 15 by the substrate surface treating apparatus shown in FIG. 1 under the conditions shown in Table 54. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 57 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this example, the value of SiF ₄ / SiH ₄ is 10 to 50 so that the content of fluorine in the photoconductive layer has a distribution form shown in FIG.
The flow rate was changed linearly within the range of ppm. When the oxygen atoms were contained in the photoconductive layer, the CO ₂ / SiH ₄ value was changed so that the distributions shown in FIGS. The three types of electrophotographic photosensitive members described above were evaluated in the same manner as in Example 31.

Table 58 shows the above results. From the table, it can be seen that when the photoconductive layer contains fluorine and oxygen and is distributed in the film thickness direction, all electrophotographic characteristics including potential shift, sensitivity, ghost, and temperature characteristics are improved. Recognize. <Example 33 and Comparative Example 9> Example 33 FIG. 32 shows a continuous manufacturing system for electrophotographic photosensitive members. In the figure, a heating container 1901, a reaction container 1902, a cooling container 1903, and a vacuum transfer container 1904 are provided, and the vacuum transfer container is moved by a rail 1921. Then, the substrate can be moved through the gate valve by moving up and down. In addition, each container and gate valve are connected with a vacuum device such as a rotary pump by sandwiching the valve. With this electrophotographic photosensitive member manufacturing system, first, the inside of the reaction container was exposed to the atmosphere and thoroughly cleaned, and then the electrophotographic photosensitive member was continuously manufactured under the manufacturing conditions shown in Table 33. The electrophotographic photosensitive member thus obtained was placed in a copying machine which was a Canon copying machine NP6650 modified for experiments, and the following evaluations were carried out. V _D : +7 kV, corona charged under the condition of 1000 μA,
The surface of the electrophotographic photosensitive member is positively charged, the surface potential at the developing device position is measured, and the value is taken as V _D. V _L : +7 kV, corona charged under the condition of 1000 μA,
The surface of the electrophotographic photosensitive member is positively charged, and the light amount is 0.7 lux.
Irradiate a sec halogen lamp. After that, the surface potential at the developing device position is measured and the value is taken as V _L.

The electrophotographic photosensitive member produced by the above-mentioned measurement 10 times continuously was evaluated, and the result is shown in FIG. Comparative Example 9 Using the same electrophotographic photoreceptor manufacturing system as in Example 33, the interior of the reaction vessel was first exposed to the atmosphere and thoroughly cleaned, and then the electrophotographic photoreceptor was continuously produced under the production conditions shown in Table 59. I did. The obtained electrophotographic photosensitive member is installed in a copying machine which is a Canon copying machine NP6650 modified for an experiment, and the same evaluation as in Example 33 is performed.
33 and 34, it can be seen that stable characteristics are obtained by the manufacturing method according to the present invention even immediately after the reaction container is exposed to the atmosphere and sufficiently cleaned. Further, the electrophotographic photosensitive member obtained by the method of the present invention was also superior in characteristics such as potential shift.

[0105]

[Table 27]

[0106]

[Table 28]

[0107]

[Table 29]

[0108]

[Table 30]

[0109]

[Table 31]

[0110]

[Table 32]

[0111]

[Table 33]

[0112]

[Table 34]

[0113]

[Table 35]

[0114]

[Table 36]

[0115]

[Table 37]

[0116]

[Table 38]

[0117]

[Table 39]

[0118]

[Table 40]

[0119]

[Table 41]

[0120]

[Table 42]

[0121]

[Table 43]

[0122]

[Table 44]

[0123]

[Table 45]

[0124]

[Table 46]

[0125]

[Table 47]

[0126]

[Table 48]

[0127]

[Table 49]

[0128]

[Table 50]

[0129]

[Table 51]

[0130]

[Table 52]

[0131]

[Table 53]

[0132]

[Table 54]

[0133]

[Table 55]

[0134]

[Table 56]

[0135]

[Table 57]

[0136]

[Table 58]

[0137]

[Table 59] (Third invention) The procedure for actually forming an electrophotographic photosensitive member having the structure shown in FIG. 5 (a) by the method for manufacturing an electrophotographic photosensitive member of the present invention using an aluminum alloy cylinder as a conductive substrate is described below. An example will be described using the pretreatment apparatus for the conductive substrate shown in FIG. 1 and the deposited film forming apparatus by the microwave CVD method shown in FIGS. 2A and 2B. Lathe with air damper for precision cutting (PNEUMO PRE
CLSION INC. Manufactured by), a diamond bite (trade name: Miracle bite, made by Tokyo Diamond),
Set to obtain a rake angle of 5 ° with respect to the cylinder center angle. Next, vacuum chuck the substrate to the rotary flange of this lathe, and spray white kerosene from the attached nozzle,
Similarly, while simultaneously using the suction of chips from the attached vacuum nozzle, the peripheral speed is 1000 m / min and the feed speed is 0.01 mm /
Under the condition of R, mirror cutting is performed so that the outer shape becomes 108 mm. With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing section 102 and a substrate transfer mechanism 103. The processing unit 102 includes a substrate loading table 111, a substrate cleaning tank 121, a pure water contact tank 131, a drying tank 141, and a substrate unloading table 151. Both the cleaning tank 121 and the pure water contact tank 131 are equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 161, and the transfer arm 161 includes the rail 16 and the transfer arm 161.
5 is composed of a moving mechanism 162 that moves above the chuck 5, a chucking mechanism 163 that holds the conductive substrate 101, and an air cylinder 164 that moves the chucking mechanism 163 up and down. After cutting, the conductive substrate 101 placed on the input table 111 is transported to the cleaning tank 121 by the transport mechanism 103. The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution 122 in the cleaning tank 121. Next, the conductive substrate 1
01 was carried to the pure water contact tank 131 by the carrying mechanism 103 and maintained at a temperature of 25 ° C. with a resistivity of 17.5 MΩ-cm.
Of pure water is sprayed from the nozzle 132 at a pressure of 50 kg · f / cm ² . The conductive substrate 101 that has undergone the pure water contact step is moved to the drying tank 141 by the transport mechanism 103, and is dried by being blown with high-temperature high-pressure air from the nozzle 142. The conductive substrate 101 after the drying process is carried to the carry-out table 151 by the carrying mechanism 103.

Next, an amorphous film was formed on the surface of the conductive substrate after the cutting and pretreatment by the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b). A deposited film mainly composed of silicon is formed. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 2.
01 is a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics, or the like) that can efficiently penetrate into 01 and maintain vacuum tightness. 20
Reference numeral 3 denotes a waveguide for transmitting microwave power, which is composed of a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. Waveguide 2
03 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212, and is electrically connected to the electrode 212. The electrophotographic photoreceptor is manufactured using such a deposited film forming apparatus as follows. First, the reaction container 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction container 201 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the heater 207 heats and holds the temperature of the substrate 205 at a predetermined temperature. Therefore, a raw material gas such as a silane gas as a raw material gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluent gas is introduced into the reaction vessel 201 through a gas introduction means (not shown). At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz, and the dielectric window 20 passes through the waveguide 203.
It is introduced into the reaction vessel 201 via the No. Further, a DC power source 211 electrically connected to the bias electrode 212 in the discharge space 206 applies a DC voltage to the bias electrode 212 with respect to the substrate 205. Thus, the conductive substrate 205
In the discharge space 206 surrounded by, the source gas is excited by the energy of microwaves and dissociates, and the electric field between the bias electrode 212 and the base 205 constantly causes ion bombardment on the conductive base 205. While the base 2
05 A deposited film is formed on the surface. At this time, the conductive substrate 2
The rotating shaft 209 on which No. 05 is installed is rotated by the motor 210, and the conductive substrate 205 is rotated around the central axis in the substrate generatrix direction to form a deposited film layer uniformly over the entire circumference of the conductive substrate 205. .

With such a manufacturing apparatus, for example, under the conditions shown in Table 2, it is possible to manufacture a light receiving member comprising a photoconductive layer and a surface layer, which are essential requirements of the present invention. According to such a procedure, the electrophotographic photosensitive member can be continuously and efficiently produced. In the present invention, the cleaning liquid used in the cleaning step is preferably water or water containing a surfactant added. The water quality can be any. The surfactant used in the washing step may be any of anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added. If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C.
C. or higher and 55.degree. C. or lower are suitable for the present invention. In the present invention, the use of ultrasonic waves in the cleaning step is important for obtaining the full effect of the present invention. The ultrasonic frequency is preferably 100 Hz or higher and 10 MHz or lower, more preferably 1 kHz or higher and 5 MHz or lower, and optimally 10 kHz or higher and 100 kHz or lower. The output of ultrasonic waves is preferably 10 W or more and 100 kW or less, more preferably 100 W or more and 10 kW or less.

Water of water used in the pure water contact step of the present invention
Quality is very important, and semiconductor grade pure water, especially ultra
LSI grade ultrapure water is preferred. Specifically, the water temperature
As the resistivity at 25 ° C, 1 MΩ-cm or more is preferable.
4 MΩ-cm or more, optimally 10 MΩ-cm or more
Suitable for the present invention. The amount of fine particles is 0.2 μm
The above is less than 100,000 pieces per milliliter, preferably
Ku or 10,000 or less, optimally 1000 or less
Suitable for light. The total number of viable bacteria is 1 mi
1000 or less, preferably 100 or less
Below, optimally 10 or less are suitable for the present invention. Organic
The physical quantity (TOC) is 100 mg or less per liter,
10 mg or less, optimally 2 mg or less is suitable for the present invention.
Is suitable. As a method of obtaining water of the above water quality,
Charcoal method, distillation method, ion exchange method, filter filtration method, reverse
Penetration method, ultraviolet sterilization method, etc. are available.
It is hoped that they will be used in combination to raise the required water quality.
Good When bringing pure water into contact with the conductive substrate surface,
It is desirable to apply pressure and spray. When spraying
If the water pressure is too weak, the effect of the present invention will be small.
If it is too strong, on the image of the obtained electrophotographic photoreceptor, especially
A pear-like pattern appears on the halftone image.
U Therefore, the pressure of water is 2 kgf / cm ² Since
Upper, 300kgf / cm² Below, preferably 10kg
・ F / cm² Above, 200kgf / cm² Below, optimal
20kgf / cm² Above 150kgf / cm
² The following are suitable for the present invention. However, in the present invention
Pressure unit kg ・ f / cm² Is the gravity kilogram per square centimeter
1 m · f / cm² Is 9806
Equal to 6.5 Pa. In the method of spraying pure water of the present invention
Sprays high pressure water from a nozzle
Method or pumping water with high pressure air and nose
Method before mixing and spraying with air pressure
Etc.

The flow rate of pure water of the present invention is 1 liter / m 2 per conductive substrate in view of the effect of the invention and economical efficiency.
in or more and 200 liters / min or less, preferably 2
Liter / min or more, 100 liter / min or less,
Optimally 5 liters / min or more, 50 liters / mi
n or less is suitable for the present invention. If the temperature of the pure water of the present invention is too high, an oxide film will be generated on the conductive substrate, which may cause peeling of the deposited film, and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of pure water is 5 ° C.
As described above, 90 ° C. or less, preferably 10 ° C. or more and 55 ° C. or less, most preferably 15 ° C. or more and 40 ° C. or less are suitable for the present invention. If the treatment time of the water contact treatment is too long, an oxide film will be formed on the conductive substrate, and if it is too short, the effect of the present invention will be small, so 10 seconds or more and 30 minutes or less, preferably 20 seconds or more, 20 Minutes or less, optimally 30 seconds or more and 10 minutes or less are suitable for the present invention. In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film. The time from cutting to water contact treatment is
If it is too long, an oxide film will be generated again on the surface of the substrate, and if it is too short, the process will not be stable. Therefore, 1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours or less, most preferably 3 minutes or more, 4 Times below are suitable for the present invention. If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable. Therefore, the time is 1 minute or more and 8 hours or less, preferably 2 minutes or more. 4 hours or less, optimally 3 minutes or more and 2 hours or less are suitable for the present invention.

As the conductive substrate used in the present invention,
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, or an electrically insulating conductive substrate such as glass or ceramics, on which at least the light receiving layer is formed is formed. A substrate whose surface is subjected to a conductive treatment can be used, but a metal is preferable from the viewpoint of mechanical strength and the like. In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive substrate in order to eliminate an image defect due to an interference fringe pattern that appears in a visible image. The unevenness provided on the surface of the conductive substrate is described in JP-A-60-168156 and JP-A-6-168156.
It is produced by a known method described in, for example, 0-178457 and 60-225854. Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. Unevenness due to a plurality of spherical trace depressions provided on the surface of the conductive substrate is disclosed in Japanese Patent Application Laid-Open No. 61-61.
It is produced by a known method described in Japanese Patent Publication No. 231561.

The photoconductive layer in the present invention is a non-single crystal silicon carbide (hereinafter referred to as nc-Si) containing silicon atoms, carbon atoms and hydrogen atoms as constituent elements from the side of the conductive substrate.
C: Abbreviated as H. And a desired photoconductive property, in particular, a charge retention property, a charge generation property, and a charge transport property. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in the planes parallel to the surface of the conductive substrate, and non-uniform in the thickness direction of the layer. At each point in the film thickness direction, the content on the side of the conductive substrate is high, and the content on the side of the surface layer is low. If the content of carbon atoms is 0.5% or less on the surface on the side where the conductive substrate is provided or in the vicinity of the surface, the function of improving the adhesiveness with the conductive substrate and preventing the injection of charges will be achieved. As a result, the effect of improving the charging ability due to the decrease in capacitance is lost. If it is 50% or more, a residual potential will be generated. Therefore, practically 0.5 to 5
It is 0 atom%, preferably 1 to 40 atom%, and most preferably 1 to 30 atom%. Further, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for making it happen. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the carbon content. Therefore, the content of hydrogen atoms on the surface of the conductive substrate is preferably 1
It is preferable to be -40 atomic%, more preferably 5-35 atomic%, and most preferably 10-30 atomic%.

In the present invention, the photoconductive layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of the film forming parameters so that desired characteristics can be obtained. Specifically, it can be formed by a glow discharge method (AC discharge CVD method such as low frequency CVD method, high frequency CVD method or microwave CVD method, or DC discharge CVD method). Among them, the microwave glow discharge method and the high-frequency glow discharge method are industrially most suitable. In order to form the nc-SiC: H photoconductive layer by the glow discharge method, basically, a raw material gas for supplying silicon that can supply silicon atoms (Si) and a C supply that can supply carbon atoms (C). A raw material gas for supplying hydrogen and a raw material gas for supplying H capable of supplying hydrogen atoms (H) are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and glow discharge is performed in the reaction vessel. A layer made of nc-SiC: H may be formed on the surface of a predetermined conductive substrate that has been caused to occur and is installed at a predetermined position in advance. Materials that can be used as a gas for supplying silicon in the present invention include SiH ₄ , Si ₂ H ₆ , and S.
Hydrogenated silicon hydrides (silanes) in a gas state such as i ₃ H ₈ and Si ₄ H ₁₀ which can be gasified are mentioned as being effectively used, and further, they are easy to handle at the time of layer formation, and silicon supply efficiency is high. SiH ₄ and Si ₂ H ₆ are preferable in terms of goodness and the like. In addition, these raw material gases for supplying silicon atoms are supplied with H ₂ , He, and A as needed.
It may be diluted with a gas such as r or Ne before use. In the present invention, it is desirable to employ, as a material that can be a raw material for introducing carbon atoms, a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions.

Can be a source gas for introducing carbon atoms (C)
The starting materials effectively used as materials are C and H.
A constituent atom, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
C2-C4 ethylene hydrocarbons, C2-C3 hydrocarbons
Cetylene hydrocarbons and the like can be mentioned. Specifically, saturation
As hydrocarbons, methane (CH_Four ), Ethane (C₂H₆
 ), Propane (C₃ H₈ ), N-butane (n-C_Four H
_Ten), Pentane (C_FiveH₁₂), As an ethylene hydrocarbon
For ethylene (C₂ H_Four ), Propylene (C ₃ H
₆ ), Butene-1 (C_Four H₈ ), Butene-2 (C_Four H
₈ ), Isobutylene (C_Four H₈ ), Penten (C_Five 
H_Ten), As acetylene hydrocarbons, acetylene
(C₂ H₂ ), Methylacetylene (C₃ H_Four ), Butin
(C_Four H₆ ) And the like. Moreover, Si and C are formed.
As the source gas used as atoms, Si (CH₃ )_Four , Si
(C₂ H_Five )_Four Can include alkyl silicides such as
It To structurally introduce hydrogen atoms into the photoconductive layer,
H₂ , Or SiH_Four , Si₂ H₆ , Si₃ 
H₈ , Si_Four H_TenSilicon hydride and silicon atoms such as
Reacts with silicon or silicon compounds to supply
It can also be done by causing the discharge to coexist in the container.
You can Controls the amount of hydrogen atoms contained in the photoconductive layer.
To control, for example, the temperature of the conductive substrate, containing hydrogen atoms
Introduce the raw material used to
The amount of discharge, the discharge power, etc. may be controlled. Light in the present invention
It is particularly effective that the conductive layer contains halogen atoms.
It Halogen atom contained in the photoconductive layer in the present invention
Suppresses the aggregation of carbon and hydrogen atoms,
Ghosts to reduce localized level density in
And it is effective in improving the uniformity of layer quality. halogen
If the number of atoms is less than 1 atom ppm, it is due to halogen atoms
The effect of improving ghost is not fully exerted, and 95 atom p
On the other hand, if it exceeds pm, the film quality will deteriorate and a ghost phenomenon will occur.
It becomes like this. Therefore, the inclusion of halogen atoms
The content is practically 1 to 95 atomic ppm, more preferably
3-80 atom ppm, optimally 5-50 atom ppm
Preferably. Especially for the photoconductive layer within the above range.
Content of halogen atoms when carbon atoms are included
By setting to within the above range,
Experiments show that the image characteristics and durability are significantly improved.
I was confirmed.

In addition, it is effective for the present invention to distribute the contained halogen atoms so as to gradually increase from the vicinity of the substrate toward the upper portion of the photoconductive layer. In order to alleviate the change in internal stress generated between the substrate side and the surface layer side as the content of carbon atoms changes in the layer thickness direction by unevenly distributing the halogen atoms in the layer thickness direction, The defects in the deposited film are reduced and the film quality is improved. As a result, it is possible to improve the so-called temperature characteristic, in which the characteristics of the light receiving member change according to the temperature change of the usage environment of the light receiving member, and the electrophotographic characteristics such as charging ability and image density unevenness between copies are improved. It Examples of such a halogen atom include fluorine, chlorine, bromine, and iodine, preferably fluorine and chlorine, more preferably fluorine. Effective as a supply gas for containing such a fluorine atom in the layer is a gaseous or gasifiable fluorine compound such as a fluorine gas, a fluoride, a halogen compound containing fluorine, or a silane derivative substituted with fluorine. Preferred examples include: Furthermore, a gaseous or gasifiable silicon hydride compound containing a fluorine atom, which contains silicon atoms and fluorine atoms as constituent elements, can also be cited as an effective one. Specific examples of the fluorine compound which can be preferably used in the present invention include F ₂ , BrF, ClF, ClF ₃ , BrF ₃ and BrF.
Examples thereof include halogen compounds such as ₅ , IF ₃ , and IF ₇ . As a silicon compound containing a fluorine atom, a so-called fluorine atom-substituted silane derivative, specifically, silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be given as preferable examples. When forming a characteristic electrophotographic light-receiving member of the present invention by glow discharge or the like using such a silicon compound containing a fluorine atom, it is not necessary to use a hydrogenated silicon gas as a silicon supply gas. Even if it is possible to form a photoconductive layer made of non-single-crystal silicon containing a fluorine atom on a predetermined support, it is possible to further control the introduction ratio of hydrogen atoms introduced into the formed photoconductive layer. In order to facilitate the formation, it is preferable that a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio. In the present invention, the above-mentioned fluorides or fluorine-containing silicon compounds are effectively used as the fluorine atom supply gas.
Fluorine-substituted silicon hydrides such as F, SiH ₃ F, SiH ₂ F ₂ , and SiHF _{3, and the} like in a gas state or a gasifiable substance can also be cited as effective raw material for forming the photoconductive layer. Among these substances, fluorinated compounds containing hydrogen atoms are introduced with hydrogen atoms, which are extremely effective for controlling electrical or photoelectric properties, at the same time as the introduction of fluorine atoms into the layer during formation of the photoconductive layer. In the present invention, it is used as a suitable gas for supplying fluorine atoms.

In the present invention, it is also effective that the photoconductive layer contains oxygen atoms in addition to halogen atoms. In this case, the synergistic action with the halogen atom relaxes the internal stress of the deposited film and suppresses the structural defect of the film. This improves the mobility of carriers in the photoconductive layer and reduces the potential shift. The content of such oxygen atoms is 10 to 5,000 atom pp within the above range of halogen atom content.
A range of m is preferred. Further, for the present invention, it is preferable to distribute the oxygen atoms contained in the photoconductive layer so as to increase from the substrate side toward the surface layer side.
At this time, the internal stress in the deposited film is effectively relieved and the structural defects of the film are suppressed, so that the mobility of carriers in the photoconductive layer is improved and the surface potential characteristics such as potential shift are further improved. In the present invention, as a raw material gas for containing oxygen atoms in the photoconductive layer, oxygen (O ₂ ) and carbon monoxide (C
O), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen oxide (N ₂ O) in small amounts are effectively added to the source gas. Further, in the present invention, it is preferable that the photoconductive layer contains an atom (M) for controlling conductivity, if necessary.
Atoms for controlling conductivity may be contained in the photoconductive layer in a uniformly distributed state, or even in a portion having a nonuniformly distributed state in the layer thickness direction. Good. Examples of the atom (M) for controlling the conductivity include so-called impurities in the semiconductor field,
Atoms belonging to Group III of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as "Group III atoms") or atoms belonging to Group V of the Periodic Table giving n-type conduction characteristics (hereinafter "Group V atoms")
Abbreviated) can be used.

The group III atom is, specifically,
Element (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl), etc., especially
B, Al and Ga are preferred. As a Group V atom,
Physically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., with P and As being particularly preferred
Is. Atoms contained in the photoconductive layer that control conductivity
The content of (M) is preferably 1 × 10^-3~ 5x
10^Four Atomic ppm, more preferably 1 × 10^-2~ 1 x 1
0 ^Four Atomic ppm, optimally 1 x 10^-1~ 5 x 10³ atom
It is desirable to set it to ppm. Especially in the photoconductive layer
The content of carbon atoms (C) is 1 × 10³ Atomic ppm or less
In this case, the content of atoms (M) contained in the photoconductive layer
Preferably 1 × 10^-3~ 1 x 10³ Atomic ppm
It is desirable that the content of carbon atoms (C) be 1 × 10
³ If it exceeds atomic ppm, the content of atom (M) shall be considered.
Preferably 1 × 10^-1~ 5 x 10^Four Atomic ppm and
It is desirable to be done. Control conductivity in the photoconductive layer
An atom, for example a Group III atom or a Group V atom,
To introduce artificially, introduce a Group III atom during layer formation.
Gas source material or group V atom introduction source material
In order to form a photoconductive layer in the reaction vessel
It can be introduced with gas. For introduction of group III atoms
Or a raw material for introducing a Group V atom
What you get is that it is gaseous or less at normal temperature and pressure.
Both of them are those that can be easily gasified under layer forming conditions.
Is desirable. Raw materials for introducing such group III atoms
Specifically as a substance, for introducing a boron atom, B
₂ H₆ , B_Four H_Ten, B_Five H₉ , B_Five H₁₁, B₆ H _Ten, B
₆ H₁₂, B₆ H₁₄Borohydride, BF, etc.₃ , BCl
₃ , BBr₃ And the like. This
Other than AlCl₃ , GaCl₃ , Ga (CH ₃ )₃ , I
nCl₃ , TlCl₃ Etc. can also be mentioned.

In the present invention, a raw material for introducing a group V atom is effectively used. For introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ , etc., PH ₄ I, PF
₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr
₅ , and phosphorus halides such as PI ₃ are included. Besides this, A
sH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , S
bCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ etc. are also V
It can be cited as an effective starting material for introducing a group atom. Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary. Further, the photoconductive layer of the light receiving member of the present invention comprises a group Ia, a group IIa,
You may contain at least 1 sort (s) of element selected from VIa group and VIII group. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is contained evenly in a uniform distribution from the viewpoint of achieving uniform properties in the in-plane direction. is necessary. As the group Ia atom, specifically,
Examples thereof include lithium (Li), sodium (Na), and potassium (K), and group IIa atoms include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). )
Etc. can be mentioned.

Further, as the group VIa atom, specifically,
Chromium (Cr), molybdenum (Mo), tungsten (W) can be mentioned, and as the Group VIII atom, iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned. In the present invention, the layer thickness of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the photoconductive layer is preferably 5 to 50 μm, and more preferably 10 to
The thickness is preferably 40 μm, and most preferably 20 to 30 μm. Nc-Si having characteristics capable of achieving the object of the present invention
In order to form the photoconductive layer made of C (H), it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction vessel as desired. The temperature (Ts) of the conductive substrate is appropriately selected according to the layer design, but in the usual case, it is preferably 20 to 500 ° C., more preferably 50.
It is desirable to set the temperature to 480 ° C, optimally 100 to 450 ° C. The surface layer in the present invention is composed of a non-single crystal material containing silicon atoms, carbon atoms, hydrogen atoms and Group III of the periodic table as constituent elements. By the surface layer of the manufacturing method of the present invention, the electrical withstand voltage can be dramatically improved, and as a result, even if there are spherical projections, which are abnormal growth of the film, to some extent, it is possible that they appear as image defects. Can be improved. Further, even when the separation charger causes an abnormal discharge in the electrophotographic process at the time of withstanding voltage, the surface of the electrophotographic photosensitive member is not dielectrically broken, and so-called leak spots can be extremely reduced.

The carbon atoms contained in the surface layer of the present invention may be uniformly distributed in the layer, or the carbon atoms contained in the layer may be distributed nonuniformly in the layer thickness direction. There may be. However, in the case of uneven distribution, it is preferable that the distribution is increased from the photoconductive layer toward the outermost surface. The content of carbon atoms contained in the entire surface layer region of the present invention is preferably a value of carbon atoms / (silicon atoms + carbon atoms) in order to achieve effects such as high dark resistance and high hardness. The content is preferably 40 to 90 atom%, more preferably 45 to 85 atom%, and most preferably 50 to 80 atom%. In order to exert the effect of the present invention, the contained Group III element of the periodic table is 1 × 1.
It is required to be 0 ⁵ atomic ppm or less. Further, it is effective that the surface layer of the present invention further contains a halogen atom. Since the halogen atom contained in the surface layer improves the water repellency, the high humidity flow due to the adsorption of water vapor is also reduced, and the electric characteristics of the electrophotographic photosensitive member are further improved. The halogen atom contained in the surface layer is 20 atom% or less, and the sum of the content of hydrogen atom and halogen atom is preferably 30 to 70 atom%, more preferably 35 to 65 atom%, most preferably It is desirable that the content be 40 to 60 atomic%. In the present invention, it is effective that the surface layer further contains an oxygen atom or a nitrogen atom. The amount of oxygen atoms and / or nitrogen atoms contained in the surface layer is preferably 1 × 10 ⁻⁴ to 30 atom%, more preferably 5 × 10 ^−4.
It is desirable that the content is -25 atom%, optimally 1 × 10 ^-3 -20 atom%. Oxygen atoms and / or nitrogen atoms contained in the surface layer compensate for dangling bonds existing in nc-SiC: H and are effective in improving the film quality, and are carriers trapped at the interface between the photoconductive layer and the surface layer. To improve the image flow. In addition, the inclusion of oxygen atoms and nitrogen atoms in the surface layer improves the adhesiveness at the interface between the surface layer and the photoconductive layer, and it becomes possible to change the structure of the surface layer itself. The surface properties of the body, the pressure resistance, the protection function of the photoconductive layer and the aluminum cylinder that is the conductive substrate are improved, and the durability of the electrophotographic photoreceptor can be dramatically improved while maintaining excellent electrical characteristics. it can.

That is, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are excellent. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the durability against high voltage is improved due to the decrease in the dielectric constant, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur. Furthermore, when recycled paper is used, the surface layer containing silicon atoms, hydrogen atoms, halogen atoms, Group III elements of the periodic table, and oxygen atoms and / or nitrogen atoms according to the method of the present invention has a surface. Prevents adhesion of sizing agents such as rosin of recycled paper to the surface of electrophotographic photoconductor due to improved altitude and environmental resistance, and eliminates toner fusion and image deletion during long-term use. Especially effective. In the present invention, nc-
To form a surface layer composed of SiC: H, a vacuum deposition method similar to the method for forming the photoconductive layer described above is adopted. In the present invention, as the silicon supply gas and the raw material gas for introducing carbon atoms (C) used in forming the surface layer, the same ones as those used in forming the photoconductive layer can be used. Is. In the present invention, as the source gas used for containing Group III of the periodic table in the surface layer, the same ones as those used for forming the photoconductive layer can be used. In the present invention, the introduced gas for allowing the surface layer to contain oxygen atoms and nitrogen atoms includes oxygen (O ₂ ) for oxygen atoms,
Examples thereof include carbon monoxide (CO), carbon dioxide (CO ₂ ), and nitrogen (N ₂ ) and ammonia (NH ₃ ) for nitrogen atoms. Nitrogen monoxide (NO), nitrogen dioxide (NO) that contain oxygen and nitrogen atoms at the same time.
₂ ) and dinitrogen oxide (N ₂ O) are preferred.

Further, in the present invention, the surface layer may contain at least one element selected from Group Ia, Group IIa, Group VIa and Group VIII of the Periodic Table. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there. Specific examples of the group Ia atom include lithium (Li), sodium (Na), and potassium (K).
Beryllium (Be), magnesium (Mg), calcium (Ca), strontium (S)
r), barium (Ba), etc. can be mentioned. Further, as the group VIa atom, specifically, chromium (C
r), molybdenum (Mo), tungsten (W), and the like, and as the Group VIII atom, iron (Fe),
Cobalt (Co), nickel (Ni), etc. can be mentioned. In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.05, from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness is ˜20 μm, optimally 0.1 to 10 μm. When forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The temperature of the conductive substrate is appropriately selected in the optimum range, but preferably 20 to
500 ° C, more preferably 50 to 480 ° C, optimally 1
It is desirable to set the temperature to 00 to 450 ° C.

The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to 3} Torr, most preferably 1 × 10 ^{5.
-4 to 1} Torr is desirable. In the present invention, the conductive base temperature for forming the surface layer, the above-mentioned range as a desirable numerical range of gas pressure,
These layer-building factors are not usually independently determined separately, but the optimum value of each layer-building factor is determined on the basis of mutual and organic relationships so as to form a surface layer having desired properties. desirable. In the light receiving member of the present invention, a layer region whose composition is continuously changed may be provided between the photoconductive layer and the surface layer. By providing the layer region, the adhesion between the layers can be further improved. Further, in the light receiving member of the present invention, the photoconductive layer has a layer region containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction on the side of the conductive substrate. Is desirable. In the present invention, the energy for generating plasma may be DC, high frequency, microwave, or the like, but the effect of the present invention is more remarkable particularly when microwave or high frequency is used as the energy for generating plasma. Will be things. In the present invention, when microwave is used for plasma generation, any microwave power may be used as long as it can generate a discharge, but 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW or less are used to carry out the present invention. It is suitable for doing this.

The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these. <Example 34 and Comparative Example 10> Example 34 Diameter 108 m made of aluminum having a purity of 99.5%
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for manufacturing an electrophotographic photosensitive member according to the present invention described above, and 15 minutes after the completion of the cutting step, as shown in FIG. The surface of the substrate was pretreated under the conditions shown in Table 60 by the surface treatment apparatus shown in FIG. However, in this example, as the surfactant, polyethylene glycol nonylphenyl ether was used as a 1 wt% aqueous solution. On the aluminum cylinder thus pretreated, the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 4 was used and the high-frequency glow discharge method was used to perform electrophotography under the manufacturing conditions shown in Table 61 according to the procedure described in detail above. A photoconductor was prepared. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. 35, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly. At this time, the carbon content at the interface of the photoconductive layer with the substrate was set to about 10 atomic%. The carbon content was measured by elemental analysis by Rutherford backscattering method. The surface layer of the produced electrophotographic photosensitive member was visually evaluated first, and then the Canon copying machine NP-7550 was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, etc. The following evaluations were made on the image characteristics after the durability test. Surface Haze The produced electrophotographic photosensitive member was visually inspected for the degree of surface haze.

⊚ does not have clouding. ◯ has partial clouding. Δ has partial clouding at several places. × has clouding on the entire surface. Charging ability / sensitivity / residual potential Charging ability: An electrophotographic photoreceptor is installed in an experimental device, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential meter measures the dark surface potential of the electrophotographic photoreceptor. To do. Sensitivity: The electrophotographic photoreceptor is charged to a constant dark surface potential. Then, the light image is immediately irradiated. The light image is emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. The exposure amount is adjusted so that the light portion surface potential becomes a predetermined potential, and the exposure amount at this time is taken as the sensitivity. Residual potential: The electrophotographic photoreceptor is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image is emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. White spots / halftone unevenness ... Put the electrophotographic photoconductor in a copier, which is a Canon copier NP-7550 modified for experiment, and transfer it by a normal electrophotographic process to form an image on a paper surface. Images were evaluated by the procedure.

White Pochi ... A diameter 0.2 within the same area of the copy image obtained when a full black chart made by Canon (part number: FY9-9073) is placed on the platen and copied.
The number of white spots having a size of mm or less was counted. Halftone unevenness ... Image density of 100 points with a circular area of 0.05 mm in diameter as one unit on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on the platen and copied. Was measured and the variation in the image density was evaluated. For each of these, ◎ is "excellently good" ○ is "good" △ is "no problem in practical use" × is "problem in practical use" Image characteristics after endurance using recycled paper ... The NP-7550 was installed in an electrophotographic apparatus modified for experiments, and a durability test of 3 million sheets was performed using recycled paper. Then, the image characteristics were evaluated as follows. Image deletion: A Canon test chart (part number: FY9-9058) consisting of all letters on a white background is placed on a document table, and an exposure amount twice the normal exposure amount is applied to make a copy. The obtained copy image was observed, and it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown.

⊚ is good ○ is partly discontinued Δ is many discontinuities but can be recognized as characters and has no practical problem Black spots ... Within the same area of the copy image obtained when a blank sheet is placed on the platen and copied. The number of black image defects having a diameter of 0.2 mm or less was counted. For each of these, ⊚ is “excellently good”, ○ is “good”, Δ is “no problem in practical use”, and “is a problem in practical use”. Comparative Example 10 A conductive substrate similar to that of Example 34 was cut in the same procedure, and the cut conductive substrate was subjected to the conventional conductive substrate cleaning apparatus shown in FIG. Was processed. The conductive substrate cleaning apparatus shown in FIG. 3 includes a processing tank 302 and a substrate transfer mechanism 303. The processing tank 302 includes a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361, and the transfer arm 361 includes a rail 365.
A moving mechanism 362 that moves up, a chucking mechanism 363 that holds the base 301, and the chucking mechanism 3
It is composed of an air cylinder 364 for raising and lowering 63.

After cutting, the substrate 3 placed on the input table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichloroethane (trade name: ETERNA VG manufactured by Asahi Kasei Kogyo Co., Ltd.) 322 in the cleaning tank 321 performs cleaning for removing cutting oil and chips adhering to the surface. After cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. The substrate thus pretreated in the conventional manner was processed in the same manner as in Example 34, and Table 64
A so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate, a charge transport layer, a charge generation layer, and a surface layer was prepared under the conditions shown in. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 34, and the results of Example 34 are shown in Table 62.
As is clear from Table 62, according to the method of the present invention, the sensitivity is improved and the residual potential is kept low. Further, it can be seen that particularly excellent characteristics are exhibited in terms of cloudiness and uneven halftone on the surface of the photoconductor, and durability characteristics with recycled paper. Furthermore, according to the present invention, 3
It can be seen that there is no problem on the image even after the durability of 1,000,000 sheets. <Example 35 and Comparative Example 11> Example 35 FIGS.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 65. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 34. As a result, exactly the same results as in Example 34 were obtained. Comparative Example 11 FIGS. 2A and 2 are formed on a conductive substrate that has been subjected to the same pretreatment as in Comparative Example 10 by the substrate surface treatment apparatus shown in FIG.
A so-called function-separated type having a three-layer structure of a substrate, a charge transport layer, a charge generation layer, and a surface layer under the conditions shown in Table 66 by a microwave glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in (b). An electrophotographic photoreceptor was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 35. As a result, the same result as in Comparative Example 11 was obtained. <Example 36 and Comparative Example 12> Example 36 On the substrate pretreated in the same manner as in Example 34 by the substrate surface treatment apparatus shown in FIG. 1, the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 was used. Follow the steps detailed above
Electrophotographic photoreceptors were produced by the high frequency glow discharge method under the production conditions shown in Table 67. In this example, in order to change the change pattern of carbon content in the photoconductive layer as shown in FIGS. 36 and 37, CH ₄ introduced at the time of forming the photoconductive layer.
Was changed to prepare two types of photoconductors. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the signal intensity by Auger spectroscopy.

[0160] The surface of the produced electrophotographic photosensitive member was visually judged to be cloudy, the Canon copying machine NP-7550 was installed in an electrophotographic apparatus modified for experiment, and the sensitivity, residual potential, and
White spots and halftone unevenness were evaluated in the same manner as in Example 34. After that, the durability of 3 million sheets was evaluated in a modified NP-7550 machine using recycled Canon copy paper, and image deletion and black spots were evaluated in the same manner as in Example 34, and the results are shown in Table 68. Comparative Example 12 An electrophotographic photosensitive member having a carbon content pattern shown in FIGS. 38 and 39 was produced on a substrate pretreated in the same manner as in Comparative Example 10 in the same manner as in Example 36. The same evaluation was performed. The results are shown in Table 68 and shown in Example 3
It is shown together with the evaluation result of 6. From Table 68, it can be seen that, in the carbon content change pattern of the photoconductive layer of the present invention, good results were obtained in both the initial characteristics and the image characteristics after endurance as compared with the results of Comparative Example 12. <Example 37 and Comparative Example 13> Example 37 Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 34 by the substrate surface treatment apparatus shown in FIG. Table 6 was conducted in the same manner as in Example 36 except that the microwave glow discharge method was used by using the manufacturing apparatus for the photographic photoreceptor.
An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in 9. In this example, the change pattern of the carbon content in the photoconductive layer is shown in FIG.
6 In order to change as shown in FIG. 37, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer was changed. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. The carbon content was measured by elemental analysis by Rutherford backscattering method. The electrophotographic photosensitive member produced produced the same results as in Example 36. Comparative Example 13 Electrophotographic sensitization with a carbon content pattern shown in FIGS. 38 and 39 was performed in the same manner as in Example 37 on a substrate pretreated in the same manner as in Comparative Example 10 by the substrate processing apparatus shown in FIG. The body was made. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 37, the same results as in Comparative Example 12 were obtained. <Example 38> The procedure described in detail above was performed on the substrate pretreated in the same manner as in Example 34 by the substrate surface treating apparatus shown in FIG. 1 by using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. In accordance with the above, an electrophotographic photoreceptor was produced by the high frequency glow discharge method under the production conditions shown in Table 61. In this example, the change pattern of the carbon content in the photoconductive layer was changed by using FIG. 35 and changing the carbon content of the surface on the substrate side by changing the flow rate of CH ₄ introduced during the formation of the photoconductive layer. The carbon content on the substrate-side surface of the photoconductive layer was identified by elemental analysis by Rutherford backscattering method.

The number of occurrences of cloudiness and spherical protrusions on the surface of the electrophotographic photosensitive member produced, and further, Canon Copier NP-75
50 was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness, and the image quality after 3 million sheets of recycled paper were evaluated. . Each item was performed by the following method. Surface haze Evaluation was performed in the same manner as in Example 34. Number of Spherical Protrusions The entire surface of the produced electrophotographic photosensitive member was observed with an optical microscope to check the number of spherical protrusions having a diameter of 20 μm or more within an area of 100 cm ² . Results were obtained for each electrophotographic photosensitive member, and the one having the largest number of spherical projections was set as 100% for relative comparison. The results are classified as follows. ⊚ is less than 60% ◯ is 80 to 60% Δ is 100 to 80% Residual potential Evaluation was made in the same manner as in Example 34. White spot / halftone unevenness White spot / halftone unevenness ... The evaluation was performed in the same manner as in Example 34. The results thus obtained are summarized in Table 70.
From these results, the carbon content on the substrate-side surface of the photoconductive layer was improved at 0.5 to 50 atomic%, and very good results were obtained at 1 to 30 atomic%. <Example 39> A substrate surface-treated as shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), the electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 65 by the microwave glow discharge method according to the procedure detailed above. . In this embodiment, the change pattern of the carbon content in the photoconductive layer is shown in FIG. 35, and the flow rate of CH ₄ introduced into the photoconductive layer at the carbon content of the substrate side surface is changed for each photoconductor. Was changed by.

As a result of evaluation in the same manner as in Example 38, exactly the same results as in Table 70 were obtained. <Example 40> On a substrate subjected to the same pretreatment as in Example 34, using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG. 4, and following the procedure detailed above, a high frequency glow discharge method was applied to Table 71. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in. In this example, the fluorine content in the photoconductive layer was measured as shown in FIG.
The flow rate of SiF ₄ introduced at the time of forming the photoconductive layer was changed in order to change it as shown in FIG. The fluorine content in the photoconductive layer is determined by SIMS (CAMECA IMS
-3F) elemental analysis showed 3 near the substrate.
at. ppm, 40 at. It was ppm. (I) Canon electrophotographic copying machine NP
-7550 was installed in the electrophotographic device modified for experiments,
White spots, halftone spots before the accelerated durability test,
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Example 34 and Example 38. The ghost was evaluated as follows. Ghost: A Canon ghost test chart (part number: FY9-9040) with a black circle with a reflection density of 1.1 and ¢ 5 mm is placed on the front edge of the image on the platen, and a Canon halftone chart is placed on it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion of the ghost chart observed on the halftone copy in the copied images when they were overlapped was measured. In each case, ◎ means "especially good", ○ means "good", Δ means "no problem in practical use", and × means "problem in practical use".

The results are summarized in Table 72. (II) Next, the produced electrophotographic photosensitive member was installed in an electrophotographic apparatus modified from Canon Copier NP-7550 for experiment, and a durability test of 3 million sheets was conducted using recycled paper.
Then, electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The results are summarized in Table 73. From the results of Table 72 and Table 73, by setting the fluorine content in the photoconductive layer in the range of 95 atomic ppm or less, it is possible to produce an electrophotographic photoreceptor having excellent image characteristics and durability. Was shown. <Example 41> By using the substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 74 in the same manner as in Example 40. Then, the produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 40. The results were exactly the same as in Table 72 and Table 73. <Example 42> A substrate subjected to the same pretreatment as in Example 34 by the substrate surface treatment apparatus shown in FIG. 1 was subjected to a high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions of 75. In this experiment, the flow rate of CH ₄ introduced at the time of forming the surface layer was changed so that the amount of carbon contained in the surface layer was changed.

The produced electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from Canon copier NP-7550 for experiments, and the charging ability, residual potential, image evaluation before endurance, and 3 million sheets of recycled paper were used. The image evaluation after the durability test was performed by the following method. Charging ability: Performed in the same manner as in Example 34. Residual potential ... The same operation as in Example 34 was performed. Image evaluation after endurance: Limit samples of 5 grades were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 grades. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 76. As is clear from the table, when the carbon content is 40 to 90 atom%, a remarkable improvement in charging ability and durability is observed. <Embodiment 43> The substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 46 in the same manner as in Example 42. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer. The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 42. As a result, the same result as in Table 76 was obtained. <Example 44> By using the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 78. In this experiment, a nitrogen atom, an oxygen atom contained in the surface layer of the produced electrophotographic photosensitive member,
When the boron atom was quantified by SIMS, the nitrogen atom and the oxygen atom were several tens ppm, and the boron atom was several mmp.

The electrophotographic photoconductor thus prepared was installed in an electrophotographic copying machine which was modified from Canon Copier NP-7550 for experiment, and 3 million sheets of images after durability were visually evaluated using recycled paper. I did. as a result,
Very good results were obtained without an increase in image deletion and white spots. <Embodiment 45> By using the substrate surface treating apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 79. In this example, the CH ₄ flow rate was changed in the surface layer so that the carbon atom content in the surface layer was distributed in the layer thickness direction so as to be maximized at the outermost surface. At this time, the flow rate of the raw material gas was changed so that the contents of boron, nitrogen and oxygen atoms in the surface layer were gradually increased. The electrophotographic photosensitive member thus prepared was installed in an electrophotographic copying apparatus which was modified from Canon Copier NP-7550 for experiment, and 3 million images after running were visually evaluated using recycled paper. as a result,
Very good results were obtained without an increase in image deletion and white spots. <Embodiment 46> The substrates shown in FIGS. 2 (a) and 2 (b) are formed on a substrate which has been pretreated in the same manner as in Example 34 under the conditions shown in Table 80 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 81 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this embodiment, the value of SiF ₄ / SiH ₄ is 10 so that the content of fluorine in the photoconductive layer becomes the distribution shown in FIGS.
Smoothly change the flow rate within the range of ~ 50ppm, 4
A variety of electrophotographic photoreceptors were made. An electrophotographic photosensitive member was also produced under the same conditions except that it did not contain fluorine.
The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, chargeability, sensitivity, residual potential, white spots, halftone unevenness, ghost ... Evaluation similar to that of Example 34 Temperature characteristics: manufactured electrophotographic photosensitive member was manufactured by Canon Copier NP-7550. Put it in a copier modified for experiments, change the surface temperature of the electrophotographic photosensitive member to 30 to 45 ° C, apply a high voltage of +6 kV to the charger, perform corona charging, and use the surface electrometer to measure the surface potential of the dark area. To measure. The change in the surface temperature of the dark portion with respect to the surface temperature of the photoconductor is approximated by a straight line, and the slope is defined as "temperature characteristic", which is expressed in units of [V / deg]. ◎ Very good. ○ Excellent. △ No problem in practical use. × It is not practical. The above results are shown in Table 82. From the table, it is understood that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, electrophotographic characteristics including ghost and temperature characteristics are improved. <Example 47> Electrons shown in FIGS. 2 (a) and 2 (b) were formed on a substrate pretreated in the same manner as in Example 34 by the substrate surface treating apparatus shown in FIG. 1 under the conditions shown in Table 81. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 83 by a microwave glow discharge method using a photographic photosensitive member manufacturing apparatus. In this embodiment, the content of fluorine in the photoconductive layer is constant,
Four kinds of electrophotographic photoconductors were produced by changing the flow rate smoothly within the range of CO ₂ / SiH ₄ value of 10 to 50 ppm so that the oxygen content has the distribution form shown in FIGS. An electrophotographic photosensitive member was also produced under the same conditions except that oxygen was not contained. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, charging ability, sensitivity, residual potential, white spots, halftone unevenness, ghost, temperature characteristics ... Evaluation similar to that of Example 46 Potential shift ... Electrophotographic photosensitive member was set in experimental apparatus and charger A high voltage of +6 kV is applied to the substrate to perform corona charging, and the surface potential of the dark portion of the electrophotographic photoreceptor is measured with a surface potential meter. At this time, the dark surface potential immediately after the voltage is applied to the charger is V _d0 and the dark surface potential after 2 minutes is V _d . Then, the difference between V _d0 and V _d is the amount of potential shift. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 84. From the table, when the photoconductive layer contains fluorine, and further contains oxygen atoms,
It can be seen that the characteristics of potential shift are improved.

[0168]

[Table 60]

[0169]

[Table 61]

[0170]

[Table 62]

[0171]

[Table 63]

[0172]

[Table 64]

[0173]

[Table 65]

[0174]

[Table 66]

[0175]

[Table 67]

[0176]

[Table 68]

[0177]

[Table 69]

[0178]

[Table 70]

[0179]

[Table 71]

[0180]

[Table 72]

[0181]

[Table 73]

[0182]

[Table 74]

[0183]

[Table 75]

[0184]

[Table 76]

[0185]

[Table 77]

[0186]

[Table 78]

[0187]

[Table 79]

[0188]

[Table 80]

[0189]

[Table 81]

[0190]

[Table 82]

[0191]

[Table 83]

[0192]

[Table 84] (Fourth Invention) Hereinafter, an example of a procedure for actually forming an electrophotographic photosensitive member having a structure shown in FIG. 5B by the method for manufacturing an electrophotographic photosensitive member of the present invention using an aluminum alloy cylinder as a conductive substrate. Is a pretreatment device for the conductive substrate shown in FIG. 1 and the microwave C shown in FIGS. 2 (a) and 2 (b).
An explanation will be given using a deposited film forming apparatus by the VD method.

Lathe with air damper for precision cutting (PNE
UMO PRECLSION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle, and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed rate was 0.01 mm. Under the condition of / R, mirror cutting is performed so that the outer shape becomes 108 mm. With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing section 102 and a substrate transfer mechanism 103. The processing unit 102 includes a substrate loading table 111, a substrate cleaning tank 121, a pure water contact tank 131, a drying tank 141, and a substrate unloading table 151. Cleaning tank 121, pure water contact tank 1
31 is equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 161.
Is composed of a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the conductive substrate 101, and an air cylinder 164 that moves the chucking mechanism 163 up and down. After cutting, the conductive substrate 101 placed on the input table 111 is transported to the cleaning tank 121 by the transport mechanism 103. The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution 122 in the cleaning tank 121. Next, the conductive substrate 101 is carried to the pure water contact tank 131 by the carrying mechanism 103 and has a resistivity of 1 kept at a temperature of 25 ° C.
50 kg of pure water of 7.5 MΩ-cm from the nozzle 132
It is sprayed at a pressure of f / cm ² . The conductive substrate 101 that has undergone the pure water contact step is moved to the drying tank 141 by the transport mechanism 103, and is dried by being blown with high-temperature high-pressure air from the nozzle 142. The conductive substrate 101 after the drying process is carried to the carry-out table 151 by the carrying mechanism 103.

Next, an amorphous film is formed on the surface of the conductive substrate after the cutting and pretreatment by the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b). A deposited film mainly composed of silicon is formed. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 2.
01 is a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics, or the like) that can efficiently penetrate into 01 and maintain vacuum tightness. 20
Reference numeral 3 denotes a waveguide for transmitting microwave power, which is composed of a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. Waveguide 2
03 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212, and is electrically connected to the electrode 212. The electrophotographic photoreceptor is manufactured using such a deposited film forming apparatus as follows. First, the reaction container 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction container 201 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the heater 207 heats and holds the temperature of the substrate 205 at a predetermined temperature. Therefore, a raw material gas such as a silane gas as a raw material gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluent gas is introduced into the reactor 201 through a gas introduction means (not shown). At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz, and the dielectric window 202 passes through the waveguide 203.
It is introduced into the reaction vessel 201 via. Further discharge space 2
A DC power supply 211 electrically connected to the bias electrode 212 in 06 applies a DC voltage to the bias electrode 212 with respect to the substrate 205. Thus, in the discharge space 206 surrounded by the conductive substrate 205, the source gas is excited and dissociated by the energy of microwaves, and the electric field between the bias electrode 212 and the substrate 205 causes the source gas to steadily stay on the conductive substrate 205. While being bombarded with ions, the base 20
5 A deposited film is formed on the surface. At this time, the conductive substrate 20
By rotating the rotating shaft 209 on which the No. 5 is installed by the motor 210 and rotating the conductive substrate 205 around the central axis in the substrate generatrix direction, a deposited film layer is formed uniformly over the entire circumference of the conductive substrate 205. .

With such a manufacturing apparatus, for example, under the conditions shown in Table 86, it is possible to manufacture a light receiving member comprising a photoconductive layer and a surface layer, which are essential requirements of the present invention. According to such a procedure, the electrophotographic photosensitive member can be continuously and efficiently produced. In the present invention, the cleaning liquid used in the cleaning step is preferably water or water containing a surfactant added. The water quality can be any. The surfactant used in the washing step may be any of anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added. If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C.
C. or higher and 55.degree. C. or lower are suitable for the present invention. In the present invention, the use of ultrasonic waves in the cleaning step is important for obtaining the full effect of the present invention. The ultrasonic frequency is preferably 100 Hz or higher and 10 MHz or lower, more preferably 1 kHz or higher and 5 MHz or lower, and optimally 10 kHz or higher and 100 kHz or lower. The output of ultrasonic waves is preferably 10 W or more and 100 kW or less, more preferably 100 W or more and 10 kW or less.

Water of water used in the pure water contacting step of the present invention
Quality is very important, and semiconductor grade pure water, especially ultra
LSI grade ultrapure water is preferred. Specifically, the water temperature
As the resistivity at 25 ° C, 1 MΩ-cm or more is preferable.
4 MΩ-cm or more, optimally 10 MΩ-cm or more
Suitable for the present invention. The amount of fine particles is 0.2 μm
The above is less than 100,000 pieces per milliliter, preferably
Ku or 10,000 or less, optimally 1000 or less
Suitable for light. The total number of viable bacteria is 1 mi
1000 or less, preferably 100 or less
Below, optimally 10 or less are suitable for the present invention. Organic
The physical quantity (TOC) is 100 mg or less per liter,
10 mg or less, optimally 2 mg or less is suitable for the present invention.
Is suitable. As a method of obtaining water of the above water quality,
Charcoal method, distillation method, ion exchange method, filter filtration method, reverse
Penetration method, ultraviolet sterilization method, etc. are available.
It is hoped that they will be used in combination to raise the required water quality.
Good When bringing pure water into contact with the conductive substrate surface,
It is desirable to apply pressure and spray. When spraying
If the water pressure is too weak, the effect of the present invention will be small.
If it is too strong, on the image of the obtained electrophotographic photoreceptor, especially
A pear-like pattern appears on the halftone image.
U Therefore, the pressure of water is 2 kgf / cm ² Since
Upper, 300kgf / cm² Below, preferably 10kg
・ F / cm² Above, 200kgf / cm² Below, optimal
20kgf / cm² Above 150kgf / cm
² The following are suitable for the present invention. However, in the present invention
Pressure unit kg ・ f / cm² Is the gravity kilogram per square centimeter
1 m · f / cm² Is 9806
Equal to 6.5 Pa. In the method of spraying pure water of the present invention
Sprays high pressure water from a nozzle
Method or pumping water with high pressure air and nose
Method before mixing and spraying with air pressure
Etc.

The flow rate of pure water of the present invention is 1 liter / mi per conductive substrate in view of the effect of the invention and economy.
n or more and 200 liters / min or less, preferably 2 liters / min or more and 100 liters / min or less, optimally 5 liters / min or more, 50 liters / min
The following are suitable for the present invention. The temperature of pure water of the present invention is
If it is too high, an oxide film is generated on the conductive substrate, which may cause peeling of the deposited film and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of pure water is 5 ° C or higher and 90 ° C or lower, preferably 10 ° C or higher and 55 ° C or lower,
Optimally, the temperature of 15 ° C or higher and 40 ° C or lower is suitable for the present invention. If the treatment time of the water contact treatment is too long, an oxide film is generated on the conductive substrate, and if it is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or longer and 30 minutes or shorter, preferably 20 minutes.
Seconds or more and 20 minutes or less, optimally 30 seconds or more and 10 minutes or less are suitable for the present invention. In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film. If the time from cutting to water contact treatment is too long, an oxide film will be generated again on the surface of the substrate, and if it is too short, the process will not be stable, so 1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours. Below, optimally 3 minutes or more, 4
Times below are suitable for the present invention. If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable. Therefore, the time is 1 minute or more and 8 hours or less, preferably 2 minutes or more. Four
It is suitable for the present invention that the time is less than or equal to the time, optimally 3 minutes or more and less than or equal to 2 hours.

As the conductive substrate used in the present invention,
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, glass, ceramic, or the like of an electrically insulating conductive substrate on which at least the light receiving layer is formed is formed. A substrate whose surface is subjected to a conductive treatment can be used, but a metal is preferable from the viewpoint of mechanical strength and the like. In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive substrate in order to eliminate an image defect due to an interference fringe pattern that appears in a visible image. The unevenness provided on the surface of the conductive substrate is described in JP-A-60-168156 and JP-A-60-168156.
It is produced by a known method described in JP-A-178457 and JP-A-60-225854. Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. Unevenness due to a plurality of spherical trace depressions provided on the surface of the conductive substrate is disclosed in Japanese Patent Application Laid-Open No. 61-61.
It is produced by a known method described in Japanese Patent Publication No. 231561.

The first photoconductive layer in the present invention comprises, as constituent elements, silicon atoms and carbon atoms from the side of the conductive substrate.
It is composed of a photoconductive layer made of nc-SiC (H) containing a hydrogen atom, and has desired photoconductive characteristics, particularly charge retention characteristics,
It has charge generation characteristics and charge transport characteristics. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in a plane parallel to the surface of the conductive substrate,
The layer is non-uniform in the thickness direction, and the content on the conductive substrate side is high and the content on the surface layer side is low at each point in the film thickness direction. If the content of carbon atoms is 0.5% or less on the surface on the side where the conductive substrate is provided or in the vicinity of the surface, the function of improving the adhesiveness with the conductive substrate and preventing the injection of charges will be achieved. As a result, the effect of improving the charging ability due to the decrease in capacitance is lost. Again 50
% Or more, a residual potential is generated. Therefore, practically 0.5 to 50 atom%, preferably 1 to 40 atom%.
And optimally 1 to 30 atomic%. Further, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for making it happen. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the carbon content. Therefore, the content of hydrogen atoms on the surface of the conductive substrate is preferably 1 to 40 atomic%, more preferably 5 to 3
It is preferably 5 atomic%, optimally 10 to 30 atomic%. In the present invention, the first photoconductive layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of the film forming parameters so that desired characteristics can be obtained. Specifically, glow discharge method (low frequency CVD method, high frequency CVD method)
Method or an AC discharge CVD method such as a microwave CVD method, or a DC discharge CVD method). In order to form the nc-SiC: H photoconductive layer by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a C supply that can supply carbon atoms (C). A raw material gas for hydrogen gas and a raw material gas for supplying H, which can supply hydrogen atoms (H), are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and glow discharge is performed in the reaction vessel. A layer made of nc-SiC: H may be formed on the surface of a predetermined conductive substrate that has been caused to occur and is installed in advance at a predetermined position.

In the present invention, the carbon content in the first photoconductive layer can be gradually changed by gradually reducing the raw material gas capable of supplying carbon atoms. In the present invention, the layer thickness of the first photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the film thickness of the first photoconductive layer is as follows.
Preferably 5 to 50 μm, more preferably 10 to 40 μm
m, most preferably 20 to 30 μm. In the present invention, the second photoconductive layer is composed of nc-SiC: H containing silicon atoms and hydrogen atoms as constituent elements, and has desired photoconductive properties, particularly charge generation properties and charge transport properties. The second photoconductive layer of the present invention improves absorption by increasing the absorption of long-wavelength light and improves the traveling property of carriers having a polarity opposite to the charging polarity than that of the first photoconductive layer.
It is provided especially for the purpose of reducing ghost. In the present invention, the second photoconductive layer can be formed by the same method as the first photoconductive layer. In order to form the nc-Si: H photoconductive layer by the glow discharge method, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and an H supply, which can supply hydrogen atoms (H). A raw material gas for use in a reaction vessel whose inside can be decompressed into a desired gas state to cause glow discharge in the reaction vessel, and a predetermined conductive substrate installed in a predetermined position in advance. A layer of nc-Si: H may be formed on the surface.
In the present invention, the layer thickness of the second photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects.
Preferably 0.5 to 15 μm, more preferably 1 to 10
[mu] m, optimally 1 to 5 [mu] m is desirable.

Fabrication of First and Second Photoconductive Layers of the Present Invention
A substance that can be used as a Si supply gas for
Then SiH_Four , Si₂ H₆ , Si₃ H₈ , Si_Four H
_TenSilicon hydride in a gaseous state such as
Orchids) are mentioned as being effectively used.
In terms of ease of handling during layer preparation, good Si supply efficiency, etc.
SiH_Four , Si₂ H₆ Are listed as preferred
It In addition, if necessary, a source gas for supplying these Si may be used.
H₂ Dilute with gas such as He, Ar, Ne
You may. In the present invention, a raw material for introducing carbon atoms
As for the quality, a gas or
Are those which can be easily gasified under at least the layer forming conditions
Is preferred. Raw material for introducing carbon atom (C)
Starting materials effectively used as potential gas
Has C and H as constituent atoms, for example, having 1 to 5 carbon atoms.
Saturated hydrocarbon, C2-C4 ethylene hydrocarbon, charcoal
Examples include acetylene hydrocarbons having a prime number of 2 to 3. Ingredient
Physically, methane (CH _Four ),
Ethane (C₂ H₆ ), Propane (C₃ H₈ ), N-pig
(N-C_Four H_Ten), Pentane (C_Five H₁₂),ethylene
Ethylene (C₂ H_Four), Polypropylene
(C₃ H₆ ), Butene-1 (C_Four H₈ ), Butene-2
(C_Four H₈), Isobutylene (C_Four H₈ ), Penten
(C_Five H_Ten), As acetylene hydrocarbons, acetyl
Ren (C₂ H₂ ), Methylacetylene (C₃ H_Four ),
Chin (C_Four H₆ ) And the like. In addition, Si and C
The raw material gas used as the constituent atoms is Si (CH₃ )_Four ,
Si (C₂ H_Five )_Four And alkyl silicides such as
it can.

In order to structurally introduce hydrogen atoms into the first and second photoconductive layers, in addition to the above, H ₂ or Si
It is also possible to cause discharge by causing silicon hydride such as H ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in a reaction vessel. You can In order to control the amount of hydrogen atoms contained in the first and second photoconductive layers, for example, the temperature of the conductive substrate and the introduction of the raw material used for containing hydrogen atoms into the reaction vessel are introduced. The amount, discharge power, etc. may be controlled. In the present invention, it is particularly effective that the first photoconductive layer contains a halogen atom. In the present invention, the halogen atom contained in the first photoconductive layer suppresses the agglomeration of carbon atoms and hydrogen atoms and reduces the localized level density in the band gap, thus improving the ghost and improving the layer quality. It is effective in improving uniformity. When the amount of halogen atoms is less than 1 atom ppm, the effect of improving the ghost by the halogen atoms is not sufficiently exerted, and when it exceeds 95 atom ppm, the film quality is deteriorated and a ghost phenomenon occurs. Therefore, the content of halogen atoms is practically 1 to 95 atom ppm, more preferably 3 to 80 atom ppm, and most preferably 5 to 50 atom ppm. In particular, when the first photoconductive layer contains carbon atoms in the above range, by setting the content of halogen atoms in the above range, the photoconductive characteristics, image characteristics and durability are remarkably improved. It was confirmed by experiments. In addition, it is particularly effective for the present invention to distribute the contained halogen atoms so as to gradually increase from the vicinity of the substrate toward the vicinity of the second photoconductive layer. In order to alleviate the change in internal stress generated between the substrate side and the surface layer side as the content of carbon atoms changes in the layer thickness direction by unevenly distributing the halogen atoms in the layer thickness direction, The defects in the deposited film are reduced and the film quality is improved. As a result, it is possible to improve the so-called temperature characteristics, which change in characteristics in accordance with the temperature change of the use environment of the electrophotographic photosensitive member, and improve the electrophotographic characteristics such as charging ability and image density unevenness between copies.

As such a halogen atom, fluorine,
There are chlorine, bromine and iodine, preferably fluorine and chlorine
Is more preferable, and fluorine is more preferable. Such a foot
Effective as a supply gas to contain elementary atoms in the layer
For example, fluorine gas, fluoride, fluorine
Kumu halogen compound, fluorine-substituted silane derivative
Gaseous or gasifiable fluorine compounds such as
Can be mentioned. In addition, silicon atoms and fluorine
A gaseous or gasifiable component of
A silicon hydride compound containing a fluorine atom is also effective.
Can be listed. Preferably used in the present invention
As the fluorine compound, ₂ , BrF, C
IF, ClF₃ , BrF₃ , BrF_Five , IF₃ , IF₇ 
And other halogen compounds. Fluorine atom
Substituted with a silicon compound containing a so-called fluorine atom
Specific examples of the silane derivative include SiF.
_Four, Si₂ F₆ Silicon fluoride such as
Can be listed. A system containing such a fluorine atom
The characteristics of the present invention can be achieved by using a recon compound and applying glow discharge and the like.
When forming a characteristic electrophotographic light-receiving member,
Do not use silicon hydride gas as gas for supplying
At least, non-single-crystal silicon containing fluorine atoms on a given substrate
It is possible to form a photoconductive layer consisting of
Of the introduction ratio of hydrogen atoms introduced into the photoconductive layer
To make it easier to control these gases
Furthermore, the gas of silicon compounds containing hydrogen gas or hydrogen atoms
It is preferable that a desired amount of the soot is mixed to form a layer. Also, each
Not only a single type of gas but also a mixture of multiple types at a specified mixing ratio
It does not matter. In the present invention, fluorine
The above-mentioned fluorides or fluorines are used as the gas for supplying atoms.
Silicon compounds containing element are used effectively
In addition to these, HF and SiH₃ F, SiH
₂ F₂ , SiHF₃ Fluorine-substituted silicon hydride, etc.
Effective light for various gases or substances that can be gasified
It can be mentioned as a raw material for forming the electrode layer. this
Among these substances, fluorine compounds containing hydrogen atoms are photoconductive.
At the same time as the introduction of fluorine atoms into the layer during layer formation, electrical
Or even a hydrogen atom, which is extremely effective in controlling the photoelectric properties,
Introduced in the present invention is suitable as a fluorogenic child.
Used as a supply gas.

In the present invention, it is also effective that the first photoconductive layer contains oxygen atoms in addition to halogen atoms. In this case, the synergistic action with the halogen atom relaxes the internal stress of the deposited film and suppresses the structural defect of the film. This improves the mobility of carriers in the photoconductive layer and reduces the potential shift. The content of such oxygen atoms is preferably in the range of 10 to 5000 atomic ppm within the above range of halogen atom content. Further, for the present invention, it is more preferable to distribute the oxygen atoms contained in the photoconductive layer so as to increase from the substrate side toward the surface layer side. At this time, the internal stress in the deposited film is effectively relieved and the structural defects of the film are suppressed, so that the mobility of carriers in the photoconductive layer is improved and the surface potential characteristics such as potential shift are further improved. In the present invention, the source gas for containing oxygen atoms in the first photoconductive layer is oxygen (O ₂ ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), dinitrogen oxide (N ₂
It is effective to add a diluting gas containing a small amount of O) to the raw material gas. Further, in the present invention, the first and second
It is preferable that the photoconductive layer (1) contains an atom (M) for controlling conductivity, if necessary. The conductivity-controlling atoms may be contained in the first and second photoconductive layers in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. There may be some parts.

As the atom (M) that controls the conductivity
Refers to so-called impurities in the semiconductor field
Which belongs to Group III of the Periodic Table, which produces
Atom (hereinafter abbreviated as "Group III atom") or n-type transmission
Atoms belonging to Group V of the Periodic Table giving conductivity (hereinafter referred to as "V
(Abbreviated as "group atom") can be used. Group III
As atoms, specifically, boron (B) aluminum
(Al), gallium (Ga), indium (In),
There is a lithium (Tl) etc., and B, Al and Ga are particularly preferable.
is there. Specific examples of the group V atom include phosphorus (P) and arsenic
(As), antimony (Sb), bismuth (Bi), etc.
Yes, P and As are particularly preferable. Contained in the photoconductive layer
The content of atoms (M) that control conductivity is
It is 1 × 10^-3~ 5 x 10^Four Atomic ppm, more preferred
Kuha 1 × 10^-2~ 1 x 10 ^Four Atomic ppm, optimally 1x
10^-1~ 5 x 10³ It is desirable to set it to atomic ppm.
In particular, the content of carbon atoms (C) in the first photoconductive layer
Is 1 × 10³ In the case of atomic ppm or less, contained in photoconductive layer
The content of the atom (M) to be generated is preferably 1 × 10
^-3~ 1 x 10³ Atomic ppm is desirable, carbon
Atom (C) content is 1 x 10³ When exceeding atomic ppm
In this case, the content of atoms (M) is preferably 1 × 1
0^-1~ 5 x 10^Four It is desirable to set it to atomic ppm. light
In the conductive layer, atoms that control conductivity, such as III
To structurally introduce a group atom or a group V atom,
When forming, a raw material for introducing a group III atom or a group III
A raw material for introducing a group V atom in a gas state in a reaction vessel,
Introduced with other gases to form the photoconductive layer
Just do it. Raw material for introducing Group III atoms or Group V
As a raw material for introducing a group atom, room temperature
Gaseous at atmospheric pressure, or at least easy under layering conditions
It is desirable to adopt a material that can be gasified. That's it
Specifically as a raw material for introducing such a group III atom,
For introducing boron atom, B₂ H₆ , B_Four H_Ten, B_Five 
H₉ , B_Five H₁₁, B₆ H _Ten, B₆ H₁₂, B₆ H₁₄Water
Boron arsenide, BF₃ , BCl₃ , BBr₃ Halogen etc.
Boron bromide etc. are mentioned. In addition, AlCl₃ , GaC
l₃ , Ga (CH ₃ )₃ , InCl₃ , TlCl₃ Etc.
Can be mentioned.

In the present invention, as a raw material for introducing a group V atom, those effectively used are phosphorus hydrides such as PH ₃ and P ₂ H ₄ , PH ₄ I and PF for introducing a phosphorus atom.
₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr
₅ , phosphorus halides such as PI ₃ may be mentioned. Besides this, A
sH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , As
F ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , S
bCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ etc. are also V
It can be cited as an effective starting material for introducing a group atom. In addition, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar or Ne, if necessary. Further, in the photoconductive layer of the light receiving member of the present invention, Group Ia, Group IIa of the periodic table,
You may contain at least 1 sort (s) of element selected from VIa group and VIII group. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there. Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and specific examples of the group IIa atom include beryllium (Be), magnesium (Mg) and calcium. (Ca), strontium (Sr), barium (Ba)
Etc. can be mentioned.

Specific examples of the Group VIa atom include chromium (Cr), molybdenum (Mo), and tungsten (W). The Group VIII atom includes iron (Fe) and Cobalt (Co), Nickel (Ni)
Etc. can be mentioned. In order to form a photoconductive layer made of nc-SiC (H) having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction vessel as desired. is there. The temperature (Ts) of the conductive substrate is appropriately selected according to the layer design, but in the usual case, it is preferably 20 to 500.
° C, more preferably 50-480 ° C, optimally 100-
The temperature is preferably 450 ° C. The surface layer in the present invention is composed of a non-single crystal material containing silicon atoms, carbon atoms, hydrogen atoms and Group III of the periodic table as constituent elements. By the surface layer of the manufacturing method of the present invention, the electrical withstand voltage can be dramatically improved, and as a result, even if there are spherical projections, which are abnormal growth of the film, to some extent, it is possible that they appear as image defects. Can be improved.
Further, even when the separation charger causes an abnormal discharge in the electrophotographic process at the time of withstanding voltage, the surface of the electrophotographic photosensitive member is not dielectrically broken, and so-called leak spots can be extremely reduced. Further, the carbon atoms contained in the surface layer of the present invention may be uniformly distributed in the layer, or there may be a portion containing carbon atoms in a non-uniform distribution in the layer thickness direction. Good. However, in the case of non-uniform distribution, it is preferable that the distribution is increased from the photoconductive layer toward the outermost surface.

The content of carbon atoms contained in the entire surface area of the surface layer in the present invention is carbon atoms / (silicon atoms + carbon atoms) in order to achieve effects such as high dark resistance and high hardness.
Is preferably 40 to 90 atom%, more preferably 45 to 90 atom%.
It is desirable that the content is 85 atom%, optimally 50 to 80 atom%. In order to exert the effect of the present invention, the contained periodic group III element is 1 × 10 ⁵ atom pp
It must be m or less. Further, it is effective that the surface layer of the present invention further contains a halogen atom. Since the halogen atom contained in the surface layer improves the water repellency, the high humidity flow due to the adsorption of water vapor is also reduced, and the electric characteristics of the electrophotographic photosensitive member are further improved. The halogen atom contained in the surface layer is 20 atom% or less, and the sum of the content of hydrogen atom and halogen atom is preferably 30 to 30%.
70 atomic%, more preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic%. In the present invention, it is effective that the surface layer further contains an oxygen atom or a nitrogen atom. The amount of oxygen atoms and / or nitrogen atoms contained in the surface layer is preferably 1 × 10 ⁻⁴ to
30 atomic%, more preferably 5 × 10 ^{−4 to} 25 atomic%,
Optimally, it is desirable to set the concentration to 1 × 10 ^{−3 to} 20 atom%.
Oxygen atoms and / or nitrogen atoms contained in the surface layer compensate for dangling bonds existing in nc-SiC: H and are effective in improving the film quality, and are carriers trapped at the interface between the photoconductive layer and the surface layer. To improve the image flow. In addition, the inclusion of oxygen atoms and nitrogen atoms in the surface layer improves the adhesiveness at the interface between the surface layer and the photoconductive layer, and it becomes possible to change the structure of the surface layer itself. The surface properties of the body, the pressure resistance, the protection function of the photoconductive layer and the aluminum cylinder that is the conductive substrate are improved, and the durability of the electrophotographic photoreceptor can be dramatically improved while maintaining excellent electrical characteristics. it can.

That is, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the durability against high voltage is improved due to the decrease in the dielectric constant, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur. Furthermore, in the case of using recycled paper, the surface layer containing silicon atoms, hydrogen atoms, halogen atoms, periodic group III elements, and further oxygen atoms and / or nitrogen atoms according to the method of the present invention has a high surface roughness. To prevent the adhesion of the sizing agent such as rosin of recycled paper to the surface of the electrophotographic photosensitive member, and to prevent the fusion of the toner and the image deletion in the long-term use. Be effective. In the present invention, nc-Si
To form the surface layer composed of C: H, a vacuum deposition method similar to the method for forming the photoconductive layer described above is adopted.
In the present invention, as the silicon supply gas and the raw material gas for introducing carbon atoms (C) used in forming the surface layer, the same ones as those used in forming the photoconductive layer can be used. Is. In the present invention, as the raw material gas used for containing Group III of the periodic table in the surface layer, the same ones as those used for forming the photoconductive layer can be used. Further, in the present invention, the surface layer includes a group Ia group, a group IIa, a group VIa of the periodic table,
It may contain at least one element selected from Group VIII. The element may be uniformly distributed in the photoconductive layer, or may be contained uniformly in the photoconductive layer, but in a state of being unevenly distributed in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there.

Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and specific examples of the group IIa atom include beryllium (Be) and magnesium (Mg). ), Calcium (C
a), strontium (Sr), barium (Ba), etc. can be mentioned. Specific examples of Group VIa atoms include chromium (Cr), molybdenum (Mo), and tungsten (W), and Group VIII atoms include iron (Fe) and cobalt (Co). ), Nickel (N
i) etc. can be mentioned. In the present invention, the layer thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, most preferably 0. 1-1
It is preferably set to 0 μm. When forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The temperature of the conductive substrate is appropriately selected in an optimum range, but is preferably 20 to 500 ° C, more preferably 50 to 500 ° C.
It is desirable that the temperature is 480 ° C., optimally 100 to 450 ° C. The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to 3} Torr, most preferably 1 × 10 ⁻⁴ to 1.
Torr is preferable. In the present invention, the ranges described above are mentioned as desirable numerical ranges of the conductive substrate temperature and the gas pressure for forming the surface layer, but these layer preparation factors are not usually independently determined separately. It is desirable to determine the optimum value of each layer production factor based on mutual and organic relations so as to form a surface layer having desired characteristics.

In the light receiving member of the present invention, a layer region whose composition is continuously changed may be provided between the photoconductive layer and the surface layer. By providing the layer region, the adhesion between the layers can be further improved. Further, in the light receiving member of the present invention, the photoconductive layer has a layer region containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction on the side of the conductive substrate. Is desirable. In the present invention, the energy for generating plasma may be DC, high frequency, microwave, or the like, but the effect of the present invention is more remarkable particularly when microwave or high frequency is used as the energy for generating plasma. Will be things. In the present invention, when microwaves are used for plasma generation, microwave power may be any as long as discharge can be generated, but 100 W or more and 10 kW or less,
Preferably, 500 W or more and 4 kW or less are suitable for carrying out the present invention. Hereinafter, the effects of the present invention will be specifically described using examples, but the present invention is not limited to these. <Example 48 and Comparative Example 14> Example 48 108 m in diameter made of aluminum having a purity of 99.5%
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for manufacturing an electrophotographic photosensitive member according to the present invention described above, and 15 minutes after the completion of the cutting step, as shown in FIG. The surface of the substrate was pretreated under the conditions shown in Table 85 by the surface treatment apparatus shown in FIG. However, in this example, as the surfactant, polyethylene glycol nonylphenyl ether was used as a 1 wt% aqueous solution. On the aluminum cylinder thus pretreated, according to the procedure detailed above, using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. A photographic photoreceptor was produced. In this example, the change pattern of the carbon content in the photoconductive layer is shown in FIG.
In order to change as described above, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer was changed linearly. At this time, the carbon content at the interface of the photoconductive layer with the substrate was set to about 10 atomic%. The carbon content was measured by elemental analysis by Rutherford backscattering method.

The surface properties of the produced electrophotographic photosensitive member were visually evaluated first, and then the copying machine NP-755 manufactured by Canon Inc.
0 was installed in an electrophotographic device modified for experiments,
The following evaluation was carried out for electrophotographic characteristics such as sensitivity and residual potential and image characteristics after endurance. Surface Haze The produced electrophotographic photosensitive member was visually inspected for the degree of surface haze. ◎: No cloudiness ◯: Partially cloudy △: Partially cloudy at several places and ×: Cloudy on the entire surface. Charging ability / sensitivity / residual potential Charging ability ………… The electrophotographic photoconductor is installed in the experimental device, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential meter dark surface potential of the electrophotographic photoconductor. To measure. Sensitivity: Charges the electrophotographic photoreceptor to a constant dark surface potential. Then, the light image is immediately irradiated. The light image is 550 nm using a xenon lamp light source and a filter.
Irradiate light excluding light in the following wavelength range. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter.
Adjust the exposure amount so that the light surface potential becomes a predetermined potential,
The exposure amount at this time is defined as the sensitivity.

Residual potential: The electrophotographic photoreceptor is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. White spots / halftone unevenness ... Put the electrophotographic photoconductor in a copier, which is a Canon copier NP-7550 modified for experiment, and transfer it by a normal electrophotographic process to form an image on a paper surface. Images were evaluated by the procedure. White Pochi ……… Canon full black chart (part number: F
The number of white spots having a diameter of 0.2 mm or less in the same area of the copy image obtained when Y9-9073) was placed on the platen and copied was counted. Halftone unevenness ... Image density of 100 points with a circular area with a diameter of 0.5 mm as one unit on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on a platen and copied. Was measured and the variation in the image density was evaluated. For each, ◎ is “excellently good” 〇 is “good” Δ is “no problem in practical use” × is “problem in practical use” Durability with recycled paper ... The manufactured electrophotographic photosensitive member was manufactured by Canon Copier NP-7550. Was installed in an electrophotographic apparatus modified for experiment and recycled paper was used to carry out a durability test of 3 million sheets. Then, the image characteristics were evaluated as follows.

Image deletion: Canon test chart (part number: FY9-9058) consisting entirely of characters on a white background
On the platen and irradiate with an exposure amount twice the normal exposure amount to make a copy. The obtained copy image was observed, and it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown. ◎ ... Good ◯ ... Partially discontinued. B: There are many breaks, but they can be recognized as characters, and there is no practical problem. Black spots: The number of black image defects with a diameter of 0.2 mm or less within the same area on the copy image obtained when a blank sheet was placed on the original plate and copied was counted. In each case, ⊚ is “excellently good” ◯ is “excellent” Δ is “no problem in practical use” x is “problem in practical use” These results are shown in Table 87. Comparative Example 14 A conductive substrate similar to that of Example 48 was cut in the same procedure, and the cut conductive substrate was treated under the conditions shown in Table 88 by the conventional conductive substrate cleaning apparatus shown in FIG. The surface was treated. The conductive substrate cleaning apparatus shown in FIG. 3 includes a processing tank 302 and a substrate transfer mechanism 303. The processing tank 302 includes a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361, and the transfer arm 361 includes the rail 36.
5, a moving mechanism 362 that moves on the upper surface 5, a chucking mechanism 363 that holds the base 301, and a chucking mechanism 36.
It is composed of an air cylinder 364 for moving up and down 3.

Substrate 3 placed on input table 311 after cutting
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichloroethane (trade name: ETERNA VG manufactured by Asahi Kasei Kogyo Co., Ltd.) 322 in the cleaning tank 321 performs cleaning for removing cutting oil and chips adhering to the surface. After cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. In the same manner as in Example 48, the 89th substrate was prepared by pretreating the conventional substrate in this manner.
Under the conditions shown in the table, a so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate, a charge transport layer, a charge generation layer and a surface layer was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 48, and the results of Example 48 are shown in Table 87. As is clear from Table 87, according to the method of the present invention, the sensitivity is improved and the residual potential is kept low. Further, it can be seen that especially the surface of the photoconductor has excellent characteristics such as cloudiness, uneven halftone, and durability characteristics with recycled paper. In particular, according to the present invention, it is understood that there is no problem on the image even after the durability of 3 million sheets using recycled paper. <Example 49 and Comparative Example 15> Example 49 FIGS. 2A and 2 are formed on a substrate obtained by pretreating the same substrate as in Example 48 using the substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 90. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 48. As a result, Example 48
The exact same result was obtained. Comparative Example 15 On a conductive substrate that was pretreated in the same manner as in Comparative Example 14 by the substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photoreceptor manufacturing apparatus shown in (b), a so-called function-separated type having a three-layer structure of a substrate, a charge transport layer, a charge generation layer, and a surface layer by the microwave glow discharge method under the conditions shown in Table 91. An electrophotographic photoreceptor was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 49. As a result, the same result as in Comparative Example 15 was obtained. <Example 50 and Comparative Example 16> Example 50 On the substrate pretreated in the same manner as in Example 48 with the substrate surface treating apparatus shown in FIG. 1, the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 was used. Follow the steps detailed above
Electrophotographic photoreceptors were produced by the high frequency glow discharge method under the production conditions shown in Table 92. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 49 and 50, CH introduced at the time of forming the photoconductive layer.
By changing the flow rate of ₄ , two types of photoconductors were produced. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. For the measurement of the carbon content, a calibration curve of the standard sample was prepared by elemental analysis by the Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the signal intensity by Auger spectroscopy.

[0216] The surface fog of the produced electrophotographic photosensitive member was visually judged and the Canon copying machine NP-7550 was installed in an electrophotographic apparatus modified for experiments.
White spots and halftone unevenness were evaluated in the same manner as in Example 48. After that, the durability of 3 million sheets was evaluated in a modified NP-7550 machine using the recycled copying paper manufactured by Canon, the image deletion and the black spot were evaluated in the same manner as in Example 48, and the results are shown in Table 93. Comparative Example 16 An electrophotographic photosensitive member having a carbon content pattern shown in FIGS. 51 and 52 was produced on a substrate pretreated in the same manner as in Comparative Example 14 in the same manner as in Example 50. The same evaluation was performed. The results are shown in Table 93 together with the evaluation results of Example 50. From Table 93, it can be seen that, in the carbon content changing pattern of the photoconductive layer of the present invention, good results were obtained in both the initial characteristics and the image characteristics after endurance as compared with the results of Comparative Example 16. <Example 51 and Comparative Example 17> Example 51 Electrons shown in FIGS. 2 (a) and 2 (b) are formed on a substrate which has been pretreated in the same manner as in Example 48 by the substrate surface treatment apparatus shown in FIG. The same procedure as in Example 50 was carried out except that a microwave glow discharge method was used by using a photographic photoreceptor manufacturing apparatus.
Electrophotographic photoreceptors were produced under the production conditions shown in Table 4. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 49 and 50, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. The carbon content was measured by elemental analysis by Rutherford backscattering method. The electrophotographic photoconductor thus produced gave the same results as in Example 50. Comparative Example 17 An electrophotographic photograph was carried out in the same manner as in Example 51 on the substrate pretreated in the same manner as in Comparative Example 14 by the substrate surface treatment apparatus shown in FIG. A photoconductor was prepared. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 51, the same results as in Comparative Example 16 were obtained. <Embodiment 52> The procedure detailed above is carried out on a substrate which has been pretreated in the same manner as in Example 48 by the substrate surface treating apparatus shown in FIG. 1 and which uses the electrophotographic photosensitive member producing apparatus shown in FIG. According to the above, an electrophotographic photosensitive member was manufactured by the high frequency glow discharge method under the manufacturing conditions shown in Table 86. In this example, the change pattern of carbon content in the photoconductive layer was changed by using FIG. 48 and changing the carbon content of the surface on the substrate side by changing the flow rate of CH ₄ introduced during the formation of the photoconductive layer. The carbon content on the substrate-side surface of the photoconductive layer was identified by elemental analysis by Rutherford backscattering method.

The number of occurrences of cloudiness and spherical projections on the surface of the electrophotographic photosensitive member thus produced, and further, Canon Copier NP-75
50 was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness, and the image quality after 3 million sheets of recycled paper were evaluated. . Each item was performed by the following method. Surface haze Evaluation was performed in the same manner as in Example 48. Number of Spherical Protrusions The entire surface of the produced electrophotographic photosensitive member was observed with an optical microscope to check the number of spherical protrusions having a diameter of 20 μm or more within an area of 100 cm ² . Results were obtained for each electrophotographic photosensitive member, and the one having the largest number of spherical projections was set as 100% for relative comparison. The results are classified as follows. ⊚ is less than 60% ◯ is 80 to 60% Δ is 100 to 80% Residual potential Evaluation was made in the same manner as in Example 48. White spot / halftone unevenness White spot / halftone unevenness ... The evaluation was performed in the same manner as in Example 48. The results thus obtained are summarized in Table 95. From these results, the carbon content on the substrate-side surface of the photoconductive layer was improved at 0.5 to 50 atomic%, and very good results were obtained at 1 to 30 atomic%. <Example 53> A substrate surface-treated with the substrate shown in FIG. 1 was pretreated in the same manner as in Example 48.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), the electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 90 according to the procedure detailed above. did. In this embodiment, the change pattern of carbon content in the photoconductive layer is shown in FIG. 48, and the carbon content of the surface on the substrate side is changed by changing the flow rate of CH ₄ introduced during the formation of the photoconductive layer for each photoconductor. Was changed by. As a result of evaluation in the same manner as in Example 52, exactly the same results as in Table 95 were obtained. <Example 54> A substrate subjected to the same pretreatment as in Example 48 was subjected to a high frequency glow discharge method in accordance with the procedure described in detail above using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in the table. In this example, the fluorine content in the photoconductive layer was measured as shown in FIG.
The flow rate of SiF ₄ introduced at the time of forming the photoconductive layer was changed in order to change it as shown in FIG. The fluorine content in the photoconductive layer is determined by SIMS (CAMECA IMS
-3F) elemental analysis showed 3 near the substrate.
at. ppm, 40 at. It was ppm. (I) Canon electrophotographic photocopier NP
-7550 was installed in the electrophotographic device modified for experiments,
White spots, halftone spots before the accelerated durability test,
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Example 1 and Example 52. The ghost was evaluated as follows.

Ghost: A ghost test chart (part number: FY9-9040) manufactured by Canon Inc. had a reflection density of 1.
1. Place a 5mm black circle pasted on the front edge of the image on the platen, and overlay a Canon halftone chart on top of it. The difference between the reflection density of 5 mm and the reflection density of the middle portion was measured. For each of them, ⊚ is “excellently good”, ◯ is “excellent”, Δ is “practical problem,” and “practical problem.” The results are summarized in Table 97. (II) Next, it was produced. The electrophotographic photosensitive member was installed in an electrophotographic apparatus modified from Canon Copier NP-7550 for experiments, and a durability test of 3 million sheets was conducted using recycled paper.
Then, electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The results are summarized in Table 98. From the results shown in Tables 97 and 98, it is possible to produce an electrophotographic photosensitive member having excellent image characteristics and durability by setting the fluorine content in the photoconductive layer in the range of 95 atomic ppm or less. Has been shown to be possible. <Example 55> By using the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 99 by the microwave glow discharge method in the same manner as in Example 54. Then, the produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 54. The results were exactly the same as in Tables 97 and 98. <Embodiment 56> A substrate which has been pretreated in the same manner as in Embodiment 48 by the substrate surface treatment apparatus shown in FIG. 1 and the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 100. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer.

The produced electrophotographic photosensitive member was installed in an electrophotographic apparatus modified from Canon Copier NP-7550 for experiments, and the charging ability, residual potential, image evaluation before endurance, and 3 million sheets of recycled paper were used. Image evaluation after the durability test was performed by the following method. Charging ability: The same as in Example 48. Residual potential ... The same operation as in Example 48 was performed. Image evaluation after endurance: Limit samples of 5 grades were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 grades. ⊚ is “especially good” ◯ is “good” Δ is “no problem in practical use” × is “problem in practical use” The above results are shown in Table 101. As is clear from the table, when the carbon content is 40 to 90 atom%, a remarkable improvement in charging ability and durability is observed. <Example 57> By using the substrate surface treating apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 102 in the same manner as in Example 56. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer. The produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 56. As a result, the same results as in Table 101 were obtained. <Example 58> The substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 103. Nitrogen atoms, oxygen atoms contained in the surface layer of the electrophotographic photoreceptor prepared in this experiment,
When the boron atom was quantified by SIMS, the nitrogen atom and the oxygen atom were several tens ppm, and the boron atom was several pmm.

The electrophotographic photosensitive member thus produced was installed in an electrophotographic copying machine which was a Canon copying machine NP-7550 modified for experiments, and 3 million sheets of images after durability were visually evaluated using recycled paper. I did. as a result,
Very good results were obtained without an increase in image deletion and white spots. <Example 59> By using the substrate surface treating apparatus shown in FIG.
Using the electrophotographic photosensitive member manufacturing apparatus shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by a microwave glow discharge method under the manufacturing conditions shown in Table 104. In this example, the CH ₄ flow rate was changed in the surface layer so that the carbon atom content in the surface layer was distributed in the layer thickness direction so as to be maximized at the outermost surface. At this time, the flow rate of the source gas was changed so that the contents of boron, nitrogen and oxygen atoms in the surface layer were gradually increased. The electrophotographic photosensitive member thus produced was installed in an electrophotographic copying apparatus modified from Canon Copier NP-7550 for experiments, and 3 million sheets of images after running were visually evaluated using recycled paper. As a result, very good results were obtained without causing image deletion and white spots. <Example 60> FIGS. 2 (a) and 2 (b) are shown on a substrate which has been pretreated in the same manner as in Example 48 under the conditions shown in Table 105 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 106 by a microwave glow discharge method using an electrophotographic photosensitive member manufacturing apparatus. In this embodiment, the content of fluorine in the photoconductive layer is shown in FIG.
SiF ₄ / SiH ₄ so that the distribution form shown in 3-56 is obtained.
By changing the flow rate smoothly within the range of 10 to 50 ppm, four types of electrophotographic photosensitive members were produced. An electrophotographic photosensitive member was also produced under the same conditions except that it did not contain fluorine. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, charging ability, sensitivity, residual potential, white spots, halftone unevenness, ghost ... Evaluation similar to that in Example 1 Temperature characteristics: The produced electrophotographic photosensitive member was manufactured by Canon Copier NP-7550. Put in a copier modified for experiment,
The surface temperature of the electrophotographic photosensitive member is changed to 30 to 45 ° C,
A high voltage of +6 kV is applied to the charger, corona charging is performed, and the surface potential of the dark part is measured by a surface potential meter. The change in the surface temperature of the dark portion with respect to the surface temperature of the photoconductor is approximated by a straight line, and the slope is defined as "temperature characteristic", which is expressed in units of [V / deg]. ⊚ ... very good. Good ... Excellent. B: No problem in practical use. ×: not practical The above results are shown in Table 107. From the table, it is understood that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, electrophotographic characteristics including ghost and temperature characteristics are improved. <Example 61> FIGS. 2 (a) and 2 (b) are provided on a substrate which has been pretreated in the same manner as in Example 48 under the conditions shown in Table 106 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the conditions shown in Table 108 by a microwave glow discharge method using an electrophotographic photosensitive member manufacturing apparatus. In this example, the content of fluorine in the photoconductive layer was kept constant, and the content of CO ₂ / SiH ₄ was 10 to 50 ppm so that the oxygen content was in the distribution form shown in FIGS. 57 to 60.
By changing the flow rate smoothly within the range of, four types of electrophotographic photosensitive members were produced. An electrophotographic photosensitive member was also produced under the same conditions except that oxygen was not contained. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, chargeability, sensitivity, residual potential, white spots, halftone unevenness, ghost, temperature characteristics ... Evaluation similar to that in Example 60 Potential shift ... Electrophotographic photosensitive member was installed in experimental apparatus and charger High voltage of + 6kV is applied to and corona charging is performed.
The surface potential of the dark part of the electrophotographic photosensitive member is measured by a surface potential meter. At this time, the dark surface potential V _d0 immediately after the voltage is applied to the charger and the dark surface potential after 2 minutes is V _d .
Then, the difference between V _d0 and V _d is the amount of potential shift. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problematic in practical use” The above results are shown in Table 109. From the table, it can be seen that even when the photoconductive layer contains fluorine and further contains oxygen atoms, the position shift characteristics are improved.

[0223]

[Table 85]

[0224]

[Table 86]

[0225]

[Table 87]

[0226]

[Table 88]

[0227]

[Table 89]

[0228]

[Table 90]

[0229]

[Table 91]

[0230]

[Table 92]

[0231]

[Table 93]

[0232]

[Table 94]

[0233]

[Table 95]

[0234]

[Table 96]

[0235]

[Table 97]

[0236]

[Table 98]

[0237]

[Table 99]

[0238]

[Table 100]

[0239]

[Table 101]

[0240]

[Table 102]

[0241]

[Table 103]

[0242]

[Table 104]

[0243]

[Table 105]

[0244]

[Table 106]

[0245]

[Table 107]

[0246]

[Table 108]

[0247]

[Table 109]

(Fifth Invention) Hereinafter, an electrophotographic photosensitive member having the structure shown in FIG. 5B is actually formed by the method for manufacturing an electrophotographic photosensitive member of the present invention, using an aluminum alloy cylinder as a conductive substrate. An example of the procedure will be described using the pretreatment apparatus for the conductive substrate shown in FIG. 1 and the deposited film forming apparatus by the microwave CVD method shown in FIGS. 2 (a) and 2 (b). In Fig. 1, a lathe with an air damper for precision cutting (manufactured by PNEUMO PRECLSION INC.)
And a diamond bite (trade name: Miracle bite, made by Tokyo Diamond) at 5 ° to the cylinder center angle.
Set to get the rake angle of. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min,
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of the feed rate of 0.01 mm / R. With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing section 102 and a substrate transfer mechanism 103.
Has become The processing unit 102 includes a substrate loading table 111,
Substrate cleaning tank 121, pure water contact tank 131, drying tank 141,
The base unloading table 151 is provided. Both the cleaning tank 121 and the pure water contact tank 131 are equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transport mechanism 103 includes a transport rail 165 and a transport arm 161, and the transport arm 161 moves on the rail 165.
2, a chucking mechanism 16 for holding the conductive substrate 101
3 and an air cylinder 164 for moving the chucking mechanism 163 up and down. After cutting, the conductive substrate 101 placed on the input table 111 is the transfer mechanism 10
3 is conveyed to the cleaning tank 121. The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution 122 in the cleaning tank 121. Next, the conductive substrate 101 is transported to the pure water contact tank 131 by the transport mechanism 103, and pure water having a resistivity of 17.5 MΩ-cm kept at a temperature of 25 ° C. is discharged from the nozzles 132 to 5
It is sprayed at a pressure of 0 kg · f / cm ² . The conductive substrate 101 that has undergone the pure water contact step is moved to the drying tank 141 by the transport mechanism 103, and is dried by being blown with high-temperature high-pressure air from the nozzle 142. The conductive substrate 101 that has undergone the drying process is transported by the transport mechanism 103 to the unloading table 15
Carried to 1.

Next, an amorphous film is formed on the surface of the conductive substrate after the cutting and pretreatment by the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b). A deposited film mainly composed of silicon is formed. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Reference numeral 202 denotes microwave power for the reaction vessel 2.
01 is a microwave introduction dielectric window formed of a material (for example, quartz glass, alumina ceramics, or the like) that can efficiently penetrate into 01 and maintain vacuum tightness. 20
Reference numeral 3 denotes a waveguide for transmitting microwave power, which is composed of a rectangular portion from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. Waveguide 2
03 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212, and is electrically connected to the electrode 212. The electrophotographic photoreceptor is manufactured using such a deposited film forming apparatus as follows. First, the reaction container 201 is evacuated through the exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction container 201 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the heater 207 heats and holds the temperature of the substrate 205 at a predetermined temperature. Therefore, a raw material gas such as a silane gas as a raw material gas for amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluent gas is introduced into the reaction vessel 201 through a gas introduction means (not shown). At the same time, a microwave power source (not shown) generates a microwave having a frequency of 2.45 GHz, and the dielectric window 20 passes through the waveguide 203.
It is introduced into the reaction vessel 201 via the No. Further, a DC power source 211 electrically connected to the bias electrode 212 in the discharge space 206 applies a DC voltage to the bias electrode 212 with respect to the substrate 205. Thus, the conductive substrate 205
In the discharge space 206 surrounded by, the source gas is excited by the energy of microwaves and dissociates, and the electric field between the bias electrode 212 and the base 205 constantly causes ion bombardment on the conductive base 205. While the base 2
05 A deposited film is formed on the surface. At this time, the conductive substrate 2
The rotating shaft 209 on which No. 05 is installed is rotated by the motor 210, and the conductive substrate 205 is rotated around the central axis in the substrate generatrix direction to form a deposited film layer uniformly over the entire circumference of the conductive substrate 205. .

With such a manufacturing apparatus, an electrophotographic photosensitive member comprising the first photoconductive layer, the second photoconductive layer, and the surface layer, which are the essential requirements of the present invention, is prepared under the conditions shown in Table 111, for example. can do. Next, the present invention will be described in detail. In the present invention, the cleaning liquid used in the cleaning step is preferably water or water containing a surfactant added. And the quality of the water is possible. The surfactant used in the washing step may be any of anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, or a mixture thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added. If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore,
The temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C or higher and 55.
C. or lower is suitable for the present invention. In the present invention, it is preferable to use ultrasonic waves in the washing step in order to bring out the effect of the present invention sufficiently. The frequency of ultrasonic waves is preferably 100 Hz
Or more, 10 MHz or less, more preferably 1 kHz or more,
5MHz or less, optimally 10kHz or more, 100kHz
The following are effective: The ultrasonic output is preferably 10
W or more and 100 kW or less, and more preferably 100 W or more and 10 kW or less are effective.

Water of water used in the pure water contact step of the present invention
Quality is very important, and semiconductor grade pure water, especially ultra
LSI grade ultrapure water is preferred. Specifically, the water temperature
As the resistivity at 25 ° C, 1 MΩ-cm or more is preferable.
4 MΩ-cm or more, optimally 10 MΩ-cm or more
Suitable for the present invention. The amount of fine particles is 0.2 μm
The above is less than 100,000 pieces per milliliter, preferably
Ku or 10,000 or less, optimally 1000 or less
Suitable for light. The total number of viable bacteria is 1 mi
1000 or less, preferably 100 or less
Below, optimally 10 or less are suitable for the present invention. Organic
The physical quantity (TOC) is 100 mg or less per liter,
10 mg or less, optimally 2 mg or less is suitable for the present invention.
Is suitable. As a method of obtaining water of the above water quality,
Charcoal method, distillation method, ion exchange method, filter filtration method, reverse
Penetration method, ultraviolet sterilization method, etc. are available.
It is hoped that they will be used in combination to raise the required water quality.
Good When bringing pure water into contact with the conductive substrate surface,
It is desirable to apply pressure and spray. When spraying
If the water pressure is too weak, the effect of the present invention will be small.
If it is too strong, on the image of the obtained electrophotographic photoreceptor, especially
A pear-like pattern appears on the halftone image.
U Therefore, the pressure of water is 2 kgf / cm ² Since
Upper, 300kgf / cm² Below, preferably 10kg
・ F / cm² Above, 200kgf / cm² Below,
Suitably 20 kg / f / cm² Above 150kgf / c
m² The following are suitable for the present invention. However, in the present invention
Pressure unit kg ・ f / cm² Is the kilogram of gravity per square
Means centimeter, 1kgf / cm² Is 980
It is equal to 66.5 Pa. Method of spraying pure water of the present invention
Spray the water pressurized by the pump from the nozzle.
Or pumping water with high pressure air and nozzle.
Method before mixing and spraying with air pressure
Etc.

From the effect of the invention and the economical efficiency, the flow rate of the pure water of the present invention is 1 liter / mi per conductive substrate.
n or more and 200 liters / min or less, preferably 2 liters / min or more and 100 liters / min or less, optimally 5 liters / min or more, 50 liters / min
The following are suitable: If the temperature of the pure water of the present invention is too high, an oxide film will be generated on the conductive substrate, which may cause peeling of the deposited film, and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of pure water is 5 ° C or higher, 90 ° C
Below, preferably 10 ℃ or more, 55 ℃ or less, optimally 1
A temperature of 5 ° C or higher and 40 ° C or lower is suitable for the present invention. If the treatment time of the water contact treatment is too long, an oxide film is generated on the conductive substrate, and if it is too short, the effect of the present invention is small, so 10 seconds or more, 30 minutes or less, preferably 20 seconds or more,
20 minutes or less, optimally 30 seconds or more and 10 minutes or less are suitable for the present invention. In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film or the like on the surface of the substrate during the formation of the deposited film. If the time from cutting to water contact treatment is too long, an oxide film will be generated again on the surface of the substrate, and if it is too short, the process will not be stable, so 1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours. Hereafter, optimally 3 minutes or more and 4 hours or less are suitable for the present invention. If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable.
Minutes or more and 8 hours or less, preferably 2 minutes or more and 4 hours or less, optimally 3 minutes or more and 2 hours or less are suitable for the present invention.

As the conductive substrate used in the present invention,
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, glass, ceramic, or the like of an electrically insulating conductive substrate on which at least the light receiving layer is formed is formed. A substrate whose surface is subjected to a conductive treatment can be used, but a metal is preferable from the viewpoint of mechanical strength and the like. In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive substrate in order to eliminate an image defect due to an interference fringe pattern that appears in a visible image. The unevenness provided on the surface of the conductive substrate is described in JP-A-60-168156 and JP-A-60-168156.
It is produced by a known method described in JP-A-178457 and JP-A-60-225854. Further, as another method for eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are smaller than the resolving power required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. Unevenness due to a plurality of spherical trace depressions provided on the surface of the conductive substrate is disclosed in Japanese Patent Application Laid-Open No. 61-61.
It is produced by a known method described in Japanese Patent Publication No. 231561.

The first photoconductive layer in the present invention comprises a silicon atom and a carbon atom as constituent elements from the side of the conductive substrate.
It is composed of a photoconductive layer made of nc-SiC (H) containing a hydrogen atom, and has desired photoconductive characteristics, particularly charge retention characteristics,
It has charge generation characteristics and charge transport characteristics. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in a plane parallel to the surface of the conductive substrate,
The layer is non-uniform in the thickness direction, and the content on the conductive substrate side is high and the content on the surface layer side is low at each point in the film thickness direction. If the content of carbon atoms is 0.5% or less on the surface on the side where the conductive substrate is provided or in the vicinity of the surface, the function of improving the adhesiveness with the conductive substrate and preventing the injection of charges will be achieved. As a result, the effect of improving the charging ability due to the decrease in capacitance is lost. Again 50
% Or more, a residual potential is generated. Therefore, practically 0.5 to 50 atom%, preferably 1 to 40 atom%.
And optimally 1 to 30 atomic%. Further, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for making it happen. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the carbon content. Therefore, the content of hydrogen atoms on the surface of the conductive substrate is preferably 1 to 40 atomic%, more preferably 5 to 3
It is preferably 5 atomic%, optimally 10 to 30 atomic%. In the present invention, the first photoconductive layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of the film forming parameters so that desired characteristics can be obtained. Specifically, glow discharge information (low frequency CVD method, high frequency CVD
Method or an AC discharge CVD method such as a microwave CVD method, or a DC discharge CVD method). In order to form the nc-SiC: H photoconductive layer by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a C supply that can supply carbon atoms (C). A raw material gas for hydrogen gas and a raw material gas for supplying H, which can supply hydrogen atoms (H), are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and glow discharge is performed in the reaction vessel. A layer made of nc-SiC: H may be formed on the surface of a predetermined conductive substrate that has been caused to occur and is installed in advance at a predetermined position.

In the present invention, the carbon content in the first photoconductive layer can be gradually changed by gradually reducing the raw material gas capable of supplying carbon atoms. In the present invention, the layer thickness of the first photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the film thickness of the first photoconductive layer is as follows.
Preferably 5 to 50 μm, more preferably 10 to 40 μm
m, most preferably 20 to 30 μm. In the present invention, the second photoconductive layer is composed of nc-Si: H containing silicon atoms and hydrogen atoms as constituent elements, and has desired photoconductive properties, particularly charge generation properties and charge transport properties. The second photoconductive layer of the present invention enhances absorption by absorbing long-wavelength light to improve sensitivity, and because the carrier having a polarity opposite to the charging polarity has better phototaxis than the first photoconductive layer, It is provided especially for the purpose of reducing ghost. In the present invention, the second photoconductive layer can be formed by the same method as the first photoconductive layer. In order to form the nc-Si: H photoconductive layer by the glow discharge method, basically, a source gas for supplying Si that can supply silicon atoms (Si) and an H supply that can supply hydrogen atoms (H). A raw material gas for use in a reaction vessel whose inside can be decompressed in a desired gas state to cause glow discharge in the reaction vessel, and a predetermined conductive substrate installed in a predetermined position in advance. A layer of nc-Si: H may be formed on the surface. In the present invention, the layer thickness of the second photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and the second photoconductive layer is preferably 0. 0.5 to 15 μm, more preferably 1 to 10 μm
m, most preferably 1 to 5 μm.

Preparation of First and Second Photoconductive Layers of the Present Invention
A substance that can be used as a Si supply gas for
Then SiH_Four , Si₂ H₆ , Si₃ H₈ , Si_Four H
_Ten, Etc. in a gaseous state or gasifiable silicon hydride
(Silanes) are mentioned as being effectively used,
In addition, the ease of handling during layer preparation, good Si supply efficiency, etc.
SiH at the point_Four , Si₂ H₆ Are preferred
Be done. In addition, these raw material gases for supplying Si are not required.
H₂ Dilute with gas such as He, Ar, Ne, etc.
May be used. In the present invention, a raw material for introducing carbon atoms
A substance that can be a substance is gaseous at normal temperature and pressure.
Are those which can be easily gasified under at least the layer forming conditions
Is preferred. Raw material for introducing carbon atom (C)
Starting materials effectively used as potential gas
Has C and H as constituent atoms, for example, having 1 to 5 carbon atoms.
Saturated hydrocarbon, C2-C4 ethylene hydrocarbon, charcoal
Examples include acetylene hydrocarbons having a prime number of 2 to 3. Ingredient
Physically, methane (CH _Four ),
Ethane (C₂ H₆ ), Propane (C₃ H₈ ), N-pig
(N-C_Four H_Ten), Pentane (C_Five H₁₂),ethylene
Ethylene (C₂ H_Four), Polypropylene
(C₃ H₆ ), Butene-1 (C_Four H₈ ), Butene-2
(C_Four H₈), Isobutylene (C_Four H₈ ), Penten
(C_Five H_Ten), As acetylene hydrocarbons, acetyl
Ren (C₂ H₂ ), Methylacetylene (C₃ H_Four ),
Chin (C_Four H₆ ) And the like. In addition, Si and C
The raw material gas used as the constituent atoms is Si (CH₃ )_Four ,
Si (C₂ H_Five )_Four And alkyl silicides such as
it can.

In order to structurally introduce hydrogen atoms into the first and second photoconductive layers, in addition to the above, H ₂ or Si
It is also possible to cause discharge by causing silicon hydride such as H ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in a reaction vessel. You can In order to control the amount of hydrogen atoms contained in the first and second photoconductive layers, for example, the temperature of the conductive substrate and the introduction of the raw material used for containing hydrogen atoms into the reaction vessel are introduced. The amount, discharge power, etc. may be controlled. In the present invention, it is particularly effective that the first photoconductive layer contains a halogen atom. In the present invention, the halogen atom contained in the first photoconductive layer suppresses the agglomeration of carbon atoms and hydrogen atoms and reduces the localized level density in the band gap, thus improving the ghost and improving the layer quality. It is effective in improving uniformity. When the amount of halogen atoms is less than 1 atom ppm, the effect of improving the ghost by the halogen atoms is not sufficiently exerted, and when it exceeds 95 atom ppm, the film quality is deteriorated and a ghost phenomenon occurs. Therefore, the content of halogen atoms is practically 1 to 95 atom ppm, more preferably 3 to 80 atom ppm, and most preferably 5 to 50 atom ppm. In particular, when the first photoconductive layer contains carbon atoms in the above range, by setting the content of halogen atoms in the above range, the photoconductive characteristics, image characteristics and durability are remarkably improved. It was confirmed by experiments. In addition, it is particularly effective for the present invention to distribute the contained halogen atoms so as to gradually increase from the vicinity of the substrate toward the vicinity of the second photoconductive layer. In order to alleviate the change in internal stress generated between the substrate side and the surface layer side as the content of carbon atoms changes in the layer thickness direction by unevenly distributing the halogen atoms in the layer thickness direction, The defects in the deposited film are reduced and the film quality is improved. As a result, it is possible to improve the so-called temperature characteristics, which change in characteristics in accordance with the temperature change of the use environment of the electrophotographic photosensitive member, and improve the electrophotographic characteristics such as charging ability and image density unevenness between copies.

As such a halogen atom, fluorine,
There are chlorine, bromine and iodine, preferably fluorine and chlorine
Is more preferable, and fluorine is more preferable. Such a foot
Effective as a supply gas to contain elementary atoms in the layer
For example, fluorine gas, fluoride, fluorine
Kumu halogen compound, fluorine-substituted silane derivative
Gaseous or gasifiable fluorine compounds such as
Can be mentioned. In addition, silicon atoms and fluorine
A gaseous or gasifiable component of
A silicon hydride compound containing a fluorine atom is also effective.
Can be listed. Preferably used in the present invention
As the fluorine compound, ₂ , BrF, C
IF, ClF₃ , BrF₃ , BrF_Five , IF₃ , IF₇ 
And other halogen compounds. Fluorine atom
Substituted with a silicon compound containing a so-called fluorine atom
Specific examples of the silane derivative include SiF.
_Four, Si₂ F₆ Silicon fluoride such as
Can be listed. A system containing such a fluorine atom
The present invention can be applied by glow discharge or the like by adopting a recon compound.
When forming a characteristic electrophotographic light-receiving member,
Using silicon hydride gas as a gas for supplying the recon
Even if it is not used, non-single-crystal silicon containing fluorine atoms on a given substrate
It is possible to form a photoconductive layer consisting of
Of the introduction ratio of hydrogen atoms introduced into the photoconductive layer
To make it easier to control these gases
Furthermore, the gas of silicon compounds containing hydrogen gas or hydrogen atoms
It is preferable that a desired amount of the soot is mixed to form a layer. Also, each
Not only a single type of gas but also a mixture of multiple types at a specified mixing ratio
It does not matter. In the present invention, fluorine
The above-mentioned fluorides or fluorines are used as the gas for supplying atoms.
Silicon compounds containing element are used effectively
In addition to these, HF and SiH₃ F, SiH
₂ F₂ , SiHF₃ Fluorine-substituted silicon hydride, etc.
Effective light for various gases or substances that can be gasified
It can be mentioned as a raw material for forming the electrode layer. this
Among these substances, the fluorinated compounds containing hydrogen atoms are photoconductive layers.
At the same time as the introduction of fluorine atoms into the layer during formation, electrical
Or a hydrogen atom, which is extremely effective for controlling the photoelectric properties,
In the present invention, a suitable fluorine atom supply
Used as a gas for use.

In the present invention, it is also effective that the first photoconductive layer contains oxygen atoms in addition to halogen atoms. In this case, the synergistic action with the halogen atom relaxes the internal stress of the deposited film and suppresses the structural defect of the film. Therefore, the traveling light property of carriers in the photoconductive layer is improved, and the potential shift is reduced. The content of such oxygen atoms is preferably in the range of 10 to 5000 atomic ppm within the above range of halogen atom content. Further, for the present invention, it is more preferable to distribute the oxygen atoms contained in the photoconductive layer so as to increase from the substrate side toward the surface layer side. At this time, the internal stress in the deposited film is effectively relieved and the structural defects of the film are suppressed, so that the mobility of carriers in the photoconductive layer is improved and the surface potential characteristics such as potential shift are further improved. In the present invention, as a raw material gas for containing oxygen atoms in the first photoconductive layer, oxygen (O
₂ ) Add a diluting gas containing trace amounts of carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ) and dinitrogen oxide (N ₂ O) to the source gas. Is effective. Further, in the present invention, it is preferable that the first and second photoconductive layers contain an atom (M) that controls conductivity, if necessary. The conductivity-controlling atoms may be contained in the first and second photoconductive layers in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. There may be some parts.

As the atom (M) that controls the conductivity
Refers to so-called impurities in the semiconductor field
Which belongs to Group III of the Periodic Table, which produces
Atom (hereinafter abbreviated as "Group III atom") or n-type transmission
Atoms belonging to Group V of the Periodic Table giving conductivity (hereinafter referred to as "V
(Abbreviated as "group atom") can be used. Group III
As atoms, specifically, boron (B), aluminum
Aluminum (Al), gallium (Ga), indium (In),
There is thallium (Tl), etc., and B, Al, and Ga are particularly preferable.
Is. Specific examples of the group V atom include phosphorus (P) and arsenic.
Elemental (As), antimony (Sb), bismuth (Bi), etc.
And P and As are particularly preferable. Contained in photoconductive layer
The content of atoms (M) controlling conductivity is
1x10 is better^-3~ 5 x 10^Four Atomic ppm, more preferred
It is 1 × 10^-2~ 1 x 10 ^Four Atomic ppm, optimally 1
× 10^-1~ 5 x 10³ I hope it is atomic ppm
Yes. In particular, the first photoconductive layer contains carbon atoms (C).
The amount is 1 × 10³ If the atomic ppm or less, the photoconductive layer
The content of atoms (M) contained is preferably 1 ×
10^-3~ 1 x 10³ It is desirable that it be atomic ppm,
The content of carbon atoms (C) is 1 × 10³ Over atomic ppm
In this case, the content of atoms (M) is preferably 1
× 10^-1~ 5 x 10^Four I hope it is atomic ppm
Yes. In the photoconductive layer, atoms that control conductivity, such as
To structurally introduce a group III atom or a group V atom
Is a raw material for introducing a group III atom during layer formation.
Or a reaction vessel in which a raw material for introducing a Group V atom is in a gas state
Introduced with other gases to form the photoconductive layer
You can do it. Raw material for introducing Group III atoms or
As a raw material for introducing Group V atoms
Is a gas at room temperature and atmospheric pressure, or at least a layer forming condition
It is desirable that those that can be easily gasified under
Yes. As a raw material for introducing such a Group III atom,
Physically, for introducing boron atom, B₂ H₆ , B_Four 
H_Ten, B_Five H₉ , B_Five H₁₁, B₆ H _Ten, B₆ H₁₂, B₆ 
H₁₄Borohydride, BF, etc.₃ , BCl₃ , BBr₃ etc
And the like. In addition, AlCl
₃ , GaCl₃ , Ga (CH ₃ )₃ , InCl₃ , Tl
Cl₃ Etc. can also be mentioned.

The present invention as a raw material for introducing a Group V atom
Is effectively used in introducing phosphorus atoms
Is PH₃ , P₂ H_Four Phosphorus hydride, PH, etc._Four I, PF
₃ , PF_Five , PCl₃ , PCl_Five , PBr₃ , PBr
_Five , PI₃ And the like. Besides this, A
sH₃ , AsF₃ , AsCl₃ , AsBr₃ , AsF
_Five , SbH₃ , SbF₃ , SbF_Five , SbCl₃ , Sb
Cl_Five , BiH₃ , BiCl ₃ , BiBr₃ And so on
The effective starting materials for introducing atoms are
it can. In addition, for the introduction of atoms that control their conductivity
If necessary, H₂ , He, Ar, Ne, etc.
You may use it after diluting it with a soot. Further, the optical receiver of the present invention
The photoconductive layer of the container includes a group Ia, a group IIa, and VI of the periodic table.
Contains at least one element selected from Group a and Group VIII
You may. The element is uniformly distributed in the photoconductive layer.
May be distributed in the photoconductive layer or evenly distributed in the photoconductive layer.
Although it is contained in a large amount, it is unevenly distributed in the layer thickness direction.
May be contained in the state of containing. But Naga
In any case, the surface parallel to the conductive substrate surface
In the in-plane direction, it is contained evenly with a uniform distribution.
Is that it aims to make the characteristics uniform in the in-plane direction.
Also needed. As the group Ia atom, specifically,
Lithium (Li), sodium (Na), potassium
(K) can be mentioned, and as the group IIa atom,
Lilium (Be), magnesium (Mg), calcium
(Ca), strontium (Sr), barium (Ba)
Etc. can be mentioned.

Further, as the group VIa atom, specifically,
Examples thereof include chromium (Cr), molybdenum (Mo), and tungsten (W).
Iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned. In order to form a photoconductive layer made of nc-SiC (H) having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction vessel as desired. is there. The temperature (Ts) of the conductive substrate is appropriately selected according to the layer design, but in the usual case, it is preferably 20 to 500 ° C, more preferably 50 to 480 ° C, and most preferably 100 to 450 ° C.
It is desirable to set the temperature to ° C. The surface layer in the present invention is composed of a non-single-crystal material containing silicon atoms and carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms as constituent elements. The surface layer in the present invention does not substantially contain a substance that controls the conductivity as contained in the photoconductive layer. The carbon atoms contained in the surface layer may be uniformly distributed in the layer, or may be contained in the layer thickness direction in a uniform manner but contained in a non-uniformly distributed state. There may be a part that does. However, in any case, in the direction parallel to the surface of the conductive substrate,
It is necessary that the content be evenly distributed so that the characteristics are uniform in the in-plane direction. The carbon atoms, oxygen atoms, and nitrogen atoms contained in the entire surface layer region of the present invention have effects such as high dark resistance and high hardness. The total content of the three atoms contained in the surface layer is preferably (carbon atom + oxygen atom + nitrogen atom) / (silicon atom + carbon atom + oxygen atom + nitrogen atom) 40 to 40. 90 atomic%, more preferably 45 to 85 atomic%, and most preferably 50 to 80 atomic%.
In order to further exert the effect of the present invention,
Both the content of oxygen atoms and the content of nitrogen atoms are preferably 10 atomic% or less.

The hydrogen atom, oxygen atom and nitrogen atom contained in the surface layer in the present invention are nc-SiC: H.
Compensation for dangling bonds existing in the interior is effective for improving the film quality, and carriers trapped at the interface between the photoconductive layer and the surface layer are reduced, so that image deletion is improved. In addition, the inclusion of oxygen atoms and nitrogen atoms in the surface layer improves the adhesiveness at the interface between the surface layer and the photoconductive layer, and it becomes possible to change the structure of the surface layer itself. The surface properties of the body, the pressure resistance, the protection function of the photoconductive layer and the aluminum cylinder that is the conductive substrate are improved, and the durability of the electrophotographic photoreceptor can be dramatically improved while maintaining excellent electrical characteristics. it can. That is, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the durability against high voltage is improved due to the decrease in the dielectric constant, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur. Further, it is effective that the surface layer of the present invention further contains a halogen atom. Since the halogen atom contained in the surface layer improves the water repellency, the high humidity flow due to the adsorption of water vapor is also reduced, and the electric characteristics of the electrophotographic photosensitive member are further improved. The halogen atom contained in the surface layer is 20 atom% or less, and the sum of the content of hydrogen atom and halogen atom is preferably 30 to 70 atom% with respect to the sum of all the atoms in the surface layer. , And more preferably 35
It is desirable that the content be ˜65 atom%, and optimally 40˜60 atom%.

In the present invention, in order to form the surface layer composed of nc-SiC: H, the same vacuum deposition method as the above-mentioned method of forming the photoconductive layer is adopted. In the present invention, as the silicon supply gas and the raw material gas for introducing carbon atoms (C) used in forming the surface layer, the same ones as those used in forming the photoconductive layer can be used. Is. In the present invention, the introduced gas for allowing the surface layer to contain oxygen atoms and nitrogen atoms includes oxygen (O ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), and nitrogen atoms for oxygen atoms. Is nitrogen (N ₂ )
Ammonia (NH ₃ ) and the like can be mentioned. In addition, nitric oxide (N
O), nitrogen dioxide (NO ₂ ) and dinitrogen oxide (N ₂ O) are preferred. Further in the present invention, the surface layer,
It may contain at least one element selected from Group Ia, Group IIa, Group VIa, and Group VIII of the Periodic Table. The element may be uniformly distributed in the photoconductive layer,
Alternatively, although it is contained in the photoconductive layer in a uniform manner,
There may be a portion containing the non-uniformly distributed state in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary that the content is evenly distributed and evenly distributed in order to achieve uniform properties in the in-plane direction. is there. Ia
Specific examples of the group atom include lithium (Li), sodium (Na) and potassium (K),
Examples of Group IIa atoms include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like.

Further, as the group VIa atom, specifically,
Examples thereof include chromium (Cr), molybdenum (Mo), and tungsten (W).
Iron (Fe), cobalt (Co), nickel (Ni), etc. can be mentioned. In the present invention, the surface layer preferably has a thickness of 0.01 to 30 μm, more preferably 0.05 to 20 μm, and most preferably 0. It is desirable that the thickness is 1 to 10 μm. In the case of forming a surface layer having properties capable of achieving the object of the present invention, the temperature of the conductive substrate,
Gas pressure is an important factor that influences the characteristics of the surface layer. The conductive substrate temperature is appropriately selected in the optimum range, but is preferably 20 to 500 ° C., more preferably 50 to 480.
It is desirable to set the temperature to 100 ° C, optimally 100 to 450 ° C. The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 ×.
10 ^{−5 to 3} Torr, optimally 1 × 10 ^{−4 to} 1 Torr
Is desirable. In the present invention, the ranges described above are mentioned as desirable numerical ranges of the conductive substrate temperature and the gas pressure for forming the surface layer, but these layer preparation factors are not usually independently determined separately. It is desirable to determine the optimum value of each layer production factor based on mutual and organic relations so as to form a surface layer having desired characteristics. In the light receiving member of the present invention,
A layer region whose composition is continuously changed may be provided between the photoconductive layer and the surface layer. By providing the layer region, the adhesion between the layers can be further improved.

Further, in the light receiving member of the present invention, a layer containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction on the side of the conductive substrate of the photoconductive layer. It is desirable to have a region. In the present invention, the energy for generating plasma may be DC, high frequency, microwave, or the like, but the effect of the present invention is more remarkable particularly when microwave or high frequency is used as the energy for generating plasma. Will be things. In the present invention, when microwaves are used to generate plasma, microwave power may be any as long as discharge can be generated, but 100 W
10kW or less, preferably 500W or more, 4kW
The following are suitable for practicing the invention. Hereinafter, the effects of the present invention will be specifically described using examples, but the present invention is not limited to these. <Example 62 and Comparative Example 18> Example 62 108 m in diameter made of aluminum having a purity of 99.5%
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention described above, and after 15 minutes from the completion of the cutting step, as shown in FIG. The surface treatment apparatus shown in FIG. 1 pretreated the surface of the substrate under the conditions shown in Table 110. However, in this example, as the surfactant, polyethylene glycol nonylphenyl ether was used as a 1 wt% aqueous solution. On the aluminum cylinder thus pretreated, according to the procedure described in detail above, using the electrophotographic photoreceptor manufacturing apparatus shown in FIG.
Electrophotographic photoreceptors were produced under the production conditions shown in Table 1. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. 61, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly. At this time, the carbon content at the interface of the photoconductive layer with the substrate was about 10 atomic%.
So that The carbon content was measured by elemental analysis by Rutherford backscattering method.

The surface properties of the produced electrophotographic photosensitive member were visually evaluated first, and then the copying machine NP-755 manufactured by Canon Inc.
0 was installed in an electrophotographic device modified for experiments,
The following evaluation was carried out for electrophotographic characteristics such as sensitivity and residual potential and image characteristics after endurance. Surface Haze The produced electrophotographic photosensitive member was visually inspected for the degree of surface haze. ◎: No cloudiness ◯: Partially cloudy △: Partially cloudy at several places and ×: Cloudy on the entire surface. Charging ability / sensitivity / residual potential Charging ability ………… The electrophotographic photoconductor is installed in the experimental device, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential meter dark surface potential of the electrophotographic photoconductor. To measure. Sensitivity: Charges the electrophotographic photoreceptor to a constant dark surface potential. Then, the light image is immediately irradiated. The light image is 550 nm using a xenon lamp light source and a filter.
Irradiate light excluding light in the following wavelength range. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter.
Adjust the exposure amount so that the light surface potential becomes a predetermined potential,
The exposure amount at this time is defined as the sensitivity.

Residual potential: The electrophotographic photosensitive member is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. White spots / halftone unevenness ... Put the electrophotographic photoconductor in a copier, which is a Canon copier NP-7550 modified for experiment, and transfer it by a normal electrophotographic process to form an image on a paper surface. Images were evaluated by the procedure. White Pochi ……… Canon full black chart (part number: F
The number of white spots having a diameter of 0.2 mm or less in the same area of the copy image obtained when Y9-9073) was placed on the platen and copied was counted. Half Tome Mura ... A halftone chart made by Canon (part number: FY9-9042) was placed on the platen and copied, and a circular area with a diameter of 0.05 mm was defined as one unit, and an image density of 100 points was set. The measurement was performed and the variation in the image density was evaluated. For each of them, ◎ is “excellently good” 〇 is “good” Δ is “no problem in practical use” × is “problem in practical use” Image characteristics after endurance ... The manufactured electrophotographic photoreceptor is a Canon copier NP-7550. Was installed in an electrophotographic apparatus modified for experiments, and an accelerated durability test equivalent to 3.5 million sheets was performed. Then, the image characteristics were evaluated as follows.

Image deletion: Canon test chart consisting of all letters on a white background (part number: FY9-9058)
On the platen and irradiate with an exposure amount twice the normal exposure amount to make a copy. The obtained copy image was observed, and it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown. ◎ ... Good ◯ ... Partially discontinued. B: There are many breaks, but they can be recognized as characters, and there is no practical problem. Black spots: The number of black image defects with a diameter of 0.2 mm or less within the same area of the copy image obtained when a blank sheet was placed on the platen and copied was counted. For each of them, ⊚ is “excellently good”, ◯ is “excellent”, Δ is “no problem in practical use”, and “is a problem in practical use”. Comparative Example 18 A conductive substrate similar to that of Example 62 was cut in the same procedure, and the cut conductive substrate was treated with the conventional conductive substrate cleaning apparatus shown in FIG. The surface was treated. The conductive substrate cleaning apparatus shown in FIG.
It comprises a processing tank 302 and a substrate transfer mechanism 303. The processing bath 302 includes a substrate loading table 311, a substrate cleaning bath 321,
The substrate unloading table 351 is provided. The cleaning tank 321 is equipped with a temperature adjusting device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361.
The moving mechanism 362 includes a moving mechanism 362 that moves above the chuck 65, a chucking mechanism 363 that holds the substrate 301, and an air cylinder 364 that moves the chucking mechanism 363 up and down.

After cutting, the substrate 3 placed on the input table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichloroethane (trade name: ETERNA VG manufactured by Asahi Kasei Kogyo Co., Ltd.) 322 in the cleaning tank 321 performs cleaning for removing cutting oil and chips adhering to the surface. After cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. In the same manner as in Example 62, the 11th substrate was prepared by pretreating the conventional substrate in this manner.
Under the conditions shown in Table 4, a so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate, a charge transport layer, a charge generation layer and a surface layer was produced. The evaluation of the obtained electrophotographic photosensitive member was carried out in Example 62.
The results are shown in Table 112 together with the result of Example 62. As is clear from Table 112, according to the method of the present invention, the sensitivity is improved and the residual potential is kept low. It can be seen that particularly excellent characteristics are exhibited with respect to haze on the surface of the photoconductor and uneven halftone. Furthermore, according to the present invention, it can be seen that there is no problem on the image even after the endurance of 3.5 million sheets. <Example 63 and Comparative Example 19> Example 63 FIGS. 2A and 2 are formed on a substrate obtained by pretreating the same substrate as in Example 62 by the substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 115. The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 62. As a result, Example 6
The same result as in 2 was obtained. Comparative Example 19 A conductive substrate which had been pretreated in the same manner as in Comparative Example 18 by the substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (b), a so-called functional separation of a three-layer structure of a substrate, a charge transport layer, a charge generation layer, and a surface layer by the microwave glow discharge method under the conditions shown in Table 116. A type electrophotographic photosensitive member was produced. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 63.
As a result, the same result as in Comparative Example 19 was obtained. <Example 64 and Comparative Example 20> Example 64 On a substrate which was subjected to the same pretreatment as in Example 62 by the substrate surface treating apparatus shown in FIG. 1, the electrophotographic photosensitive member manufacturing apparatus shown in FIG. 4 was used. Follow the steps detailed above
An electrophotographic photosensitive member was manufactured by the high frequency glow discharge method under the manufacturing conditions shown in Table 117. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 62 and 63, C introduced at the time of forming the photoconductive layer was used.
Two types of photoconductors were produced by changing the flow rate of H ₄ . In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the signal intensity by Auger spectroscopy.

[0243] The produced electrophotographic photosensitive member was visually inspected for cloudiness, and the Canon copying machine NP-7550 was installed in an electrophotographic apparatus modified for experiments.
White spots and halftone unevenness were evaluated in the same manner as in Example 62. Then, the accelerated durability tester
The evaluation of about 0,000 sheets was performed, and the image deletion and the black spot were evaluated in the same manner as in Example 62. The results are shown in Table 118. Comparative Example 20 An electrophotographic photosensitive member was produced on the substrate pretreated in the same manner as in Comparative Example 18 in the same manner as in Example 64 with the carbon content patterns shown in FIGS. 64 and 65. The same evaluation was performed. The results are shown in Table 118 together with the evaluation results of Example 64. From Table 118, it can be seen that, in the carbon content change pattern of the photoconductive layer of the present invention, good results were obtained in both initial characteristics and image characteristics after endurance, as compared with the results of Comparative Example 20. <Example 65 and Comparative Example 21> Example 65 Electrons shown in FIGS. 2 (a) and 2 (b) are formed on a substrate which has been pretreated in the same manner as in Example 62 by the substrate surface treatment apparatus shown in FIG. Eleventh Embodiment In the same manner as in Example 64, except that the microwave glow discharge method is used by using the manufacturing apparatus for the photographic photosensitive member.
An electrophotographic photoreceptor was produced under the production conditions shown in Table 9. In this example, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 62 and 63, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed. In any of the patterns, the carbon content on the substrate-side surface of the photoconductive layer was set to be about 10 atom%. The carbon content was measured by elemental analysis by Rutherford backscattering method. The electrophotographic photoconductor thus produced gave the same results as in Example 64. Comparative Example 21 An electrophotographic photograph was carried out in the same manner as in Example 65 on the substrate pretreated by the substrate surface treating apparatus shown in FIG. 3 in the same manner as in Example 65, with the carbon content patterns shown in FIGS. A photoconductor was prepared. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 65, the same results as in Comparative Example 20 were obtained. <Example 66> The procedure described in detail above was carried out on the substrate pretreated in the same manner as in Example 62 by the substrate surface treating apparatus shown in FIG. 1 using the electrophotographic photosensitive member producing apparatus shown in FIG. In accordance with the above, an electrophotographic photosensitive member was manufactured by the high frequency glow discharge method under the manufacturing conditions shown in Table 111. In this example, the change pattern of the carbon content in the photoconductive layer is shown in FIG.
Was used to change the carbon content on the surface of the substrate by changing the flow rate of CH ₄ introduced at the time of forming the photoconductive layer.
The carbon content on the substrate-side surface of the photoconductive layer was identified by elemental analysis by Rutherford backscattering method.

The number of occurrences of cloudiness and spherical projections on the surface of the electrophotographic photosensitive member produced, and further, a copying machine NP-75 manufactured by Canon Inc.
The No. 50 was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness, and the image quality after endurance of 3.5 million sheets were evaluated. Each item was evaluated by the following methods. Surface haze Evaluation was performed in the same manner as in Example 62. Number of Spherical Protrusions The entire surface of the produced electrophotographic photosensitive member was observed with an optical microscope to check the number of spherical protrusions having a diameter of 20 μm or more within an area of 100 cm ² . Results were obtained for each electrophotographic photosensitive member, and the one having the largest number of spherical projections was set as 100% for relative comparison. The results are classified as follows. ⊚ is less than 60% ◯ is 80 to 60% Δ is 100 to 80% Residual potential Evaluation was performed in the same manner as in Example 62. White spot / halftone unevenness White spot / halftone unevenness ... The evaluation was performed in the same manner as in Example 62. The results thus obtained are summarized in Table 120. From these results, the carbon content on the substrate-side surface of the photoconductive layer was improved at 0.5 to 50 atomic%, and very good results were obtained at 1 to 30 atomic%. <Example 67> A substrate surface-treated with the substrate shown in FIG. 1 was pretreated in the same manner as in Example 62.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and (b), an electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 115 by the microwave glow discharge method according to the procedure detailed above. did. In this example, the pattern for changing the carbon content in the photoconductive layer is shown in FIG. 61, and the flow rate of CH ₄ introduced into the photoconductive layer to change the carbon content of the surface on the substrate side is changed for each photoconductor. Was changed by. As a result of evaluation in the same manner as in Example 66, exactly the same results as in Table 120 were obtained. <Example 68> On a substrate pretreated in the same manner as in Example 62, using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in the table. In this example, the fluorine content in the photoconductive layer was measured as shown in FIG.
In order to change as shown in 6, the flow rate of SiF ₄ introduced at the time of forming the photoconductive layer was changed. The fluorine content in the photoconductive layer is determined by SIMS (CAMECA IM
S-3F) elemental analysis showed 3 at. ppm, 40 at. It was ppm. (I) Canon electrophotographic photocopier NP
-8580 was installed in the electrophotographic device modified for the experiment,
White spot, half tome unevenness before the accelerated durability test,
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Example 62 and Example 66. The ghost was evaluated as follows.

Ghost ... A Canon ghost test chart (part number: FY9-9040) has a reflection density of 1.
1. Place a black circle with a diameter of 5 mm on the edge of the image on the platen, and place a Canon halftone chart on top of it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion was measured. In each case, ⊚ represents “excellently good”, ◯ represents “excellent”, Δ represents “no problem in practical use”, and × represents “problem in practical use”. The results are summarized in Table 122. (II) Next, the produced electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-8580 for an experiment, and an accelerated durability test equivalent to 3.5 million sheets was conducted. And
The electrophotographic characteristics such as white spots, uneven halftone, and ghost were evaluated in the same manner as in (I). The result is 123
It is summarized in the table. From the results shown in Tables 122 and 123, it is necessary to prepare an electrophotographic photosensitive member having excellent image characteristics and durability by setting the fluorine content in the photoconductive layer in the range of 95 atomic ppm or less. Has been shown to be possible. <Embodiment 69> By using the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 124 in the same manner as in Example 68. The produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 68. The results are shown in Tables 122 and 12
It was exactly the same as in Table 3. <Example 70> A substrate which has been pretreated in the same manner as in Example 62 by the substrate surface treating apparatus shown in FIG. 1 is used to produce a first image by the high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. Electrophotographic photoreceptors were produced under the production conditions shown in Table 125. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so that the amount of carbon contained in the surface layer was changed.

The produced electrophotographic photosensitive member was set in a Canon electrophotographic copying machine NP-7550 which had been modified for experiments, and the charging ability, residual potential, image evaluation before endurance, 350.
Image evaluation after an accelerated durability test equivalent to 10,000 sheets was performed by the following method. Chargeability: The same operation as in Example 62 was performed. Residual potential ... The same operation as in Example 62 was performed. Image evaluation after endurance: Limit samples of 5 grades were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 grades. ⊚ is “especially good” ◯ is “good” Δ is “no problem in practical use” × is “problem in practical use” The above results are shown in Table 126. As is clear from the table, when the carbon content is 40 to 90 atom%, a remarkable improvement in charging ability and durability is observed. <Example 71> By using the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 127 in the same manner as in Example 70. In this experiment, the CH ₄ flow rate introduced at the time of forming the surface layer was changed so as to change the amount of carbon contained in the surface layer. The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 9. As a result, the same results as in Table 126 were obtained. <Example 72> A substrate pretreated in the same manner as in Example 62 by the substrate surface treatment apparatus shown in FIG. 1 was used to perform a high frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 128. In this experiment, the flow rates of H ₂ and / or SiF ₄ introduced at the time of forming the surface layer were changed so as to change the amounts of hydrogen atoms and fluorine atoms contained in the surface layer.

The produced electrophotographic photosensitive member was set in an electrophotographic apparatus which was a Canon copying machine NP-7550 modified for experiment, and three items of residual potential, sensitivity and image deletion were evaluated. Residual potential ... The same operation as in Example 62 was performed. Sensitivity: Same as in Example 62. The results obtained are shown in Table 129. As is clear from Table 129, the sum of the hydrogen content and the fluorine content in the surface layer was 30 to 70 atomic%, and the fluorine content was 20.
It was found that by setting the content to be in the range of atomic% or less, good results were obtained for both the residual potential and the sensitivity, and the image deletion at strong exposure could be significantly suppressed. <Example 73> By using the substrate surface treating apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and 2 (b), an electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the manufacturing conditions shown in Table 130 in the same manner as in Example 71. The He flow rate is 2000 including the H ₂ flow rate.
The internal pressure was kept constant by changing the sccm to be constant. The produced electrophotographic photosensitive member was evaluated by the same procedure as in Example 71. As a result, the same results as in Table 129 were obtained. <Example 74> FIGS. 2 (a) and 2 (b) are shown on a substrate which has been subjected to the same pretreatment as in Example 62 under the conditions shown in Table 131 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 132 using an electrophotographic photosensitive member manufacturing apparatus. In this example, the content of fluorine in the photoconductive layer is shown in FIG.
~ SiF ₄ / SiH _{4 to} have the distribution shown in FIG.
By changing the flow rate smoothly within the range of 10 to 50 ppm, four types of electrophotographic photosensitive members were produced. An electrophotographic photosensitive member was also produced under the same conditions except that it did not contain fluorine. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, chargeability, sensitivity, residual potential, white spots, halftone unevenness, ghost ... Evaluation similar to that of Example 62 Temperature characteristics ... Experiment of manufactured electrophotographic photoreceptor with Canon copier NP8580 Put it in a copier modified for use, change the surface temperature of the electrophotographic photosensitive member to 30 to 45 ° C, apply a high voltage of +6 kV to the charger, perform corona charging, and use the surface potentiometer to adjust the surface potential of the dark area. taking measurement. The change in the surface temperature of the dark portion with respect to the surface temperature of the photoconductor is approximated by a straight line, and the slope is defined as "temperature characteristic", which is expressed in units of [V / deg]. ⊚ ... very good. ◯: Excellent Δ: No problem in practical use ×: Not practical Practical results are shown in Table 133. From the table, it is understood that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, electrophotographic characteristics including ghost and temperature characteristics are improved. <Example 75> FIGS. 2 (a) and 2 (b) are shown on a substrate which has been pretreated in the same manner as in Example 62 under the conditions shown in Table 131 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photosensitive member was manufactured by the microwave glow discharge method under the conditions shown in Table 132 using an electrophotographic photosensitive member manufacturing apparatus. In this example, the content of fluorine in the photoconductive layer was kept constant, and the content of CO ₂ / SiH ₄ was within the range of 10 to 50 ppm so that the oxygen content was in the distribution form shown in FIGS. 70 to 73. The flow rate was changed smoothly with 4 to prepare four types of electrophotographic photosensitive members. An electrophotographic photosensitive member was also produced under the same conditions except that oxygen was not contained. The following 5 types of electrophotographic photosensitive members were evaluated.

Surface haze, charging ability, sensitivity, residual potential, white spots, halftone unevenness, ghost, temperature characteristics ... Evaluation similar to that of Example 74 Potential shift ... Electrophotographic photoreceptor was set in experimental apparatus and charger High voltage of + 6kV is applied to and corona charging is performed.
The surface potential of the dark part of the electrophotographic photosensitive member is measured by a surface potential meter. At this time, the dark surface potential immediately after the voltage is applied to the charger is V _d0 and the dark surface potential after 2 minutes is V _d . Then, the difference between V _d0 and V _d is the amount of potential shift. ⊚ is “particularly good” ◯ is “good” Δ is “no problem in practical use” x is “problem in practical use” The above results are shown in Table 135. From the table, it can be seen that when the photoconductive layer contains fluorine and further contains oxygen atoms, there is an effect on the potential shift characteristics.

[0278]

[Table 110]

[0279]

[Table 111]

[0280]

[Table 112]

[0281]

[Table 113]

[0282]

[Table 114]

[0283]

[Table 115]

[0284]

[Table 116]

[0285]

[Table 117]

[0286]

[Table 118]

[0287]

[Table 119]

[0288]

[Table 120]

[0289]

[Table 121]

[0290]

[Table 122]

[0291]

[Table 123]

[0292]

[Table 124]

[0293]

[Table 125]

[0294]

[Table 126]

[0295]

[Table 127]

[0296]

[Table 128]

[0297]

[Table 129]

[0298]

[Table 130]

[0299]

[Table 131]

[0300]

[Table 132]

[0301]

[Table 133]

[0302]

[Table 134]

[0303]

[Table 135]

(Sixth and Seventh Inventions) In the light receiving member of the present invention, the surface of the support supports a plurality of spherical ice particles by allowing the plurality of spherical ice particles to fall or jet under pressure. By having unevenness due to a plurality of trace dents obtained by colliding with the surface of the body, the reflected light from each layer interface of the light receiving layer of the multilayer structure and the reflected light from the surface of the light receiving member are respectively Since the reflection directions are different, shearing interference corresponding to the so-called Newton's ring phenomenon occurs, and the interference fringes are dispersed in the trace depressions. The method for producing a light-receiving member of the present invention is a method in which a plurality of spherical ice particles are naturally dropped or pressure-jetted, and a plurality of spherical ice particles are collided with the surface of a support to form a plurality of particles on the surface of the support. Since the shape of the trace dent can be changed by freely changing the diameter of the ice particles by having the unevenness forming step of forming the unevenness by the trace dent, it is possible to easily cope with various preparation conditions. .
In addition, even if there is dirt such as fats and oils on the surface of the support, the fats and oils are cooled by the ice particles and hardened and contracted,
Because it is crushed by ice particles and repelled,
The surface of the support can be cleaned during the unevenness forming step.

[0305]

1 is a sectional view showing an embodiment of a light receiving member of the present invention. The light receiving member 1100 includes a support 110.
1 and a light receiving layer 1102 formed on the support 1101.
(A photoconductive layer), the surface of the support 1101 has a plurality of spherical traces obtained by allowing a plurality of spherical ice particles to naturally fall and colliding the plurality of ice particles with the surface of the support 1101. It has unevenness due to depressions (dimples).
The light receiving layer 1102 is the first layer 1102 ₁ sequentially formed on the support 1101 along the inclined surface of the unevenness.
And the second layer 1102 ₂ , the second layer 1102
The surface of ₂ is a free surface 1103. Next, the shape of the surface of the support 1101 and an example of a preferable method for forming the irregularities will be described in detail with reference to FIGS. 77 and 78. FIG. 77 is a schematic diagram showing one method of forming irregularities on the surface of the support 1101. In the method shown in FIG. 77, spherical ice particles 1403 are naturally dropped from a position at a predetermined height h from the surface 1101 ₁ of the support 1101 to allow the ice particles 1403 to move to the surface 11 of the support 1101.
The dimple 1404 is formed by colliding with 01 ₁ . Then, spherical ice particles 14 having substantially the same diameter R
By using a plurality of 03 and dropping them simultaneously or sequentially from the same height h, the radius of curvature R is almost the same.
And forming a plurality of dimples 1404 having the same width D on the surface 1101 ₁ of the support 1101.

78A to 78D are respectively shown in FIG.
The surface unevenness due to multiple dimples
1 shows a typical example of a support formed on the above. FIG. 78
In the typical example shown in (A), the surface 150 of the support 1501
1₁ Of different spherical ice pieces with almost the same diameter
Particles 1503 are naturally dropped from the same height.
The plurality of ice particles 1503 on the surface of the support 1501.
1501 ₁ And the same curvature and
And a plurality of dimples 1504 having substantially the same width to each other.
Densely generated so that they overlap each other, forming irregularities regularly
It was done. The dimples 15 that overlap each other
04 to form the surface 1501 of the support 1501.₁ 
The ice particles 1503 collide with each other at different times
Then, let some ice particles 1503 fall naturally,
Particles 1503 on the surface 1501 of the support 1501₁ Crash into
It goes without saying that it is necessary to let them do it. FIG. 78 (B)
In the typical example shown in, two types of spherical ice particles with different diameters are used.
1503 ₁ , 1503₂ To fall from almost the same height
Let each ice particle 1503₁ , 1503₂ The support 1
Surface 501 of 501₁ Curvature by colliding with
And two types of dimples 1504 with different widths₁ , 15
04₂ Are densely generated alternately and overlapping each other.
The unevenness of the height is irregular on the surface 15 of the support 1501.
01₁ It was formed in. FIG. 78 (C) and
In the typical example shown in (D), the surface 150 of the support 1501.
1 ₁ In addition, ice particles 1503 of a plurality of ball fields of almost the same diameter
Randomly fall from almost the same height, and each ice grain
The surface 1501 of the support 1501₁ Crashed into
To have almost the same curvature and multiple widths.
The dimples 1504 that overlap
The surface of the support 1501 has irregular irregularities.₁ Formed into
It was done.

As described above, a plurality of spherical ice particles are allowed to fall naturally, and a plurality of spherical ice particles are made to collide with the surface of the support to form irregularities due to dimples on the surface of the support. Is possible. Further, in the method shown in FIG. 77, since the irregularities are formed by dimples using spherical ice particles, there is a great feature that the support can be washed at the same time when the irregularities are formed. That is,
Dirt such as oil and fat on the surface of the support is cooled and contracted by the spherical ice particles. At this time, the fats and oils are likely to be peeled off due to the difference in the contraction rate with the support, and are further crushed by the spherical ice particles and repelled to be removed. Therefore, since the cleaning process is indispensable in the semiconductor device manufacturing process that requires a cleaning atmosphere, the method shown in FIG. 77 also serves as the cleaning process, and therefore the semiconductor device manufacturing process can be simplified. Very advantageous. In the method shown in FIG. 77, a plurality of spherical ice particles are allowed to naturally fall, and a plurality of ice particles are made to collide with the surface of the support to form irregularities due to dimples on the surface of the support. Instead of letting a plurality of spherical ice particles fall naturally, a plurality of spherical ice particles may be pressurized and jetted. Diameter of spherical ice particles,
The height of natural drop, the pressure when pressure is applied, the hardness of the spherical ice particles and the surface of the support, and the spherical ice particles which are allowed to naturally fall or are pressed to collide with the surface of the support. By properly selecting various conditions such as the amount, a plurality of dimples having a desired radius of curvature and width can be formed on the surface of the support at a predetermined density. That is, by selecting the above conditions, it becomes possible to freely adjust the height and pitch of the unevenness formed on the surface of the support according to the purpose, and obtain a support having the desired unevenness on the surface. You can Also, since the spherical ice particles used are always fresh particles, there is no deterioration with long-term use unlike conventional metallic hard spheres, so they are formed on the surface of the support. It becomes possible to repeatedly form dimples with good reproducibility in terms of quality and shape, reduce the incidence of defective products resulting from the dimple forming process, and improve the product yield. Therefore, by forming dimples on the surface of the support by colliding spherical ice particles on the surface of the support, all the conventional problems are solved, and unevenness of a desired shape is provided on the surface and a semiconductor device is obtained. A support having a sufficiently clean surface required can be efficiently and conveniently prepared.

Next, an example of a manufacturing apparatus for forming irregularities on the surface of the support when the light receiving member according to the present invention is used as a light receiving member for electrophotography will be described with reference to FIG. In this manufacturing apparatus, an aluminum cylinder 1601 for making a support, which rotates about a rotary shaft 1602 in the direction of the arrow in the figure, and a spraying means 1603 for spraying a plurality of spherical ice particles 1605 toward the aluminum cylinder 1601. And a pressurizing gas cylinder 1604 for supplying a pressurizing gas for pressurizing the ice particles 1605 to the jetting means 1603, an ice maker 1606 for making the ice particles 1605 and supplying them to the jetting means 1603, and in the vapor phase Spray nozzle 1607 to disperse pure water in the form of mist
A cooling means 1608 for freezing the pure water dispersed by the spray nozzle 1607, which is introduced into the upper part of the ice making device 1606 during ice making, a pure water tank 1609 for supplying pure water to the spray nozzle 1607, and a pure water tank Pure water pressurizing gas cylinder 1610 for supplying pure water pressurizing gas to 1609
And a pure water supply pipe 1611 for supplying pure water to the pure water tank 1609. Here, the aluminum cylinder 1601 may be preliminarily finished so that the surface has an appropriate smoothness. The aluminum cylinder 1601 is rotatably supported by a rotating shaft 1602 around an axis, and is driven by an appropriate driving unit (not shown) such as a motor. The rotation speed of the aluminum cylinder 1601 is appropriately determined and controlled in consideration of the density of dimples to be formed and the supply amount of spherical ice particles 1605.

The treatment and cleaning of the surface of the support with the spherical ice particles 1605 are carried out as follows. Pure water is introduced into a pure water tank 1609 from a pure water tank (not shown) via a pure water supply pipe 1611. Subsequently, the pure water pressurizing gas sent from the pure water pressurizing gas cylinder 1610 pressurizes the pure water in the pure water tank 1609 and introduces it into the ice maker 1606. After being atomized, the particles are frozen into ice particles 1605 by the cooling means 1608 introduced into the ice maker 1606. At this time, spherical ice particles 160
In order to obtain 5, it is necessary to control the flow rate and flow rate of pure water to be introduced, the shape of the spray nozzle 1607, the cooling temperature, and the like. Further, the size of the ice particles 1605 is similarly adjusted by controlling the flow rate and flow rate of the pure water to be introduced. Spherical ice particles 1605 thus obtained
Is pressurized by the pressurizing gas 1604 in the injection unit 1603, and is also pressurized and injected by the injection unit 1603 toward the aluminum cylinder 1601. The ice particles 1605 pressure-jetted by the jetting means 1603 are
The aluminum cylinder 1601 collides with the surface of the aluminum cylinder 1601 to form dimples, and at the same time, the aluminum cylinder 16
The surface of No. 01 is washed. Liquid nitrogen or the like is desirable as cooling means 1608. Also, as pure water, especially semiconductor grade pure water, optimally ultra LSI
Grade ultrapure water is preferred. Specifically, water temperature 25 ℃
Resistivity is 1 MΩ-cm or more, preferably 10 M
Ω-cm or more, optimally 16 MΩ-cm or more is suitable. It is suitable that the amount of fine particles in pure water is 500 or less, preferably 100 or less, and most preferably 50 or less, in 1 ml of fine particles of 0.2 μm or more. As the amount of microorganisms in pure water, it is suitable that the total viable cell count is 10 or less, preferably 1 or less, and optimally 0.1 or less in 1 ml. The amount of organic matter (TOC) in pure water is 1 mg or less per 1 liter,
Suitably 0.2 mg or less, optimally 0.1 mg or less. As a method for obtaining such pure water, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse dipping method, an ultraviolet sterilization method, and the like. It is desirable to raise

The particle size required for the spherical ice particles 1605 to collide with the surface of the aluminum cylinder 1601 is 10 μm or more and 10 mm or less, preferably 20 μm.
m or more and 7 mm or less, optimally 30 μm or more and 5 mm or less. Further, the circularity of the ice particles 1605 is such that the difference in length between the diameters of the particles in two directions at right angles is within 20%, preferably within 10%, and most preferably within 5%. In the above description, the spherical ice particles 16
No. 05 was obtained by cooling pure water in a gas phase, but it is also effective when other methods are used as a method for producing spherical ice particles. For example, crushing a relatively large piece of ice and removing the corners by heat treatment or mechanical treatment to form spherical particles, or introducing pure water into a spherical mold and cooling it to form spherical particles. Examples include a method of forming particles. Next, the light receiving member 11 shown in FIG.
The reason why the problem of the interference fringe pattern can be solved in No. 00 will be described with reference to FIGS. 75 and 76. FIG. 75 is an enlarged view showing a part of a conventional light-receiving member in which a light-receiving layer having a multilayer structure is deposited on a support whose surface is regularly roughened. When the surface of the support (not shown) is simply roughened by means such as cutting, the light receiving layer is usually formed along the irregularities of the surface of the support, and thus The uneven surface of the light receiving layer and the uneven surface of the light receiving layer have a parallel relationship. Therefore, in the light receiving member 1300 as shown in FIG. 3 in which the light receiving layer has a multi-layered structure including the first layer 1302 ₁ and the second layer 1302 ₂ , the first layer 1302 Interface 1304 between ₁ and second layer 1302 ₂ and free surface 1303
Because there is a parallel relationship, the reflected light r ₂ of the reflected light r ₁ and the free surface 1303 of the interface 1304 direction coincides, interference fringes occur in accordance with the thickness of the second layer 1302 _2.

FIG. 76 shows the light receiving member 110 shown in FIG.
It is the figure which expanded a part of 0. Photoreceptive member according to the present invention
In the 1100, unevenness due to a plurality of minute dimples is supported.
It is formed on the surface of the holder 1101 and receives light along the irregularities.
The layer 1102 is deposited so that the photoreceptor layer 1102 is first
Layer 1102₁ And the second layer 1102₂ Consists of two layers
In the light receiving member 1100 having a multilayer structure, the first layer 1
102₁ And the second layer 1102₂ Interface 1104 with
Unevenness due to dimples is also formed on the free surface 1103.
Be done. Radius of curvature of dimples formed on the interface 1104
R₁ And dimples formed on the free surface 1103
Radius of curvature of R₂ Then R₁ ≠ R₂ Therefore, the interface
Reflected light r at 1104₁ And reflected light on the free surface 1103
r ₂ And the reflection angle θ₁ , Θ₂ (Θ₁ ≠ θ
₂ ), The reflection direction is different. Also, in FIG.
Each length L shown₁ , L₂ , L₃ By L₁ + L₂ -L₃ 
Two reflected lights r₁ , R₂ Deviation of wavelength is constant
Since it does not change and changes, the so-called Newton ring
Sharing interference corresponding to the phenomenon occurs, and the interference fringes are
It is dispersed in the sample. Thereby, the light receiving member 11
The image displayed through 00 has microscopic interference fringes.
Even if they appear, they are visually recognizable.
It will not be heard. Therefore, as shown in FIG.
On the support 1101 having a surface shape like
Light receiving member 110 formed by forming a light receiving layer 1102
At 0, the light passing through the light receiving layer 1102 is at the layer interface and
The light reflected by the surface of the support interferes with each reflected light.
It is possible to effectively prevent the image from becoming a striped pattern.
Therefore, an excellent image can be formed.

The radius of curvature R and the width D of the unevenness due to the dimples formed on the surface of the support 1101 are for efficiently achieving the effect of preventing the occurrence of interference fringes in the light receiving member 1100 according to the present invention. It is an important factor. In the conventional light receiving member, the condition of the dimples is set by setting the constant X represented by X ≦ D / R (1) to approximately 0.035, and the Newton ring due to the shearing interference is set to 0. By having 5 or more of them, a certain effect was achieved. However, in practice, the value of the constant X exists in the refractive index n of the light-receiving layer, the layer thickness d, and the wavelength λ of the incident laser. Therefore, in order to obtain a more accurate and high-quality image at the minimum cost, The value of the width D, the value of the radius of curvature R, and the ratio D / R of the width D and the radius of curvature R are
It became necessary to set the optimum values (depending on the tourist) depending on the conditions such as the wavelength of the laser light used, the particle size of the toner, and the shape of the cylinder. The inventors have found that it is important to control the conditions of the dimple processing depending on the usage conditions of the photoconductor in order to more effectively develop the function of the dimples than the conventional dimple processing. That is, when the toner to be used is made into fine particles, the diameter and thickness of the support are changed, and the wavelength of the laser used is changed, the optimum dimple width D and curvature radius R for each condition are Since they are different, it is necessary to change the diameter of the rigid sphere used or the strength with which the support is made to collide. Specifically, if the width D of the unevenness due to the dimples is too large, the interference fringes in the dimples are visually recognized, so that the width D is at most about 500 μm, preferably 200 μm or less, more preferably 100 μm or less.
It is desirable that the thickness be less than or equal to μm. Further, the optimum value of the radius of curvature R varies depending on each light receiving member depending on the particle diameter of the toner, the wavelength of the laser, the manufacturing cost, and the like. For example, when a fine particle toner is used, in consideration of its cleaning property, the surface property of the support is required to be higher in smoothness as long as it has the ability to disperse the interference fringes in the dimples. That is, it is desirable that the radius of curvature R be as large as possible if the value of the width D is limited to within 500 μm based on the above conditions. On the other hand, when the diameter of the support is small, or when the thickness of the support is thin, when the surface of the support is processed with a rigid sphere having a large radius of curvature R, the support itself is damaged. It is not preferable because it is received.

As another specific example, for example, a lower model of a copying machine (that is, a low-speed model) uses a long-wavelength laser because of its cost limitation. However, in order to exert the effect of preventing the interference phenomenon, it is necessary to have a large optical distance as compared with the case of a short wavelength (that is, the ratio D / R needs a larger value). Further, as the wavelength of the incident laser light becomes longer, the refractive index of the light receiving layer also becomes smaller, so that the ratio D / R also needs to have a larger value. However, since the size of the width D is limited as described above, it is necessary to make the radius of curvature R relatively small. In order to reduce the radius of curvature R, it is essential to reduce the diameter of the spherical particles that collide with the support, but it is difficult to process a metal rigid sphere with a small diameter required under the above conditions. Therefore, the manufacturing cost is very high. Furthermore, a hard metal sphere with a small diameter is difficult to handle, resulting in reduced workability, and it has lower durability than a hard sphere with a large diameter, requiring frequent replacement, which is a factor in cost increase. In addition, the rigid metal sphere with a small diameter has low accuracy such as roundness, and the quality of the support processed using this,
The yield will be low. On the other hand, in higher-end models of copying machines (that is, high-speed models), the process speed is fast, so it is necessary to use a relatively short wavelength laser with a large absorption coefficient of the photosensitive layer in order to increase sensitivity. It is possible in terms of cost. By using a short-wavelength laser, hard spheres having a relatively large particle size can be used for processing the support. Therefore, in this way, the processing conditions of the support required depending on the type of copying machine also differ, and inevitably, in the conventional dimple processing using a metal hard sphere, it is necessary to use the metal hard sphere properly according to the application. Will be complicated and will lead to higher costs. On the other hand, in the light receiving member according to the present invention, since ice particles are used in place of the hard metal balls, the diameter can be freely changed by appropriately adjusting the flow rate of pure water or the cooling means. Furthermore, since the pressure with which the ice particles collide with the surface of the support is also variable, dimples satisfying the respective requirements can be formed without using a special operation.

For the preparation of the light receiving layer according to the present invention,
Since it is necessary to precisely control the film thickness at the optical level in order to efficiently achieve the above-mentioned object of the present invention,
As a method of forming a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (optical CVD method), a method of decomposing a source gas by plasma (plasma CVD method ) Etc. can be adopted, but among them, the raw material gas is decomposed by direct current or high frequency, microwave glow discharge, etc., and is applied on a substrate such as glass, quartz, heat resistant synthetic resin film, stainless steel, aluminum, etc. A plasma CVD method for forming a deposited film on a thin film is suitable for the present invention. Next, the support 110 of the light receiving member 1100 shown in FIG.
1 and the light receiving layer 1102 will be described in detail. (1) Support 1101 The support 1101 has an uneven surface with a plurality of dimples that is smaller than the resolving power required for the light receiving member 1100. The support 1101 may be conductive or electrically insulating.
Examples of the conductive support include NiCr, stainless steel Al, Cr, Mo, Au, Nb, Ta, V, Ti, P.
Examples thereof include metals such as t and Pb or alloys thereof.
Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and poloamide, and paper. It is preferable that one surface of each of these electrically insulating supports is subjected to a conductive treatment, and a light receiving layer is provided on the surface side subjected to the conductive treatment. For example, in the case of synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Z
n, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
A thin film of a metal such as Tl or Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like, or the surface is laminated with the metal to impart conductivity to the surface.

As the support material, Al (aluminum) is preferable because of the good workability of dimples formed by ice particles. When Al is used as the support material, it is desirable to contain 1 to 10% by weight of magnesium in order to improve the machinability. Further, the purity of aluminum before containing magnesium is 98% by weight or more, preferably 99% by weight or more. The shape of the support 1101 may be an arbitrary shape such as a cylindrical shape, a belt shape, or a plate shape, and may be appropriately determined depending on the application or desire. For example, when the light receiving member 1100 shown in FIG. 74 is used as an electrophotographic image forming member and continuous high speed copying is performed, it is desirable that the endless belt or the cylinder is used. The thickness of the support 1101 is set as desired for the light receiving member 1.
Although it is appropriately determined so that 100 can be formed, when flexibility is required as the light receiving member 1100, the light receiving member 1100 can be made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, in terms of manufacturing, handling, and mechanical strength of the support 1101, the support 11
The thickness of 01 is 10 μm or more. As a support for the light receiving member for electrophotography, aluminum alloy is subjected to normal extrusion processing to form a boathole tube or a mandrel tube, and a drawn tube obtained by further drawing is subjected to heat treatment or adjustment if necessary. A cylindrical (cylindrical) substrate that has been subjected to treatments such as quality is used. (2) Photoreceptive Layer 1102 The photoreceptive member 1100 shown in FIG.
It has a light receiving layer 1102 on it. Photoreceptive layer 1
102 is composed of a-Si: (H, X), and can contain a conductive material as necessary. The light-receiving layer of the light-receiving member according to the present invention has a multi-layered structure. For example, the light-receiving layer 110 shown in FIG.
2 is comprised of a first layer 1102 ₁ and the second layer 1102 ₂ Prefecture, the second layer 1102 ₂ and the support 1101 side is a layer of opposite sides of the light-receiving layer 1102, the free surface 1103
have.

Specific examples of the halogen atom (X) to be contained in the light receiving layer 1102 include fluorine, chlorine, bromine and iodine, with fluorine and chlorine being particularly preferable. Then, the light receiving layer 1102
The amount of hydrogen atoms (H), the amount of halogen atoms (X), and the sum of the amounts of hydrogen atoms and halogen atoms (H + X) contained in each are usually 1 to 40 atom%, preferably 5 to 30 atoms. It is desirable to be set to%. The layer thickness of the light receiving layer 1102 in the light receiving member 1100 according to the present invention is one of the important factors for efficiently achieving the object of the present invention, and the light receiving member 1100 is provided with desired characteristics. As described above, it is necessary to pay sufficient attention when designing the light receiving member 1100, which is usually 1 to 100 μm, preferably 1 to 80 μm, more preferably 2 to 50 μm.
μm. In the present invention, in order to effectively achieve the object, the light receiving layer 1 formed on the support 1101.
102 has the following semiconductor characteristics, and is made of a-Si: (H, X) that exhibits photoconductivity with respect to the irradiation light. p-type a-Si: (H, X) ... containing only acceptors. Or, it includes both a donor and an acceptor,
High relative concentration of acceptor. p ^- type a-Si: (H, X) ... In the above types, the acceptor concentration (Na) is low or the relative acceptor concentration is low. n-type a-Si: (H, X) ... Those containing only a donor.
Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the donor.

N ^- type a-Si: (H, X) ... In the above types, the concentration of the donor (Nd) is low or the relative concentration of the acceptor is low. i-type a-Si: (H, X) ... Na≈Nd≈0,
Or Na≈Nd. In the light receiving member 1100 according to the present invention, the light receiving layer 1102 may contain a substance that controls conductivity in the entire layer region or a part of the layer region in a uniform or non-uniform distribution state. In the field of semiconductors, so-called impurities can be cited as substances that control conductivity, and atoms belonging to Group III of the periodic table that give p-type conductivity (hereinafter simply referred to as "Group III atoms"), or , An atom belonging to Group V of the periodic table that gives n-type conductivity (hereinafter, simply referred to as “Group V atom”) is used. Specifically,
Group III atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl.
(Thallium) and the like can be mentioned, but B and Ga are particularly preferable. Further, as group V atoms, P (phosphorus), As (arsenic), Sb (antimony), B
Although i (bismuth) and the like can be mentioned, particularly preferable ones are P and Sb. The light-receiving layer 1102 contains a group III atom or a group V atom, which is a substance that controls conductivity.
When it is contained in the whole layer region, whether it is contained in the whole layer region or a part of the layer region depends on the intended place and the expected action and effect, and therefore, the contained amount also differs. Become. That is, when the main purpose is to control the conductivity type and / or conductivity of the light receiving layer 1102, the light receiving layer 1
102 in all regions, in which case the content of group III atoms or group V atoms may be relatively small, usually 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm, preferably 5 × 10 ^{-2 to} 5 × 10 ² ppm, optimally 1 × 10 ^-1
˜2 × 10 ² atomic ppm. In addition, the support 1101
When a group III atom or a group V atom is contained in a uniform distribution state in a part of the layer region which is in contact with
When it is contained so as to have a high concentration on the side in contact with 01, a partial layer region containing such a group III atom or a group V atom or a region containing a high concentration functions as a charge injection blocking layer. By the way. That is, when the group III atom is contained, when the free surface 1103 of the light-receiving layer 1102 is subjected to the electrification treatment of + polarity, the support 1
The movement of electrons injected into the light receiving layer 1102 from the 101 side can be blocked more efficiently, and when a group V atom is contained, the free surface 1103 of the light receiving layer 1102 becomes − The support 11 is subjected to a charging treatment to polarize.
The movement of holes injected from the 01 side into the light receiving layer 1102 can be blocked more efficiently. The content in this case is relatively large. Specifically, it is generally 30 to 5 × 10 ⁴ atomic ppm, but preferably 5
0 to 1 × 10 ⁴ atomic ppm, optimally 1 × 10 ^{2 to} 5
× 10 ³ atomic ppm. In order to achieve this effect efficiently, when the layer thickness of a part of the layer region is t and the layer thickness of the other light receiving layer is t ₀ , t / (t + t
It is desirable that the relationship of ₀ ) ≦ 0.4 is satisfied, more preferably 0.35 or less, and optimally 0.3 or less. The layer thickness of this layer region is generally 3 × 10 ^{−3 to} 10 μm, preferably 4 ×.
10 ^{−3 to} 8 μm, optimally 5 × 10 ^{−3 to} 5 μm.

The amount of the group III atom or the group V atom contained in the light receiving layer 1102 is relatively large on the support 1101 side and decreases from the support 1101 side toward the free surface 1103 side. The group III atoms or the group V atoms may be distributed so that the amount is relatively small or is substantially close to zero near the end on the free surface 1103 side. In the case where the portion of the light receiving layer 1102 closer to the support 1101 has a portion where the distribution concentration C of the group III atom or the group V atom is considerably low or a portion where the concentration C is substantially close to zero. In this case, a localized region having a relatively high concentration distribution of group III atoms or group V atoms is provided in a portion near the support 1101 side, and preferably, this localized region is formed in the support 1101. By providing within 5 μm from the interface position that contacts the surface,
The above-described effect that the layer region in which the distribution concentration of the group III atom or the group V atom is high forms the charge injection blocking layer is more effectively exhibited. As described above, the action and effect have been individually described for the distribution state of the group III atoms or the group V atoms.
In order to obtain 00, the state of distribution of these group III atoms or group V atoms and the group III atoms contained in the light-receiving layer are included.
It goes without saying that the amounts of the group atom or the group V atom are appropriately combined and used as necessary. For example, when a charge injection blocking layer is provided at the end of the light receiving layer 1102 on the support 1101 side, the conductivity contained in the charge injection blocking layer is controlled in the light receiving layer 1102 other than the charge injection blocking layer. A substance that controls conduction of a polarity different from the polarity of the substance may be contained, or a substance that controls conductivity of the same polarity may be contained in a much smaller amount than that contained in the charge blocking layer. You may let me.

Furthermore, in the light receiving member 1100 of the present invention,
The layer structure provided at the end on the side of the support 1101.
Instead of the charge injection blocking layer, it consists of an electrically insulating material
It is also possible to provide a so-called barrier layer or this barrier
Both the layer and the charge injection blocking layer may be constituent layers.
It As a material forming such a barrier layer, Al is used.₂ O
₃ , SiO₂ , Si₃ N_Four Inorganic electrical insulation materials such as
To mention organic electrically insulating materials such as carbonates
it can. Next, a method of forming the light receiving layer 1102 will be described.
Reveal Any amorphous material that constitutes the light receiving layer 1102
This is also a method that decomposes the raw material gas by the sputtering method and heat.
Method (thermal CVD method), method of decomposing raw material gas by light
(Photo-CVD method), direct-current or high-frequency source gas, microphone
Plasma generated by decomposition by microwave glow discharge
For the method of decomposing the raw material gas by plasma (plasma CVD method)
Done more. These manufacturing methods are based on manufacturing conditions and capital investment.
Lower load level, manufacturing scale, created light receiving member 110
Depending on factors such as the characteristics desired to be 0,
A light receiving member 1100 that is employed but has desired characteristics
It is relatively easy to control the conditions for creating
The conductivity of carbon and hydrogen atoms along with silicon atoms.
Plasma CVD for reasons such as easy entry
Method or sputtering method is preferred. And plastic
Zuma CVD method and sputtering method are used together in the same system.
May be used. For example, by the plasma CVD method,
To form a layer composed of a-Si: (H, X),
Basically, Si supply that can supply silicon atoms (Si)
Raw material gas for introducing hydrogen atoms (H) together with the raw material gas for
Gas for introducing hydrogen and / or halogen atom (X)
Is introduced into the deposition chamber where the pressure inside can be reduced, and
Pre-installed at a predetermined position by causing glow discharge
A layer of a-Si: (H, X) on the surface of the support of
Form.

As a source gas for supplying Si, SiH
_Four , Si₂ H₆ , Si₃ H₈ , Si_FourH_TenSuch as gaseous
Silicon hydrides (silanes) that can be vaporized or gasified include
In particular, the ease of layer formation work and the good Si supply efficiency
At what point, SiH_Four , Si₂ H ₆ Is preferred. Also,
Many halogens are used as the source gas for introducing the rogen atom.
Compounds include, for example, halogen gas, halogen
Compounds, interhalogen compounds, halogen-substituted silanes
Gas state or gasifying halogen compound such as derivative
The thing is preferable. Specifically, fluorine, chlorine, bromine, iodine
Elementary halogen gas, Br, F, ClF, ClF₃ , B
rF_Five , BrF₃ , IF₇ , ICl, IBr, etc.
Intergenic compounds and SiF_Four , Si₂ F₆ , SiCl_Four ，
SiBr_FourAnd the like, such as silicon halide. Up
The gas state or gasification of silicon halide as described above
When using a gas, separate source gas for Si supply
A-S containing a halogen atom without using
This is particularly effective because a layer composed of i can be formed.
As a raw material gas for supplying hydrogen atoms, hydrogen gas, HF,
Halides such as HCl, HBr, HI, SiH_Four ，
Si₂ H₆ , Si₃ H₈ , Si_Four H_TenSilicon hydride such as
Or SiH₂ F₂ , SiH₂ I₂ , Si₂ Cl₂ , Si
HCl₃ , SiH₂ Br₂ , SiHBr₃ Such as halo
Gas state of gas substituted or hydrogenated
Can be used, and when using these source gases
Is extremely superior in terms of controlling electrical or photoconductive properties.
Control the content of hydrogen atoms (H), which is effective.
It is effective because it can be performed easily. And halo
When using hydrogen genide or halogen-substituted silicon hydride
At the same time as the introduction of the halogen atom, the hydrogen atom (H) is also introduced.
It is especially effective because it is included. Contained in a-Si layer
Hydrogen atom (H) and / or halogen atom (X)
The amount of hydrogen is controlled by, for example, the temperature of the support 1101 and hydrogen.
Introduce atom (H) and / or halogen atom (X)
Amount of starting material used for the purpose of being introduced into the deposition chamber, discharge
This is done by controlling the electric power respectively.

To form a layer of a-Si: (H, X) by the reactive sputtering method or the ion plating method, for example, in the case of the sputtering method, a halogen compound or A silicon compound gas containing a halogen atom may be introduced into the deposition chamber to form a plasma atmosphere of the gas. For example, in the case of the reactive sputtering method, S
Using an i target, a gas for introducing a halogen atom and a hydrogen gas, including an inert gas such as He or Ar, if necessary, are introduced into the deposition chamber to form a plasma atmosphere,
A layer made of a-Si: (H, X) is formed on the support by sputtering a Si target.
Amorphous, in which a-Si: (H, X) further contains a group III atom or a group V atom, an oxygen atom, a carbon atom or a nitrogen atom by using a plasma CVD method, a sputtering method or an ion plating method. In order to form a layer composed of a high-quality material, a starting material for introducing a Group III atom or a Group V atom during the formation of the a-Si: (H, X) layer,
The starting material for introducing an oxygen atom, the starting material for introducing a carbon atom, or the starting material for introducing a nitrogen atom is the above-mentioned a-Si:
By using with the starting materials for the formation of (H, X) and their controlled inclusion in the layers to be formed. For example, using a plasma CVD method, a sputtering method or an ion plating method,
A-Si containing a group atom or a group V atom: (H,
To form a layer or layer region composed of X), when forming the layer composed of a-Si: (H, X) described above,
The starting material for introducing a Group III atom or a Group V atom is a-
Si: (H, X) used with starting material to form
It is carried out by controlling the amount of them to be contained in the layer to be formed.

As a starting material for introducing a Group III atom,
Specifically, for introducing a boron atom, B₂ H₆ , B
_Four H_Ten, B_Five H₉ , B_Five H₁₁, B₆ H_Ten, B₆ H₁₂, B
₆ H ₁₄Borohydride and BF₃ , BCl₃ , BB
r₃ Examples thereof include boron halides and the like. this
Others, AlCl₃ , CaCl₃ , G (CH₃ )₂ , InC
l₃ TlCl₃ And so on. Also, V
As a starting material for introducing a group atom, specifically, a phosphorus atom
For introduction, PH₃ , P₂ H₆ Such as phosphorus hydride,
PH_Four I, PF₃ , PF_Five , PCl₃ , PCl_Five , PB
r₃ , PBr_Five , Pl₃ And phosphorus halides such as
It Besides this, AsH₃ , AsF₃ , AsCl₃ , AsB
r₃ , AsF_Five , SbH₃ , SbF₃ , SbF_Five , Sb
Cl₃ , SbCl_Five , BiH₃ , BiCl₃ , BiBr
_Five Are also valid starting materials for introducing Group V atoms.
Can be listed. Layer or layer containing oxygen atoms
When using the plasma CVD method to form the region
Is selected from the above-mentioned starting materials for forming the light-receiving layer.
Therefore, in the selected one, the starting material for introducing oxygen atom
Added. As a starting material for introducing such oxygen atoms
Is a gaseous substance that contains at least oxygen atoms as constituent atoms.
Uses most quality or gasifiable substances
it can. For example, silicon atoms (Si) as constituent atoms
Raw material gas and raw material containing oxygen atoms (O) as constituent atoms
Gas and optionally hydrogen atoms (H) and / or
A source gas containing a rogen atom (X) as a constituent atom is desired.
Use by mixing at a mixing ratio or silicon atoms
Source gas containing (Si) as a constituent atom, and oxygen atom (O)
And a source gas containing hydrogen atoms (H) as constituent atoms,
This can also be mixed in the desired mixing ratio or
Source gas containing oxygen atoms (Si) as constituent atoms, and oxygen atoms
Source gas containing (O) and hydrogen atom (H) as constituent atoms
And, also in the desired mixing ratio, or
A source gas containing silicon atoms (Si) as constituent atoms
Recon atom (Si), oxygen atom (O), hydrogen atom (H)
Used as a mixture with a source gas that has three of the constituent atoms
be able to. In addition to this, silicon atoms (S
i), a source gas containing hydrogen atoms (H) as constituent atoms,
A raw material gas containing oxygen atoms (O) as a constituent atom is mixed and used.
May be used. Specifically, for example, oxygen (O₂ ),
Ozone (O₃ ), Nitric oxide (NO), nitrogen dioxide (N
O₂ ), Nitrous oxide (N₂ O), dinitrogen trioxide (N₂ 
O₃ ), Nitrous oxide (N₂ O_Four ), Dinitrogen pentoxide (N
₂ O_Five ), Nitric oxide (NO₃ ), Silicon atom (S
i), oxygen atom (O), hydrogen atom (H)
Child lower siloxane (eg, disiloxane (H
₃ SiOSiH₃ ), Trisiloxane (H₃ SiOSi
H₂ OSiH ₃ )) And the like.

To form a layer or layer region containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer, a SiO ₂ wafer or Si and Si is used.
It may be carried out by using a wafer containing O ₂ mixed therein as a target and sputtering these in various gas atmospheres. For example, when a Si wafer is used as a target, a raw material gas for introducing oxygen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas as needed, and then is deposited in a deposition chamber for sputtering. Then, the Si wafer may be sputtered by forming these gas plasmas.
Separately, as a separate target Si and SiO _2, or Si and by the use of single target obtained by mixing of SiO _2, in an atmosphere of diluent gas as a gas for sputtering or at least hydrogen, It can be formed by sputtering in a gas atmosphere containing atoms (H) and / or halogen atoms (X) as constituent atoms. As the raw material gas for introducing hydrogen atoms, the raw material gas for introducing oxygen atoms in the raw material gases shown in the above-described example of the plasma CVD method can be used as an effective gas also in the case of sputtering. When the plasma CVD method is used to form a layer or layer region containing a nitrogen atom, a starting material for introducing a nitrogen atom is selected from the above-mentioned starting materials for forming the light-receiving layer as desired. Add substance. As such a starting material for introducing nitrogen atoms, almost any material can be used as long as it is a gaseous or gasifiable substance containing at least nitrogen atoms as constituent atoms. For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing nitrogen atoms (N) as constituent atoms, and optionally hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. Or a raw material gas containing silicon atoms (Si) as constituent atoms and a nitrogen atom (N).
And a source gas containing hydrogen atoms (H) as constituent atoms,
This can also be mixed and used in a desired mixing ratio. In addition, separately, a nitrogen atom (N) is added to a source gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms.
You may mix and use the raw material gas which makes a constituent atom.
A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) used in forming a layer or a layer region containing a nitrogen atom is N as a constituent atom or N and H.
And nitrogen as constituent atoms, such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), or the like. Mention may be made of nitrogen compounds such as gasifiable nitrogen, nitrides and azides. Besides this,
In addition to the introduction of the nitrogen atom (N), it is possible to introduce the halogen atom (X), so that nitrogen trifluoride (F ₃ N),
Mention may be made of halogenated nitrogen compounds such as dinitrogen tetrafluoride (F ₄ N ₂ ).

By a sputtering method, nitrogen atoms are contained.
To form a layer or layer region having a single crystal or poly
Crystalline Si wafer, Si₃ N_Four With wafer or Si
Si ₃ N_Four A wafer containing and mixed with
As a target, these are sputtered in various gas atmospheres.
It can be done by For example, Si wafer
When using Her as a target,
If necessary, introduce hydrogen atom and / or halogen atom.
If necessary, dilute the raw material gas to be introduced with a diluent gas
After that, by introducing it into the deposition chamber for sputtering,
By forming these gas plasmas, the Si wafer is sputtered.
Just tatter. Also, separately, Si and Si₃ N
_Four As separate targets, or Si and Si₃ 
N_Four By using a single target mixed with
In a diluting gas atmosphere as a gas for sputtering.
Or at least hydrogen atom (H) and / or halogen
In a gas atmosphere containing a nitrogen atom (X) as a constituent atom
It can be formed by sputtering. Nitrogen atom
As the raw material gas for introduction, the above-mentioned plasma CVD
The gas for introducing nitrogen atoms in the source gas shown in the example
It can also be used as an effective gas in the case of tattering. Well
In addition, for example, a-Si containing a carbon atom: (H,
To form the X) layer by the plasma CVD method,
Source gas containing carbon atoms (Si) as constituent atoms, and carbon atoms
Source gas containing (C) as constituent atoms, and hydrogen if necessary
Constituting atoms (H) and / or halogen atoms (X)
The raw material gas used as a child is mixed at a desired mixing ratio and used.
Or, an atom whose constituent atoms are silicon atoms (Si)
Source gas and carbon atom (C) and hydrogen atom (H)
The raw material gas to be used as a child is also mixed at a desired mixing ratio.
Or use silicon atoms (Si) as constituent atoms
Raw material gas, silicon atom (Si), carbon atom (C)
And a source gas containing hydrogen atoms (H) as constituent atoms
Or even silicon atoms (Si) and hydrogen atoms
A source gas containing (H) as a constituent atom and a carbon atom (C) are composed.
The raw material gas used as the atom is mixed and used.

A-Si by sputtering method:
To form the light receiving layer 102 composed of (H, X)
Is a monocrystalline or polycrystalline Si wafer, C (grapher
Wafer) or a mixture of Si and C contained
Target the target wafers and
The sputtering is performed in an atmosphere. Was
For example, when using a Si wafer as a target
Is a carbon atom, a hydrogen atom and / or a halogen atom.
The raw material gas for introducing the gas is Ar, He
Dilute with any dilution gas into the deposition chamber for sputtering
These gas plasmas are formed by introducing
Then, the Si wafer may be sputtered. Also,
Si and C should be different targets, or Si
When using as a single target that is a mixture of C and C
Include hydrogen atoms and / or as a gas for sputtering.
Alternatively, a gas for introducing halogen atoms may be diluted as needed.
And dilute it into a deposition chamber for sputtering.
By forming a gas plasma and sputtering
do it. For introducing each atom used in the sputtering method
The source gas is the source gas used in the plasma CVD method described above.
The raw gas can be used as it is. With such a source gas
Effectively used with Si and H as constituent atoms
SiH_Four , Si₂ H₆ , Si₃ H₈ , Si_Four H_TenSuch as
Silicon hydride gas such as silanes, C
Saturated carbon having 1 to 4 carbon atoms, for example, saturated carbon having 1 to 4 carbon atoms
Hydrogen chloride, ethylene-based hydrocarbons having 2 to 4 carbon atoms, 2 carbon atoms
~ 3 acetylene hydrocarbons and the like. concrete
The saturated hydrocarbons include methane (CH_Four ),Professional
Bread (C₃ H₈ ), N-butane (n-C_Four H_Ten),pen
Tan (C _Five H₁₂) Etc., and also ethylene-based coal
As hydrogen fluoride, ethylene (C₂H_Four ),propylene
(C₃ H₆ ), Butene-1 (C_Four H₈ ), Butene-2
(C_FourH₈ ), Isobutylene (C_Four H₈ ), Penten
(C_Five H_Ten) Etc., and further, acetylene-based coal
As hydrogen chloride, acetylene (C₂ H₂ ), Methylacetate
Chiren (C₃ H_Four ), Butin (C_Four H₆ ) Etc.
Be done. As a source gas containing Si, C and H as constituent atoms
Is Si (CH₃ )_Four , Si (C₂ H_Five )_Four Silicidation
Mention may be made of alkyl. Of these source gases
Other source gases for introducing H include H₂ Can also be used.

When the photoreceptive layer 1102 according to the present invention is formed by the plasma CVD method, the sputtering method or the ion plating method, the oxygen atom, carbon atom and nitrogen atom to be introduced into a-Si: (H, X), the IIIth group. The content of the group atom or the group V atom is controlled by controlling the gas flow rate and the gas flow rate ratio of the starting material introduced into the deposition chamber. In addition, conditions such as the temperature of the support 1101 at the time of forming the light receiving layer 1102, the gas pressure in the deposition chamber, and the discharge power are important factors for obtaining the light receiving member 1100 having desired characteristics. It is appropriately selected in consideration of the function of the layer. Further, these layer forming conditions may differ depending on the type and amount of each of the above-mentioned atoms contained in the light-receiving layer 1102. Therefore, it is necessary to determine in consideration of the type or amount of the contained atoms. There is. Specifically, the support 1101
The temperature on the surface of is usually 50 to 350 ° C, particularly preferably 50 to 250 ° C. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, and particularly preferably 0.1 to 0.5 Torr. The discharge power is usually 0.005 to 50 W / cm ² ,
It is more preferably 0.01 to 30 W / cm ² , and particularly preferably 0.01 to 20 W / cm ² . However, the specific conditions of the temperature of the support 1101, the discharge power, and the gas pressure in the deposition chamber for forming these layers are usually difficult to determine individually. Therefore, in order to form an amorphous material layer having a desired characteristic, it is desirable to determine the optimum conditions for layer formation based on mutual and organic relationships.

By the way, in order to make the distribution of oxygen atoms, carbon atoms, nitrogen atoms, group III atoms or group V atoms, hydrogen atoms and / or halogen atoms contained in the light receiving layer 1102 uniform, It is necessary to keep the above conditions constant when forming the receiving layer 1102. Further, when the light receiving layer 1102 is formed, the light receiving layer 1
Oxygen atom, carbon atom, nitrogen atom contained in 102,
In order to form the light receiving layer 1102 having a desired distribution state in the layer thickness direction by changing the distribution concentration of the group III atom or the group V atom in the layer thickness direction, if a plasma CVD method is used, Change the gas flow rate when introducing the starting gas for introducing the oxygen atom, carbon atom, nitrogen atom, group III atom or group V atom into the deposition chamber according to the desired rate of change, and keep other conditions constant. Form while keeping it. Then, in order to change the gas flow rate, specifically, for example, manually or by some commonly used method such as an external drive motor, gradually open the opening of a predetermined needle valve provided in the middle of the gas flow path system. It suffices to perform an operation to change. At this time, the rate of change of the flow rate does not have to be a curve type, and the flow rate can be controlled according to a previously designed rate of change curve using, for example, a microcomputer to obtain a desired content rate curve. In the case where the light-receiving layer 1102 is formed by a sputtering method, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, group III atoms, or group V atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired value. In order to form a state of distribution in the layer thickness direction of the same, a starting material for introducing oxygen atoms, carbon atoms, nitrogen atoms, group III atoms or group V atoms is used in a gas state as in the case of using the plasma CVD method. The gas flow rate when introducing these gases into the deposition chamber is changed according to the desired rate of change.

Next, the light receiving member according to the present invention was tested in Experimental Example 1.
-Experimental Example 3 and Example 76-Example 84 and Comparative Example 22 and Comparative Example 23 will be described in more detail. In each prototype, the light receiving layer was formed by using the plasma CVD method. FIG. 80 is a schematic configuration diagram showing an apparatus for manufacturing a light receiving member by the plasma CVD method. Each gas cylinder 1702, 1703, 1704, 1705, 1706 is sealed with a raw material gas for forming each layer,
As an example, for example, the gas cylinder 1702 is made of Si.
H ₄ gas (purity 99.999%) cylinder, gas cylinder 1
703 is B ₂ H ₆ gas diluted with H ₂ (purity 99.9).
99%, hereinafter referred to as "B ₂ H ₆ / H ₂ gas". ) The cylinder and gas cylinder 1704 are CH ₄ gas (purity 99.9).
99%) cylinder, gas cylinder 1705 is SiF ₄ gas (purity 99.999%) cylinder, and gas cylinder 1706 is H ₂ gas (purity 99.999%) cylinder. In order to make these source gases flow into the reaction chamber 1701, the valves 1722 to 172 of the gas cylinders 1702 to 1706 are used.
6 and the leak valve 1735 are all closed, and each inflow valve 1712-1716.
And each outflow valve 1717 to 1721 and each auxiliary valve 17
After confirming that all of 32 and 1733 are open, the main valve 1734 is opened to exhaust the reaction chamber 1701 and each gas pipe. Next, when the reading of the vacuum gauge 1736 reaches about 5 × 10 ⁻⁶ Torr, each auxiliary valve 1732, 1733 and each outflow valve 1717-1.
Close each 721.

Then, the light reception is performed on the base cylinder 1737.
An example of forming a layer is shown. Gas cylinder 1702
SiH_Four Gas, gas cylinder 1703 B₂ H₆ / H
₂ CH from gas, gas cylinder 1704_Four Gas each valve
Open 1722, 1723, 1724, 1726 respectively
After exiting, each outlet pressure gauge 1727, 1728, 172
Pressure of 9,1731 is 1 kg / cm² Adjust to
Inflow valves 1712, 1713, 1714, 1716
Gradually open each to each mass flow controller
Each gas in 1707, 1708, 1709, 1711
Inflow each. Subsequently, each outflow valve 171
7, 1718, 1719, 1721, each auxiliary valve 17
Open 32 and 1733 gradually to react each gas
Each is made to flow into the chamber 1701. SiH at this time
_Four Gas flow rate, B₂ H₆ / H₂Gas flow rate, CH_Four Gas flow
And H₂ Make sure that the gas flow ratios are the desired values
In addition, each outflow valve 1717, 1718, 1719, 17
21 and adjust the pressure inside the reaction chamber 1701.
Check the reading of the vacuum gauge 1736 so that is the desired value.
Adjust the opening of the main valve 1734. And the basis
The temperature of the body cylinder 1737 becomes the heater 1738
Be set to a temperature in the range of 50 to 400 ° C
After checking, set the power supply 1740 to the desired power
In addition to causing glow discharge in the reaction chamber 1701,
Pre-set using a microcomputer (not shown)
SiH according to the measured rate of change line_Four Gas flow rate, B₂ H₆ 
/ H₂ Gas flow rate, CH_Four Gas flow rate and H₂ Gas flow rate
Charging on the base cylinder 1737 while controlling each
A-Si containing elementary atoms and boron atoms: (H, X)
To form a layer composed of. After a predetermined time, B₂ H₆ 
/ H₂ Valve for introducing gas into the reaction chamber 1701
1726, inflow valve 1713 and outflow valve 171
Close all 8 and SiH_Four Gas, CH_Four Gas and H
₂ By introducing only gas into the reaction chamber 1701,
A-Si containing a carbon atom and a boron atom: (H,
X) containing a carbon atom on top of the layer
Consists of a-Si containing no elementary atoms: (H, X)
Layers can be formed.

It is needless to say that all the outflow valves other than the gas outflow valves necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is in the reaction chamber 1701. , Each outflow valve 1717-1
In order to avoid remaining in each gas pipe from 721 to the inside of the reaction chamber 1701, each outflow valve 1717-17
21 are all closed and each auxiliary valve 1732, 1733
And the main valve 1734 are fully opened, and the system is once evacuated to a high vacuum if necessary. Experimental Example 1 Pure water (resistivity 1 MΩcm: 25 ° C., 0.2
Number of fine particles of μm or more 500 pieces / 1 ml, total number of viable bacteria 10 pieces / ml, organic matter amount (TOC) ≦ 1 m
The relationship between the amount of pure water and the particle size of ice particles was investigated by producing spherical ice particles using the manufacturing apparatus shown in FIG. 79 using g) and liquid nitrogen as a cooling means. .
The results are shown in Table 136.

[0331]

[Table 136] As is clear from Table 136, in the manufacturing apparatus shown in FIG. 79, by appropriately adjusting the amount of pure water,
It is possible to obtain spherical ice particles having an arbitrary particle size. [Experimental Example 2] Spherical ice particles having various particle sizes were prepared in the same manner as in Experimental Example 1, and the injection pressure, the distance between the injection means of the ice particles and the support, the rotation speed of the support, and the like were determined. By varying the surface of the aluminum alloy cylinder (diameter 60 mm, length 298 mm), irregularities were formed. Then, the relationship between the diameter Ri of the ice particles, the injection pressure p, and the curvature R and the width D of the dimples was examined. It was confirmed that it was decided by.
Also, the dimple pitch (dimple density,
It was confirmed that the pitch of the irregularities can be controlled to a desired pitch by controlling the rotation speed and the rotation speed of the aluminum alloy cylinder, the falling amount of spherical ice particles, and the like.

[Experimental Example 3] In order to confirm the cleaning effect, an oil polybutene LV-10 for cylinder cutting (manufactured by Nippon Petrochemical Co., Ltd.) was applied to the surface of an aluminum alloy cylinder (diameter 60 mm, length 298 mm). Then, the support is washed by colliding spherical ice particles, the surface of the support after washing is observed with a microscope, and India ink is applied to the surface of the support, depending on the cissing condition of the ink. The degree of cleaning was evaluated. Table 2 shows the evaluation results. Here, for the "surface state", ◎ means "very good", ○ means "good", △ means "no problem in practical use", × means "impractical", and "rejection" means ◎ means "very good", ○ means "good", △ means "partially repelled", and x means "mostly repelled".

[0333]

[Table 137] From this evaluation result, it was confirmed that the dimple processing using ice particles also has a cleaning effect. Example 76 Pure water (resistivity 1 MΩcm: 25 ° C., 0.
Number of fine particles of 2 μm or more 500 pieces / 1 ml, total number of viable bacteria 10 pieces / ml, amount of organic matter (TOC) ≦ 1 m
Using g) and liquid nitrogen (cooling means), the production conditions shown in FIG. 79 were used to change the production conditions to produce spherical ice particles. Furthermore, the spraying pressure of ice particles, the distance between the spraying means of ice particles and the support, and the rotation speed of the support are 2 to 5 kg / cm ² , 20 to 80 mm, and 300 to 8, respectively.
00 rpm. And the surface of an aluminum alloy cylinder (diameter: 60 mm, length: 298 mm) is treated to obtain a cylindrical aluminum support having a width D and a ratio D / R shown in the upper column of Table 138 (cylinder No. . 101-106) was obtained.

[0334]

[Table 138] Next, a cylindrical aluminum support (cylinder No. 1
01-106) under the layer forming conditions shown in Table 139, a light-receiving layer was formed by the manufacturing apparatus shown in FIG.

[0335]

[Table 139] Regarding these light receiving members, a wavelength of 780 nm was obtained by using the image exposure apparatus shown in FIGS.
Image exposure was performed by irradiating a laser beam having a spot diameter of 80 μm, and development transfer was performed to obtain an image. The occurrence of interference fringes in the obtained image is as shown in the lower column of Table 138. In Table 138, ⊚ is “very good”, ◯ is “good”,
Δ indicates “no problem in practical use”, and × indicates “impractical use”.

The image exposure apparatus used is as shown in FIG.
As shown in (A) and (B), a semiconductor laser 1802
A polygon mirror 1804 for deflecting the laser light emitted from the semiconductor laser 1802, and the polygon mirror 1
And a fθ lens 803 for forming an image of the laser light reflected by 804 on the scanning surface of the light receiving member 1801. [Comparative Example 22] Next, as a comparison, an aluminum alloy cylinder (diameter 60 mm, length 298 mm, uneven pitch 100, which has been surface-treated with a conventional diamond bite.
μ, unevenness depth 3 μm, cylinder No. 107) was used to prepare a light receiving member in the same manner as in Example 76.
When the obtained light receiving member was observed with an electron microscope, the surface of the support and the layer interface between the light receiving layer and the surface of the light receiving layer were parallel to each other. An image was formed using this light receiving member in the same manner as described above, and the obtained image was evaluated in the same manner as described above. The results are shown in the lower column of Table 138 together with the result of Example 76. From Table 138, it was confirmed that the dimple according to the present invention can efficiently prevent the interference phenomenon due to the laser light which is the coherent light. [Example 77] The width D shown in Tables 140 and 141 was obtained by treating the surface of an aluminum alloy cylinder in the same manner as in Example 76 using the manufacturing apparatus shown in FIG. 79.
And a cylindrical aluminum support having a ratio D / R (cylinder Nos. 108 to 119) was obtained.

[0337]

[Table 140]

[0338]

[Table 141] Next, using this cylinder, a light receiving member was prepared under the same conditions as in Example 76. Using the prepared light-receiving member, the normal toner, and the experimentally prepared toner having a particle size of about ½, the light-receiving member was incorporated into the image exposure apparatus shown in FIG. Image exposure was performed by irradiating a laser beam having a diameter of 80 μm, and development transfer was performed to obtain an image. This operation was repeated to produce 100,000 images, and then the light receiving member was taken out to evaluate the cleaning property. The evaluation results are shown in Tables 140 and 141.
Here, the ratio D / R was changed as a relative value with the conventional value being 1. In Tables 140 and 141, ⊚ represents “very good”, ◯ represents “good”, Δ represents “no practical problem”, and × represents “impractical”.

From Tables 140 and 141, it was confirmed that the optimum curvature radius R exists depending on the particle size of the toner used. At the same time, in the present invention, it was confirmed that by appropriately adjusting the diameter of the ice particles and the pressure with which the ice particles collide with the support, it is possible to easily cope with the case where the toner particles used have different particle diameters. Example 78 Similar to Example 77, a cylindrical aluminum support having a width D and a ratio D / R shown in Tables 140 and 141 (cylinder Nos. 108 to 119).
Got Next, using this cylinder, a light receiving member was prepared under the same conditions as in Example 76. Similar to Example 76, the prepared light receiving member was incorporated into the image exposure apparatus shown in FIG. 81, and image exposure was performed using laser light of two kinds of wavelengths (one wavelength is 1.5 times the other wavelength), Development transfer was performed to obtain an image. The obtained image was evaluated in the same manner as in Example 76. The evaluation results are shown in Tables 140 and 141 together with the evaluation results of Example 77. Here, the ratio D / R was changed as a relative value with the conventional value being 1. From Table 140 and Table 141, it was confirmed that the optimum radius of curvature R exists depending on the wavelength of the laser used. It was also confirmed that the diameter of the ice particles and the pressure for colliding with the support can be adjusted appropriately to easily cope with different wavelengths of the laser used. [Examples 79 to 83] On the cylindrical aluminum support of Example 76 (cylinder Nos. 103 to 106), Table 1
No. 42 to Table 146, except that the light receiving layer was formed according to the layer forming conditions, a light receiving member was prepared in the same manner as in Example 76. Similar to the obtained light receiving member, Example 7
Image formation was performed in the same manner as in No. 6.

[0340]

[Table 142]

[0341]

[Table 143]

[0342]

[Table 144]

[0343]

[Table 145]

[0344]

[Table 146] In each of the obtained images, no occurrence of interference fringes was observed,
And it was of very good quality.

From the above results, it was confirmed that the dimples according to the present invention exhibit a sufficient function regardless of the formulation of the light receiving layer. [Embodiment 84] A cylinder No. 1 is manufactured using the manufacturing apparatus shown in FIG. Dimple treatment was performed on the surface of 1000 cylinders under the condition of 105, and the surface of the cylinder was observed every 100th cylinder with a microscope, and then a light-receiving member was prepared under the same conditions as in Example 76. After performing image formation on the obtained light receiving member in the same manner as in Example 76,
Image evaluation was performed. The evaluation results are shown in Table 147. In Table 147, as for the “surface condition”, ○ is “good”, Δ is “partially scratched”, and × is “scratch is many”.
Regarding “image evaluation”, “◯” indicates “good”, “Δ” indicates “no practical problem”, and “x” indicates “impractical”.

[0346]

[Table 147] [Comparative Example 23] The same evaluation as that of Example 84 was performed after performing the same experiment as in Example 84 except that the dimple treatment was performed using a conventional metallic hard sphere. The evaluation results are shown in Table 147 together with the evaluation results of Example 84. From Table 147, it was confirmed that when the hard spheres are made of metal, the hard spheres may deteriorate after long-term use, and the surface of the support may be damaged by chips or the like. On the other hand, in the method for treating dimples according to the present invention, since fresh spherical ice particles are constantly supplied, the surface of the support is not damaged even after long-term use.

[0347]

As described above, according to the first aspect of the present invention, in the method of manufacturing an electrophotographic photosensitive member including the step of forming a functional film on a metal substrate, the present invention is particularly applied to a metal substrate. In an electrophotographic photoreceptor manufacturing method including a step of forming an electrophotographic photoreceptor film having a layer structure of amorphous silicon as a base material by a plasma CVD method, before the step of forming the light receiving layer, A step of cutting the surface layer with a predetermined accuracy, a step of cleaning the surface of the cut conductive substrate and a step of bringing the surface of the cleaned conductive substrate into contact with pure water after the cutting step are performed. Therefore, it is possible to inexpensively and stably manufacture an electrophotographic photosensitive member which gives a uniform and high-quality image without worrying about environmental pollution. Further, according to the present invention, by continuously changing carbon atoms from the conductive substrate in the photoconductive layer, an important function for the electrophotographic photosensitive member is to generate charges (photocarriers) and transport the generated charges. Can be connected smoothly, and the optical energy gap between the charge generation layer and the charge transport layer, which is a problem in the so-called function-separated type light-receiving member in which the conventional charge generation layer and the charge transport layer are separated, becomes a problem. Prevents poor charge transfer due to the difference, and contributes to improvement of photosensitivity and reduction of residual potential. In addition, since the photoconductive layer contains carbon, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced, and high charging ability and photosensitivity can be achieved. Significant improvement is seen and the withstand voltage against high voltage is also improved.

By disposing a layer containing a large amount of carbon on the side of the conductive substrate, the chargeability is improved by preventing the injection of charges from the conductive substrate, and the adhesion between the conductive substrate and the photoconductive layer is improved. The property is improved, and peeling of the film and generation of minute defects can be suppressed. By using the photoconductive layer of the present invention, it is possible to dramatically improve durability while maintaining high electric charging ability, high sensitivity, low residual potential, and excellent electrical characteristics. That is, since the adhesion of the film is improved, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the dielectric constant is lowered and the durability against high voltage is also improved, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur.
Since the surface layer of the present invention is rich in water repellency, it has improved moisture resistance. Furthermore, the mechanical strength and electrical withstand voltage are improved, and it is possible to effectively prevent the injection of electric charges from the surface when subjected to electrification treatment, and to improve the charging ability, operating environment characteristics, durability and electrical withstand voltage. Can be improved. Further, since the absorption of light in the surface layer is reduced, the sensitivity can be improved. Further, according to the present invention, it is possible to greatly improve the yield due to a defective appearance such as clouding of the surface of the photoreceptor after remodeling. According to a second aspect of the present invention, there is provided an electrophotographic photosensitive member manufacturing method including a step of forming a functional film on a metal substrate, wherein an electron having an amorphous silicon layered structure of the present invention as a host is formed on the metal substrate. In an electrophotographic photoreceptor manufacturing method including a step of forming a photographic photoreceptor film by a plasma CVD method, before the step of forming the light receiving layer,
A step of cutting the surface layer of the conductive substrate with a predetermined accuracy, a step of washing the cut conductive substrate surface after the cutting step, and a step of bringing the surface of the washed conductive substrate into contact with pure water Therefore, it is possible to inexpensively and stably manufacture an electrophotographic photosensitive member which gives a uniform and high-quality image without concern about environmental pollution.

Furthermore, according to the present invention, the photoconductive layer is formed by continuously changing carbon atoms from the conductive substrate.
It is possible to smoothly connect the important functions of the electrophotographic photosensitive member, that is, the generation of electric charges (photocarriers) and the transportation of the generated electric charges, and the so-called function separation in which the conventional charge generation layer and the charge transport layer are separated. To provide a photoconductor having improved photosensitivity and reduced residual potential, which can prevent defective running of charges due to a difference in optical energy gap between a charge generation layer and a charge transport layer, which is a problem in a mold type light receiving member. it can. In addition, since the photoconductive layer contains carbon, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced, and high charging ability and photosensitivity can be achieved. It is possible to provide a photosensitive member which is remarkably improved and has improved withstand voltage against high voltage. By placing a layer containing a large amount of carbon on the side of the conductive substrate, the chargeability is improved by blocking the injection of charges from the conductive substrate, and the adhesion between the conductive substrate and the photoconductive layer is improved. However, it is possible to provide a photoconductor in which peeling of the film and generation of minute defects are suppressed. By using the photoconductive layer of the present invention, it is possible to dramatically improve durability while maintaining high electric charging ability, high sensitivity, low residual potential, and excellent electrical characteristics. That is, since the adhesion of the film is improved, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Further, since the dielectric constant is lowered and the durability against a high voltage is also improved, it is possible to provide a photoreceptor in which "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur.

The above-mentioned effects are obtained by, for example, microwave C
This is particularly noticeable when a layer is formed by increasing the deposition rate as in the VD method. Further, since the film quality becomes dense, it is possible to effectively prevent the charge from being injected from the surface when it is subjected to a charging treatment, and it is possible to improve charging ability, use environment characteristics, durability and electrical withstand voltage. . Furthermore, since the accumulation of carriers at the interface between the photoconductive layer and the surface layer can be reduced, image deletion can be suppressed even if the chargeability is kept high. Further, it is possible to provide a photoconductor in which the ghost is greatly improved. According to the present invention, it is possible to further significantly improve the yield of defective appearance such as cloudiness on the surface of the photoconductor after manufacturing. Further, according to the present invention, there is provided a method for stably supplying a photoconductor having uniform characteristics by eliminating the variation in the properties of the electrophotographic photoconductor manufactured immediately after the periodic cleaning of the reaction container. According to the third aspect of the invention, an electrophotographic photosensitive member film having amorphous silicon as a base material is formed on the substrate by plasma CVD.
In a method of manufacturing an electrophotographic photosensitive member including a step of forming by a method, a step of cutting the surface of the base body with a predetermined accuracy before the step of forming the light receiving layer, and a conductive layer cut after the cutting step. By carrying out the step of washing the surface of the conductive substrate and the step of bringing the surface of the washed conductive substrate into contact with pure water, the electrophotographic photoreceptor that gives a uniform high-quality image can be manufactured inexpensively and stably. Moreover, it has become possible to manufacture without worrying about environmental pollution.

Furthermore, according to the present invention, the photoconductive layer is formed by continuously changing carbon atoms from the conductive substrate.
It is possible to smoothly connect the important functions of the electrophotographic photosensitive member, that is, the generation of electric charges (photocarriers) and the transportation of the generated electric charges, and the so-called function separation in which the conventional charge generation layer and the charge transport layer are separated. This prevents defective running of charges due to a difference in optical energy gap between the charge generation layer and the charge transport layer, which is a problem in the mold type light receiving member, and contributes to improvement of photosensitivity and reduction of residual potential. In addition, since the photoconductive layer contains carbon, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced, and high charging ability and photosensitivity can be achieved. Significant improvement is seen and the withstand voltage against high voltage is also improved. By placing a layer containing a large amount of carbon on the side of the conductive substrate, the chargeability is improved by blocking the injection of charges from the conductive substrate, and the adhesion between the conductive substrate and the photoconductive layer is improved. However, peeling of the film and generation of minute defects can be suppressed. By using the photoconductive layer of the present invention, it is possible to dramatically improve durability while maintaining high electric charging ability, high sensitivity, low residual potential, and excellent electrical characteristics. That is, since the adhesion of the film is improved, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the dielectric constant is lowered and the durability against high voltage is also improved, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur.

The surface layer produced by the method of the present invention is rich in water repellency and therefore has improved moisture resistance. Furthermore, the mechanical strength and electrical withstand voltage are improved, and the charge can be effectively prevented from injecting charges from the surface when subjected to a charging treatment.
It is possible to improve use environment characteristics, durability, and electrical pressure resistance. Further, since the absorption of light in the surface layer is reduced, the sensitivity can be improved. In addition, especially when recycled paper is used, the durability can be significantly extended. Further, according to the present invention, it is possible to greatly improve the yield due to the appearance defect such as clouding on the surface of the photoreceptor after remodeling. According to a fourth aspect of the present invention, in the electrophotographic photosensitive member manufacturing method including the step of forming an electrophotographic photosensitive member film having amorphous silicon as a base material on the substrate by a plasma CVD method, First, a step of cutting the surface of the base body with a predetermined accuracy, a step of cleaning the surface of the cut conductive base material after the cutting step, and a step of bringing the surface of the cleaned conductive base material into contact with pure water. By performing the above, it becomes possible to inexpensively and stably manufacture an electrophotographic photosensitive member which gives a uniform high-quality image and without fear of environmental pollution. Further, according to the present invention, by continuously changing carbon atoms from the conductive substrate in the photoconductive layer, an important function for the electrophotographic photosensitive member is to generate charges (photocarriers) and transport the generated charges. Can be connected smoothly, and the optical energy gap between the charge generation layer and the charge transport layer, which is a problem in the so-called function-separated type light-receiving member in which the conventional charge generation layer and the charge transport layer are separated, becomes a problem. Prevents poor charge transfer due to the difference, and contributes to improvement of photosensitivity and reduction of residual potential.

Since carbon is contained in the photoconductive layer, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced and high charging ability can be obtained. The photosensitivity is remarkably improved, and the withstand voltage against high voltage is also improved. Then, by placing a layer containing a large amount of carbon on the side of the conductive substrate, the chargeability is improved by preventing the injection of charges from the conductive substrate, and the adhesion between the conductive substrate and the photoconductive layer is improved. Then
It is possible to suppress peeling of the film and generation of minute defects.
By using the photoconductive layer of the present invention, it is possible to dramatically improve durability while maintaining high electric charging ability, high sensitivity, low residual potential, and excellent electrical characteristics. That is, since the adhesion of the film is improved, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the dielectric constant is lowered and the durability against high voltage is also improved, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur. The surface layer produced by the method of the present invention is rich in water repellency and therefore has improved moisture resistance. Furthermore, the mechanical strength and electrical withstand voltage are improved, and it is possible to effectively prevent the injection of electric charges from the surface when subjected to electrification treatment, and to improve the charging ability, operating environment characteristics, durability and electrical withstand voltage. Can be improved. Further, since the absorption of light in the surface layer is reduced, the sensitivity can be improved. In addition, especially when recycled paper is used, the durability can be significantly extended.

Further, according to the present invention, it is possible to greatly improve the yield due to poor appearance such as clouding on the surface of the photoreceptor after remodeling. According to a fifth aspect of the present invention, in an electrophotographic photosensitive member manufacturing method including a step of forming a functional film on a metal substrate, in particular, a layer of amorphous silicon of the present invention is used as a matrix on the metal substrate. In the method of manufacturing an electrophotographic photosensitive member including the step of forming the electrophotographic photosensitive member film by a plasma CVD method, the surface layer of the conductive substrate is cut with a predetermined accuracy before the step of forming the light receiving layer. Since the step and the step of cleaning the surface of the cut conductive substrate after this cutting step and the step of bringing the surface of the washed conductive substrate into contact with pure water are performed, a uniform high-quality image is obtained. It is possible to inexpensively and stably manufacture the electrophotographic photosensitive member to be given, without worrying about environmental pollution. Further, according to the present invention, by continuously changing carbon atoms from the conductive substrate in the photoconductive layer, an important function for the electrophotographic photosensitive member is to generate charges (photocarriers) and transport the generated charges. Can be connected smoothly, and the optical energy gap between the charge generation layer and the charge transport layer, which is a problem in the so-called function-separated type light-receiving member in which the conventional charge generation layer and the charge transport layer are separated, becomes a problem. Prevents poor charge transfer due to the difference, and contributes to improvement of photosensitivity and reduction of residual potential. In addition, since the photoconductive layer contains carbon, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced, and high charging ability and photosensitivity can be achieved. Significant improvement is seen and the withstand voltage against high voltage is also improved.

By disposing a layer containing a large amount of carbon on the side of the conductive substrate, the chargeability is improved by preventing the injection of charges from the conductive substrate, and the adhesion between the conductive substrate and the photoconductive layer is improved. The property is improved, and peeling of the film and generation of minute defects can be suppressed. By using the photoconductive layer of the present invention, it is possible to dramatically improve durability while maintaining high electric charging ability, high sensitivity, low residual potential, and excellent electrical characteristics. That is, since the adhesion of the film is improved, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the dielectric constant is lowered and the durability against high voltage is also improved, "leak spots" caused by dielectric breakdown of a part of the light receiving member are less likely to occur.
Since the surface layer of the present invention is rich in water repellency, it has improved moisture resistance. Furthermore, the mechanical strength and electrical withstand voltage are improved, and it is possible to effectively prevent the injection of electric charges from the surface when subjected to electrification treatment, and to improve the charging ability, operating environment characteristics, durability and electrical withstand voltage. Can be improved. Further, since the absorption of light in the surface layer is reduced, the sensitivity can be improved. Further, according to the present invention, it is possible to greatly improve the yield due to a defective appearance such as clouding of the surface of the photoreceptor after remodeling. Further, the light receiving member of the sixth invention is composed of conventional amorphous silicon because the surface of the support has irregularities due to trace pits obtained by colliding spherical ice particles with the surface of the support. It is possible to solve all of the problems that have occurred in the light receiving member having a light receiving layer, and even when a laser light which is a coherent monochromatic light is used as a light source, an interference fringe pattern in a formed image due to an interference phenomenon is generated. It is possible to remarkably prevent the appearance and form a very good visible image. In particular, when applied as a light receiving member for electrophotography, even if the particle size of the toner used changes, there is no effect of residual potential on image formation, and its electrical characteristics are stable and high. Sensitivity and high SN ratio, excellent in light resistance and repeated use characteristics,
It is possible to stably and repeatedly obtain a high-quality image with high density, clear halftone, and high resolution.

Further, the method for producing a light receiving member of the seventh invention is
Since the spherical shape for forming the trace pit is ice particles, the shape of the trace pit can be easily adjusted. The characteristics of the receiving member can be expressed. In particular, it is possible to prepare a light receiving member which is excellent in matching with a semiconductor laser, has a fast photoresponse, and has extremely excellent electrical, optical and photoconductive properties, electrical withstand voltage properties and use environment properties. In addition, it is possible to wash the support without using an organic solvent, which is extremely effective against environmental problems, and because the work process can be simplified easily, it is easy to reduce the manufacturing cost. Becomes

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a substrate surface treatment apparatus used to carry out an electrophotographic photosensitive member manufacturing method of the present invention.

FIG. 2A is a schematic vertical cross-sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method. (B) is the same cross-sectional view.

FIG. 3 is a schematic cross-sectional view of a cleaning device for cleaning a substrate as a pretreatment for forming a deposited film in a conventional method.

FIG. 4 is a schematic vertical cross-sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a high frequency plasma CVD method.

5 (a) and 5 (b) are layer configurations formed in the method for producing an electrophotographic photosensitive member of the present invention.

FIG. 6 is a sectional view showing a layer structure of a conventional electrophotographic photosensitive member.

FIG. 7 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 8 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 9 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 10 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 11 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 12 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 13 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 14 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 15 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 16 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 17 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 18 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 19 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 20 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 21 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 22 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 23 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 24 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 25 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 26 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 27 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 28 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 29 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 30 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 31 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 32 is a system for continuously producing an electrophotographic photosensitive member by a microwave plasma CVD method.

FIG. 33 shows changes in characteristics when the electrophotographic photosensitive member according to the present invention is continuously manufactured.

FIG. 34 shows changes in characteristics when electrophotographic photoreceptors according to the present invention are continuously manufactured.

FIG. 35 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 36 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 37 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 38 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 39 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 40 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 41 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 42 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 43 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 44 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 45 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 46 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 47 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 48 is a distribution pattern of carbon content in the photoconductive layer of the present invention.

FIG. 49 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 50 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 51 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 52 is a carbon content distribution pattern in the photoconductive layer according to the present invention.

FIG. 53 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 54 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 55 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 56 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 57 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 58 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 59 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 60 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 61 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 62 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 63 is a carbon content distribution pattern in the photoconductive layer of the present invention.

FIG. 64 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 65 is a distribution pattern of carbon content in the photoconductive layer outside the present invention.

FIG. 66 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 67 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 68 is a distribution pattern of fluorine content in the photoconductive layer of the present invention.

FIG. 69 is a fluorine content distribution pattern in the photoconductive layer of the present invention.

FIG. 70 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 71 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 72 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 73 is a distribution pattern of oxygen content in the photoconductive layer of the present invention.

FIG. 74 is a cross-sectional view showing an example of the light receiving member of the present invention.

FIG. 75 is an enlarged view showing a part of a conventional light receiving member in which a light receiving layer having a multilayer structure is deposited on a support whose surface is regularly roughened.

FIG. 76 is an enlarged view of a part of the light receiving member shown in FIG. 74.

77 is a schematic diagram showing one method for forming irregularities on the surface of the support shown in FIG. 74. FIG.

FIG. 78 shows a typical example of a support having unevenness formed by a plurality of dimples on the surface by the method shown in FIG. 77.

FIG. 79 is a schematic configuration diagram showing an example of a manufacturing apparatus for forming irregularities on the surface of a support when the light receiving member according to the present invention is used as a light receiving member for electrophotography.

FIG. 80 is a schematic configuration diagram showing an apparatus for manufacturing a light receiving member by a plasma CVD method.

FIG. 81 is a schematic configuration diagram showing an image exposure apparatus using laser light used for evaluation.

[Explanation of symbols]

101 Substrate 102 Treatment Layer 103 Substrate Transfer Mechanism 111 Substrate Loading Table 121 Substrate Cleaning Tank 122 Cleaning Solution 131 Pure Water Contact Tank 132, 142 Nozzle 141 Drying Tank 151 Substrate Unloading Table 161 Transfer Arm 162 Moving Mechanism 163 Chucking Mechanism 164 Air Cylinder 165 Rail 201 Reaction Vessel 202 Microwave Introducing Window 203 Waveguide 204 Exhaust Pipe 205 Cylindrical Substrate 206 Discharge Space 207 Heater 209 Rotating Shaft 210 Motor 211 DC Bias Power Supply 212 Biasing Electrode 301 Substrate 302 Processing Tank 303 Substrate Transfer Mechanism 311 Substrate Loading Table 321 Base substrate cleaning tank 322 Cleaning liquid 351 Substrate carry-out table 361 Transfer arm 362 Moving mechanism 363 Chucking machine 364 Air cylinder 365 Rail 400 Deposited film forming device 4 1 Reaction Container 402 Cylindrical Substrate 403 Heater for Heating Cylindrical Substrate 404 Raw Material Gas Introduction Pipe 405 High Frequency Matching Box 406 Raw Material Gas Introduction Pipe 407 Reaction Vessel Leak Valve 408 Main Exhaust Valve 409 Vacuum Gauge 410 Raw Material Gas Supply Device 411-416 Mass Flow Controllers 417 to 422 Raw material gas cylinders 423 to 428 Raw material gas cylinder valves 429 to 434 Raw material gas inflow valves 435 to 440 Raw material gas outflow valves 441 to 446 Pressure regulators 447 Valves 501,601 Substrate 502 Photoconductive layer 502 'First photoconductive layer 503 ′ Second photoconductive layer 504,604 Surface layer 505,605 Electrophotographic photoreceptor 602 Charge transport layer 603 Charge generation layer 1100,1300,1801 Photoreceptive member 1101,1501 Support 1 101 ₁ , 1501 ₁ Surface 1102 Photoreceptive Layer 1102 ₁ , 1302 ₁ First Layer 1102 ₂ , 1302 ₂ Second Layer 1103, 1303 Free Surface 1104, 1304 Interface 1403, 1503, 1503 ₁ , 1503 ₂ , 160
5 ice particles 1404,1504,1504 _1, 1504 ₂ dimple 1601 aluminum cylinder 1602 rotates shaft 1603 injection unit 1604 pressurizing gas canister 1606 icemaker 1607 spray nozzles 1608 cooling means 1609 pure water tank 1610 pure pressurizing gas canister 1611 Jun Water supply pipe 1701 Reaction chamber 1702 to 1706 Gas cylinder 1707 to 1711 Mass flow controller 1712 to 1716 Inflow valve 1717 to 1721 Outflow valve 1722 to 1726 Valve 1901 Heating container 1902 Reaction container 1903 Cooling container 1904 Vacuum transfer container 1905 to 1910 Valve 1911 to 1914 Gate valve 1915 to 1920 Vacuum device 1921 Rail

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuyoshi Takai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Kya Non-Incorporated (72) Inventor Yoshio Seki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (56)

[Claims] 1. A step of cutting the surface of a conductive substrate with a predetermined accuracy, a step of washing the surface of the substrate after cutting with water, a step of bringing the surface of the conductive substrate into contact with pure water, and the conductive substrate. A method for producing an electrophotographic photosensitive member, comprising the step of forming a photoreceptive layer composed of a photoconductive layer and a surface layer composed of a non-single-crystal material having a silicon atom as a base, wherein the photoconductive layer is formed. Containing carbon atoms and hydrogen atoms throughout the layer in the layer, the content of the carbon atoms is unevenly distributed in the layer thickness direction, and is highly distributed on the side of the conductive substrate,
A method for producing an electrophotographic photosensitive member, characterized in that a photoreceptive layer containing carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms in the surface layer is formed on a conductive substrate by a plasma CVD method. 2. The sum of the content of carbon atoms, oxygen atoms and nitrogen atoms in the surface layer is (carbon atom + oxygen atom + nitrogen atom) / (silicon atom + carbon atom + oxygen atom + nitrogen atom). The value represented is 40 to 90 atom%, and contains halogen, the content of the halogen atom is 20 atom% or less, and the sum of the content of hydrogen atom and the halogen atom is 30 to
The method for producing an electrophotographic photosensitive member according to claim 1, wherein the content is 70 atomic%. 3. The content of carbon atoms in the photoconductive layer is 0.5 to 50 atomic% at the interface with the conductive substrate,
The electrophotographic photosensitive member according to claim 1 or 2, wherein the content of hydrogen atoms in the interface with the surface layer is substantially 0%, and the content of hydrogen atoms in the photoconductive layer is 1 to 40 atom%. Manufacturing method. 4. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the photoconductive layer contains a halogen atom. 5. The production of an electrophotographic photosensitive member according to claim 4, wherein the halogen atoms in the photoconductive layer are distributed so as to have a maximum value at the interface with the surface layer or in the vicinity of the interface. Method. 6. The surface layer is characterized in that the total content of carbon atoms, oxygen atoms, and nitrogen atoms in the surface layer is distributed so as to increase from the surface of the photoconductive layer toward the outermost surface. Manufacturing method of electrophotographic photosensitive member. 7. A step of cutting the surface of a conductive substrate with a predetermined accuracy, a step of washing the surface of the substrate after cutting with water, a step of bringing the surface of the conductive substrate into contact with pure water, and the conductive substrate. A method for producing an electrophotographic photosensitive member, comprising the step of forming a photoreceptive layer composed of a photoconductive layer and a surface layer composed of a non-single-crystal material having a silicon atom as a base, wherein the photoconductive layer is formed. The layer contains carbon atoms, hydrogen atoms, halogen atoms, and oxygen atoms throughout the layer, and the content of the carbon atoms is unevenly distributed in the layer thickness direction, and is highly distributed on the side of the conductive substrate. The method for producing an electrophotographic photosensitive member is characterized in that a photoreceptive layer containing carbon atoms and hydrogen atoms in the surface layer is formed on a conductive substrate by a plasma CVD method. 8. A second photoconductive layer having a silicon atom as a host and comprising a hydrogen atom and / or a halogen atom and having substantially 0 carbon% carbon atoms is provided between the photoconductive layer and the surface layer. The method for manufacturing an electrophotographic photoreceptor according to claim 7, wherein the method is provided. 9. The content of carbon atoms in the photoconductive layer is 0.5 to 50 atom% at the interface with the conductive substrate, and substantially 0 atom% at the interface with the surface layer or in the vicinity of the interface. And the content of hydrogen atoms in the photoconductive layer is 1 to 4
The method for producing an electrophotographic photosensitive member according to claim 7, wherein the content is 0 atom%. 10. The photoconductive layer contains 1 to 95 atomic ppm of halogen atoms and 10 to 50 oxygen atoms.
8. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the content is 00 atom ppm. 11. The electrophotographic photosensitive material according to claim 7, wherein the halogen atoms contained in the photoconductive layer are distributed so as to have a maximum value at an interface with the surface layer side or in the vicinity of the interface. Body manufacturing method. 12. The oxygen atoms contained in the photoconductive layer are distributed so as to have a maximum value at the interface with the surface layer side or in the vicinity of the interface.
A method for producing the electrophotographic photosensitive member described. 13. The content of carbon atoms in the surface layer is
11. The method according to claim 10, wherein the content is 40 to 90 atom%, and the content of the halogen atom is 20 atom% or less and the sum of the content of hydrogen atom and the halogen atom is 30 to 70 atom%. Manufacturing method of electrophotographic photoreceptor. 14. A step of cutting the surface of a conductive substrate with a predetermined accuracy, a step of cleaning the surface of the substrate after cutting with water, a step of bringing the surface of the conductive substrate into contact with pure water, and the conductive substrate. A method for producing an electrophotographic photosensitive member, comprising the step of forming a photoreceptive layer composed of a photoconductive layer and a surface layer composed of a non-single-crystal material having a silicon atom as a base, wherein the photoconductive layer is formed. Containing carbon atoms and hydrogen atoms throughout the layer in the layer, the content of the carbon atoms is unevenly distributed in the layer thickness direction, and is highly distributed on the side of the conductive substrate,
A method for producing an electrophotographic photosensitive member, characterized in that a photoreceptive layer containing carbon atoms, hydrogen atoms and Group III elements of the periodic table in the surface layer is formed on a conductive substrate by a plasma CVD method. . 15. The content of carbon atoms in the surface layer is
The value represented by carbon atom / (silicon atom + carbon atom) is 40 to 90 atom%, and contains halogen, the content of the halogen atom is 20 atom% or less, and the content of hydrogen atom and halogen atom. The method for producing an electrophotographic photosensitive member according to claim 14, wherein the sum of the amounts is 30 to 70 atomic%. 16. The content of carbon atoms in the photoconductive layer is 0.5 to 50 atomic% at the interface with the conductive substrate, and substantially 0% at the interface with the surface layer,
The method for producing an electrophotographic photosensitive member according to claim 14 or 15, wherein the content of hydrogen atoms in the photoconductive layer is 1 to 40 atom%. 17. The method for producing an electrophotographic photosensitive member according to claim 14, wherein the photoconductive layer contains a halogen atom. 18. The production of an electrophotographic photosensitive member according to claim 17, wherein the halogen atoms in the photoconductive layer are distributed so as to have a maximum value at the interface with the surface layer or in the vicinity of the interface. Method. 19. The photoconductive layer further contains an oxygen atom in addition to a halogen atom.
A method for producing the electrophotographic photosensitive member described. 20. The electrophotographic photosensitive member according to claim 17, wherein the oxygen atoms contained in the photoconductive layer are distributed so as to have a maximum value at the interface with the surface layer or in the vicinity of the interface. Production method. 21. A periodic table of the periodic table contained in the surface layer.
The method for producing an electrophotographic photosensitive member according to claim 15, wherein the content of the group III is 1 × 10 ⁵ ppm or less based on the total number of atoms. 22. The method for producing an electrophotographic photosensitive member according to claim 15, wherein the content of carbon atoms in the surface layer is distributed so as to increase from the surface of the photoconductive layer toward the outermost surface. . 23. The method for producing an electrophotographic photosensitive member according to claim 14, wherein the surface layer further contains an oxygen atom and a nitrogen atom. 24. (a) A step of cutting the surface of a conductive substrate with a predetermined accuracy, (b) a step of washing the surface of the substrate after cutting with water, (c) contacting the washed substrate surface with pure water. And (d) the cleaned substrate surface contains carbon atoms and hydrogen atoms, and the content of the carbon atoms is non-uniform in the layer thickness direction and highly distributed on the side of the conductive substrate. Forming a first photoconductive layer composed of a non-single-crystal material having silicon atoms and carbon as a base material by the plasma CVD method, and (e) a silicon atom on the formed first photoconductive layer. Forming a second photoconductive layer having as a matrix by a plasma CVD method, (f) a silicon atom as a matrix on the formed second photoconductive layer, a carbon atom, a hydrogen atom and a periodic table III. Plas a surface layer containing group elements Forming by CVD process for producing an electrophotographic photoreceptor characterized by having each of the above steps. 25. The content of carbon atoms in the surface layer is
The value represented by carbon atom / (silicon atom + carbon atom) is 40 to 90 atom%, and contains halogen, the content of the halogen atom is 20 atom% or less, and the content of hydrogen atom and halogen atom. 25. The method for producing an electrophotographic photosensitive member according to claim 24, wherein the sum of the amounts is 30 to 70 atomic%. 26. The content of carbon atoms in the first photoconductive layer is 0.5 to 50 at the interface with the conductive substrate.
26. The electron according to claim 24, wherein the atomic% is substantially 0% at the interface with the surface layer, and the content of hydrogen atoms in the photoconductive layer is 1 to 40 atomic%. Manufacturing method of photographic photoreceptor. 27. The method for producing an electrophotographic photosensitive member according to claim 24, wherein the first photoconductive layer contains a halogen atom. 28. The halogen atom in the first photoconductive layer is distributed so as to have a maximum value at or near an interface with the surface layer.
A method for producing the electrophotographic photosensitive member described. 29. The method for producing an electrophotographic photosensitive member according to claim 27, wherein the first photoconductive layer further contains oxygen atoms in addition to halogen atoms. 30. The oxygen atoms contained in the first photoconductive layer are distributed so as to have a maximum value at or near the interface with the surface layer.
7. The method for producing an electrophotographic photosensitive member according to 7. 31. A periodic table of the periodic table contained in the surface layer.
Group III content is 1 × 10 ⁵ atoms pp with respect to the total number of atoms
26. The method for producing an electrophotographic photosensitive member according to claim 25, which is m or less. 32. The electrophotographic photosensitive member according to claim 25, wherein the carbon atom content in the surface layer is distributed so as to increase from the surface of the second photoconductive layer toward the outermost surface. Manufacturing method. 33. The method for producing an electrophotographic photosensitive member according to claim 24, wherein the surface layer further contains an oxygen atom and a nitrogen atom. 34. (a) A step of cutting the surface of a conductive substrate with a predetermined accuracy, (b) a step of washing the substrate surface after cutting with water, (c) contacting the washed substrate surface with pure water. And (d) the cleaned substrate surface contains carbon atoms and hydrogen atoms, and the content of the carbon atoms is non-uniform in the layer thickness direction and highly distributed on the side of the conductive substrate. Forming a first photoconductive layer composed of a non-single-crystal material having silicon atoms and carbon as a base material by the plasma CVD method, and (e) a silicon atom on the formed first photoconductive layer. A step of forming a second photoconductive layer having as a matrix by a plasma CVD method, (f) a silicon atom as a matrix on the formed second photoconductive layer, carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen Plas a surface layer containing atoms A method of manufacturing an electrophotographic photosensitive member, which comprises the step of forming by a CVD method and the above-mentioned steps. 35. A carbon atom, an oxygen atom in the surface layer,
The sum of the content of nitrogen atoms is a value represented by (carbon atom + oxygen atom + nitrogen atom) / (silicon atom + carbon atom + oxygen atom + nitrogen atom), and is 40 to 90 atom%, and halogen. 35. The content of the halogen atom is 20 atom% or less with respect to the total atom content in the surface layer, and the sum of the content of hydrogen atom and the halogen atom is 30 to 70 atom%. Manufacturing method of electrophotographic photosensitive member. 36. The carbon atom content in the first photoconductive layer is 0.5 to 50 at the interface with the conductive substrate.
Atomic%, substantially 0% at the interface with the second photoconductive layer, and the content of hydrogen atoms in the first photoconductive layer is 1 to 40 atomic%. Item 34. A method for producing an electrophotographic photosensitive member according to Item 35. 37. The method for producing an electrophotographic photosensitive member according to claim 34, wherein the first photoconductive layer contains a halogen atom. 38. The halogen atom in the first photoconductive layer is distributed so as to have a maximum value at an interface with the second photoconductive layer or in the vicinity of the interface. Manufacturing method of electrophotographic photosensitive member. 39. The method for producing an electrophotographic photosensitive member according to claim 37, wherein the first photoconductive layer further contains an oxygen atom. 40. The oxygen atom in the photoconductive layer according to the first aspect is distributed so as to have a maximum value at an interface with the second photoconductive layer or in the vicinity of the interface. Manufacturing method of electrophotographic photosensitive member. 41. A carbon atom, an oxygen atom in the surface layer,
36. The method for producing an electrophotographic photosensitive member according to claim 35, wherein the sum of the content of nitrogen atoms is distributed so as to increase from the interface with the second photoconductive layer toward the outermost surface. 42. A support, and a multi-layered light-receiving layer formed on the support, wherein the surface of the support causes a plurality of spherical ice particles to spontaneously drop or be pressure-jetted. A light receiving member, characterized in that it has irregularities due to a plurality of trace depressions obtained by causing a plurality of spherical ice particles to collide with the surface of the support. 43. The light receiving member according to claim 42, wherein the unevenness due to the plurality of trace pits is the unevenness due to the spherical trace dents having substantially the same radius of curvature. 44. The light receiving member according to claim 42 or 43, wherein the unevenness due to the plurality of trace dents is the unevenness due to the spherical trace dents having substantially the same radius of curvature and substantially the same width. 45. The unevenness due to the plurality of trace depressions causes a plurality of spherical ice particles of substantially the same size to spontaneously fall from substantially the same height or to be pressurized and jetted at substantially the same pressure, so that the plurality of spherical shapes. 45. The light receiving member according to any one of claims 42 to 44, wherein the light receiving member is obtained by colliding the ice particles of 1. with the surface of the support. 46. The plurality of spherical ice particles are produced by atomizing pure water in a gas phase and freezing the dispersed pure water by a cooling means. 45. The light receiving member according to any one of to 45. 47. The light receiving member according to claim 42, wherein the width of the trace recess is 500 μm or less. 48. The diameter of the spherical ice particles is 10 μm.
48. The light receiving member according to claim 42, wherein the light receiving member has a length of 10 mm. 49. The support according to claim 42, which is a metal body.
49. The light receiving member according to any one of 48 to 48. 50. A method for producing a light-receiving member comprising a support and a light-receiving layer having a multi-layered structure formed on the support, wherein a plurality of spherical ice particles are naturally dropped or added. Pressure injection,
An unevenness forming step of causing the plurality of spherical ice particles to collide with the surface of the support to form unevenness due to a plurality of trace depressions on the surface of the support; and forming the light receiving layer on the support. And a light receiving layer forming step. 51. The unevenness forming step comprises spontaneously dropping a plurality of spherical ice particles of substantially the same size from substantially the same height or pressurizing and ejecting the plurality of spherical ice particles to form a plurality of the spherical ice particles. 51. The method for producing a light receiving member according to claim 50, wherein particles are made to collide with the surface of the support. 52. In the unevenness forming step, pure water is dispersed in a gas phase in a mist state, and the dispersed pure water is frozen by a cooling means to produce the plurality of spherical ice particles. 52. The method for producing a light receiving member according to claim 50 or 51, further comprising an ice making step. 53. The fall distance or the pressure of pressure injection of the plurality of spherical ice particles is set so that the width of the trace dent is 500 μm or less. Method for producing light receiving member. 54. The method for producing a light-receiving member according to claim 50, wherein the unevenness forming step also serves as a support washing step of washing the support. 55. The diameter of the spherical ice particles is 10 μm.
55. The method for producing a light receiving member according to claim 50, wherein the method is 10 mm. 56. The support according to claim 50, which is a metal body.
55. A method for producing a light receiving member according to any one of 55 to 55.