JPH05134441A - Method for formation of light receiving member for electrophotograph - Google Patents

Abstract

PURPOSE:To provide a method for the formation of electrophotographic light receiving member excellent in electric characteristics, picture image characteristics, and durability. CONSTITUTION:An electrophotographic light receiving member 10 consists of a conductive base body 11 and a photoconductive layer 12 comprising noncrystalline material made of silicon atom as a mother material and a surface layer 13 successively formed on the supporting body. The photoconductive layer 12 contains hydrogen atom and carbon atom which is distributed in a manner that the amt. of carbon atom is larger in the supporting body 11 side and smaller in the surface layer 13 side. Further, the photoconductive layer 12 is formed by varying the forming rate of the deposition film in a manner that the rate is fast in the supporting body 11 side and late in the surface layer 13 side. The surface layer 13 contains silicon, carbon, hydrogen, halogen, oxygen and nitrogen atoms at one time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a photoreceptive member for electrophotography in which a photoreceptive layer having a silicon atom as a matrix is formed on a conductive substrate. The electrophotographic light-receiving member formed by the present invention can be widely used in electrophotographic technology application fields such as electrophotographic copying machines, laser beam printers, LED printers, liquid crystal printers, and laser plate making machines.

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity and
High SN ratio [photocurrent (Ip) / dark current (Id)], having an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave irradiated, having fast photoresponsiveness and having a desired dark resistance value, during use Be harmless to the human body at
And other characteristics are required. Particularly, in the case of an electrophotographic light receiving member incorporated in an electrophotographic apparatus used as an office machine in an office, the pollution-free property at the time of use is an important point.

Based on this point of view, amorphous silicon (hereinafter referred to as “A
-Si "), for example, German published patent No.
No. 2746967, No. 2855718 and the like describe application as a light receiving member for electrophotography.

FIG. 3 is a sectional view schematically showing the layer structure of a conventional electrophotographic light-receiving member 20, wherein 21 is a conductive support and 22 is a light-receiving layer made of A-Si. Such a light-receiving member for electrophotography is generally a method in which the conductive support 21 is heated to 50 to 400 ° C., a vacuum deposition method is performed on the support,
Sputtering method, ion plating method, thermal CVD
A by a film forming method such as
The light-receiving layer 22 made of -Si is produced. Among them, the plasma CVD method, that is, the method of decomposing the source gas by direct current or high frequency or microwave glow discharge to form the A-Si deposited film on the support is put to practical use as a suitable one.

In Japanese Patent Laid-Open No. 56-83746, a conductive support and A-Si containing a halogen atom as a constituent element are disclosed.
An electrophotographic light-receiving member comprising a photoconductive layer has been proposed. In this publication, a halogen atom is added to A-Si in an amount of 1 to 4
By containing 0 atomic%, it is possible to compensate for dangling bonds, reduce the localized level density in the energy gap, and obtain electrical and optical characteristics suitable as a light receiving layer of a light receiving member for electrophotography. It is supposed to be possible.

On the other hand, amorphous silicon carbide (hereinafter,
"A-SiC") has high heat resistance and surface hardness, has a high dark resistivity as compared with A-Si, and has an optical band gap of 1. depending on the carbon content.
It is known that it can be changed over the range of 6 to 2.8 eV. An electrophotographic light-receiving member having a photoconductive layer made of such A-SiC is proposed in JP-A-54-145540. In this publication, by using A-Si containing 0.1 to 30 atomic% of carbon as a chemical modifier as a photoconductive layer of a photoreceptive member for electrophotography, a high dark resistance and excellent photosensitivity are obtained. It is disclosed to exhibit photographic properties.

Further, in Japanese Patent Publication No. 63-35026, A-Si (hereinafter referred to as A-S) containing carbon atoms, hydrogen atoms and / or fluorine atoms as constituent elements on a conductive support.
An electrophotographic photoreceptor having an intermediate layer (denoted as iC (H, F)) and an A-Si photoconductive layer has been proposed, and A-SiC containing at least a hydrogen atom and / or a fluorine atom.
It is said that the (H, F) intermediate layer can reduce cracks and peeling of the A-Si photoconductive layer without impairing the photoconductive property.

[0008]

However, a conventional electrophotographic light-receiving member having a photoconductive layer formed of an A-Si material has a low electrical resistance such as dark resistance, photosensitivity, and photoresponsiveness. In terms of optical characteristics, photoconductive characteristics, and use environment characteristics, as well as stability over time and durability, individual characteristics have been improved, but in order to improve overall characteristics, The reality is that there is room for further improvement.

In recent years, in particular, electrophotographic apparatuses are desired to have higher image quality, higher speed and higher durability. As a result, in the electrophotographic light-receiving member, it is required to further improve the electrical characteristics and the photoconductive characteristics, and at the same time, to significantly extend the durability performance in all environments while maintaining high charging ability and high sensitivity. ..

For example, when an A-Si material is applied to a light-receiving member for electrophotography, if it is attempted to achieve high sensitivity and high dark resistance at the same time, in the conventional case, the potential may remain during use. It is often observed. When this type of light receiving member is used for a long period of time, fatigue builds up due to repeated use, resulting in an afterimage, a so-called "ghost".
There were many inconveniences such as the occurrence of a phenomenon. Further, conventionally, it has been difficult to achieve both high chargeability and prevention of image deletion at a high level.

Further, when the A-Si material is applied to a light receiving member for electrophotography, a change in room temperature or a rise of a device for heating the light receiving member so as to stabilize the electrostatic latent image, or the like. Due to the variation in temperature control, the dark resistance changes because the temperature of the light receiving member changes, and as a result,
When copying images are obtained continuously, there is an inconvenience that unevenness in image density occurs between the images. Further, in the past, it was often observed that, when used for a long period of time, the above-mentioned unevenness in image density between images became more remarkable due to fatigue due to repeated use.

When the light-receiving layer is made of an A-Si material, a hydrogen atom (H), a fluorine atom (F) or a chlorine atom is used in order to improve its electrical and photoconductive properties. (Cl) and other halogen atoms (X), boron atoms (B) and phosphorus atoms (P) for controlling the electric conductivity type, or other atoms for improving other characteristics. It is contained as atoms in the photoconductive layer, but depending on how these constituent atoms are contained, problems may occur in the electrical or photoconductive properties of the formed layer or in its uniformity. That is, if there is a non-uniform portion in the charge transport ability of the photoconductive layer, uneven image density occurs, which is particularly noticeable in a halftone image, so that there is a high degree of structural, electrical, and optical film quality. Uniform uniformity is required. Further, in recent years, electrophotographic copying machines are desired to have higher image quality and higher functions, and therefore it is also indispensable to faithfully reproduce originals including halftone such as photographs. Therefore, the electrophotographic photosensitive member is particularly desired to reduce unevenness in halftone. 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.

Further, as a result of improvement of an optical exposure system, a developing device, a transfer device and the like in the electrophotographic apparatus in order to improve the image characteristics of the electrophotographic apparatus, even in the light receiving member for electrophotography, an image higher than the conventional image can be obtained. It has become necessary to improve the characteristics. In particular, as a result of improving the resolution of the image, nonuniformity in a fine area of image density commonly called "Gasaki" is reduced, and black spot or white spot image defects commonly called "Pochi" are reduced. In particular, there has been a demand for a reduction in the "pochi" of a minute size, which has not been regarded as a problem in the past.

[0014] Especially regarding "potty", most of the causes are abnormal growth of a film called spherical projection, and it is important to reduce the number of occurrence. In addition, when a large number of images are continuously formed, a phenomenon in which “pochi” increases from the initial image may be seen, and the increase in “pochi” due to such long-term use may be reduced. It has been demanded. One of the reasons for this is that by continuously forming images, some of the paper dust on the transfer paper accumulates on the charging wire of the separation charger and induces abnormal discharge, causing a part of the light-receiving member to undergo dielectric breakdown. It is caused by being done. The so-called "leak point" can be mentioned. Furthermore, the presence of abnormal growth on the surface of the light-receiving member damages the cleaning blade during repeated image formation, resulting in poor cleaning, resulting in poor image quality. Due to the scattering of the residual toner, the toner is accumulated on the charging wire of the separation charging device to easily induce abnormal discharge, which also causes "leak spots". Furthermore, the fact that the relatively large abnormal growth portion is missing due to the light receiving member rubbing against the transfer paper or the cleaning blade also causes an increase in “potency”. As described above, in order to reduce the "potency" caused by several causes, it has become necessary to improve the material properties of the electrophotographic light-receiving member and take "potty" measures including the manufacturing process. ..

Further, due to the inherently high durability characteristic of the amorphous silicon photoconductor, the photoconductor is not regarded as a consumable item but is regarded as a part of parts of the copying machine, and there is a possibility that the photoconductor is free from maintenance such as replacement of the photoconductor. 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 electrophotographic light-receiving members are required to have high electrical properties and photoconductive properties. It is hoped that the durability will be further extended while maintaining.

Further, in recent years, in order to reduce the manufacturing cost of the electrophotographic light-receiving member, for example, the electrophotographic light is increased in a state where the deposition rate is increased by a deposition film forming method such as a microwave plasma CVD method described later. When the photoconductive layer of the receiving member is formed, there is a problem that the film quality becomes non-uniform, and the stress inside the film causes minute cracks and peeling of the A-Si film to reduce the yield in productivity. ..

Therefore, while the characteristics of the A-Si material itself are improved, the layer constitution and the chemical composition of each layer are solved so as to solve the above problems when designing the electrophotographic light-receiving member. , And it is necessary to improve from a comprehensive point of view including the manufacturing process of the electrophotographic light-receiving member.

The present invention has been made in view of the above points, and has various problems in the light receiving member for electrophotography having the conventional light receiving layer composed of the material having the silicon atom as the base as described above. The purpose is to resolve. That is, the main purpose of the present invention is electrical, optical,
The photoconductive properties are practically always stable with almost no dependence on the operating environment, have excellent light fatigue resistance, do not cause deterioration phenomena during repeated use, and have no image defects or changes in image deletion during long-term use. , High concentration, extremely excellent durability and moisture resistance, and almost no residual potential observed, providing a photoreceptive member for electrophotography having a photoreceptive layer composed of a material having a silicon atom as a base material with high yield. To do.

Another object of the present invention is to provide a uniform and high layer quality silicon atom as a base material, which is excellent in adhesion between layers provided on the support and between the support and between layers of the laminated layers. Another object of the present invention is to provide a photoreceptive member for electrophotography, which has a photoreceptive layer composed of the above material.

Still another object of the present invention is that, when it is applied as a light receiving member for electrophotography, it has a sufficient charge holding ability at the time of charging treatment for electrostatic image formation and produces a clear halftone. In addition, a photoreceptive layer made of a material having a silicon atom as a base material, which has excellent electrophotographic characteristics and can be effectively applied to ordinary electrophotography, capable of easily obtaining high-quality images with high resolution. Another object of the present invention is to provide an electrophotographic light-receiving member having the following.

[0021]

The method for forming a light-receiving member for electrophotography according to the present invention comprises forming a photoconductive layer and a surface layer on a conductive support in order to form a light-receiving member for electrophotography. In the method, the photoconductive layer has a silicon atom as a base material, contains at least carbon atoms and hydrogen atoms over the entire layer, and distributes the carbon atoms nonuniformly in the layer thickness direction, and the content thereof is the conductivity. It is composed of a non-single-crystal material in which the carbon atoms are distributed so that the number of carbon atoms is large on the support side and small on the surface layer side, and the surface layer has a silicon atom as a base and also has carbon atoms, hydrogen atoms, and halogen atoms. ,
It is composed of a non-single-crystal material containing oxygen atoms and nitrogen atoms at the same time, and changes the deposition film formation rate of the photoconductive layer in the layer thickness direction so that it becomes faster on the side of the conductive support and slower on the side of the surface layer. Thus, the photoconductive layer is formed.

In the present invention, the photoconductive layer comprises a photoconductive layer second region formed on the conductive support side and a photoconductive layer first region formed on the surface layer side. The layer second region contains at least carbon atoms and hydrogen atoms over the entire layer, the carbon atoms are unevenly distributed in the layer thickness direction, and the content is large on the side of the conductive support,
A non-single crystal composed of a non-single-crystal material in which the carbon atoms are distributed so as to be reduced on the photoconductive layer first region side, and the photoconductive layer first region contains 1 to 40 atomic% of hydrogen atoms. It is also characterized by being composed of materials.

The following are examples of embodiments of the present invention.

1. Formation of a deposited film on the surface of the photoconductive layer (or photoconductive layer second region, the same applies hereinafter) on the surface layer (photoconductive layer first region in the case of photoconductive layer second region, the same applies below) side The rate may be 30 to 90% with respect to the rate of the deposited film formation on the surface on the conductive support side or in the vicinity of the surface.

2. The content of the carbon atoms in the photoconductive layer is 0.5 to 5 on the surface of the conductive support side or in the vicinity of the surface.
0 atomic%, substantially 0% on the surface of the surface layer side or near the surface, the content of the hydrogen atoms in the photoconductive layer is 1
It may be up to 40 atom%.

3. The photoconductive layer may contain fluorine atoms.

4. The fluorine atoms in the photoconductive layer may be non-uniformly distributed in the layer thickness direction.

5. The photoconductive layer may further contain oxygen atoms at the same time.

6. The oxygen atoms in the photoconductive layer may be non-uniformly distributed in the layer thickness direction.

7. In the surface layer, the sum of the contents of carbon atoms, oxygen atoms and nitrogen atoms in the surface layer is 40 to 90 atom% with respect to the sum of the contents of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. The halogen atom content may be 20 atomic% or less, and the sum of the hydrogen atom content and the halogen atom content may be 30 to 70 atomic%.

8. The surface layer may be formed so that the sum of the contents of the oxygen atom and the nitrogen atom in the surface layer is 10 atom% or less.

9. When the photoconductive layer is composed of two regions, the photoconductive layer second region and the photoconductive layer first region, the film thickness of the photoconductive layer first region may be 0.5 to 15 μm.

[0033]

In the present invention, the photoconductive layer is formed in such a manner that the distribution of carbon atoms continuously changes from the side of the conductive support in the layer thickness direction, whereby charges (photocarriers) are formed.
It is possible to smoothly connect the generation of electric charges and the transportation of the generated electric charges, which is an important function for the electrophotographic light-receiving member. 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 member, and contributes to improvement of photosensitivity and reduction of residual potential. Further, in particular, when the photoconductive layer is composed of the above-mentioned two regions, by providing the photoconductive layer first region containing no carbon atom on the surface layer side, the absorption rate of long-wavelength light is improved and further light absorption is improved. An improvement in sensitivity can be achieved.

Further, since the photoconductive layer contains carbon atoms, the dielectric constant of the photoreceptive layer can be reduced, so that the capacitance per layer thickness can be reduced and a high charging ability can be realized. However, the photosensitivity is remarkably improved, and the withstand voltage against a high voltage is also improved.

By disposing a layer containing a large amount of carbon on the side of the support, the injection of charges from the support can be prevented, so that the charging ability is improved and the adhesion between the support and the photoconductive layer is improved. Therefore, peeling of the film and generation of minute defects can be suppressed.

Further, in the present invention, the content of carbon atoms in the photoconductive layer changes in the layer thickness direction by increasing the deposition film formation rate of the photoconductive layer on the support side and slowing it on the surface layer side. The stress in the deposited film caused by the above is effectively relieved, and the denseness of the deposited film is improved by the synergistic effect of the change in the deposition film formation rate and the change in the carbon content, so that the uniformity of the deposited film is improved. And the defects in the deposited film are reduced. As a result, in particular, image defects such as uneven halftone can be improved, and injection of charges from the surface layer side can be blocked more effectively, and higher charging ability can be obtained. Furthermore, peeling of the deposited film and generation of minute defects can be significantly suppressed.

The effect is that the deposition film forming rate on the surface on the surface layer side or near the surface is 30 to 90 with respect to the deposition film forming rate on the surface on the conductive support side or in the vicinity of the surface.
It becomes more prominent when set to%.

Further, in the present invention, it is effective that the photoconductive layer contains a fluorine atom. Fluorine atoms have the effect of suppressing the aggregation of carbon atoms and hydrogen atoms contained in the photoconductive layer, and reducing the localized level density in the band gap,
Ghost and halftone unevenness are further improved.

Further, in the present invention, it is also effective that at least the fluorine atoms contained in the photoconductive layer are nonuniformly distributed in the layer thickness direction. By unevenly distributing fluorine atoms in the layer thickness direction, in order to further alleviate the change in internal stress on the support side and the surface layer side that occurs as the content of carbon atoms changes 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 environment in which the light receiving member is used, and it is possible to improve the charging ability and the image density unevenness between copy images. ..

Further, in the present invention, it is possible to further contain oxygen atoms in the photoconductive layer. In this case, the stress of the deposited film can be more effectively relieved by the synergistic effect with the fluorine atoms. Suppresses structural defects in the film. Therefore, the potential shift which is a problem in the A-SiC based photoconductive layer is improved.

In addition, in the present invention, at least the oxygen atoms contained in the photoconductive layer are non-uniformly distributed in the layer thickness direction, whereby the stress of the deposited film can be alleviated more effectively, It is possible to significantly improve the structural defect of. Therefore, since deterioration of the photoconductive layer due to continuous use for a long period of time is suppressed, electrophotographic properties such as sensitivity, residual potential, and potential shift after long-term use can be significantly improved.

According to the present invention, high chargeability, high sensitivity, low residual potential, ghost, rustling, and image density unevenness between copy images are maintained, and durability is dramatically improved while maintaining excellent electrical characteristics. An improved electrophotographic light-receiving member can be obtained, and the yield in productivity can be greatly improved.

The effects as described above are obtained by, for example, the microwave C.
This is particularly noticeable when a layer is formed by increasing the deposition rate as in the VD method.

Further, in the present invention, by containing carbon atoms, oxygen atoms and nitrogen atoms at the same time in the surface layer, it is possible to obtain a dense and high mechanical strength film which conventional surface layers do not have. When the content of halogen atoms is 20 atom% or less, the water repellency of the surface of the photoreceptor is increased, so that the moisture resistance is improved, and image deletion is less likely to occur even in an environment of high temperature and high humidity. Furthermore, since the film quality becomes dense, it is possible to effectively prevent the injection of electric charges from the surface when subjected to a charging treatment, and to improve the charging ability, operating environment characteristics,
It is possible to improve durability and electrical pressure resistance. Further, since the absorption of light in the surface layer is reduced, the sensitivity can be improved. 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 maintained at a high level.

The light receiving member for electrophotography according to the present invention will be described in detail below with reference to the drawings with reference to specific examples.

FIGS. 1 and 2 are schematic views schematically showing a preferred layer structure of the electrophotographic light-receiving member of the present invention. An electrophotographic light-receiving member 10 shown in FIG. 1 has a layer structure composed of a photoconductive layer 12 and a surface layer 13 on a conductive support 11 for an electrophotographic light-receiving member, and has a free surface. 14 is provided. Further, FIG. 2 shows an example in which the photoconductive layer 12 in FIG. 1 is composed of a photoconductive layer second region 15 and a photoconductive layer first region 16.

Conductive support 1 used in the present invention
1 is, for example, Al, Cr, Mo, Au, In,
Examples thereof include metals such as Nb, Te, 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 at least a photoconductive layer forming side of an electrically insulating support such as glass or ceramics. It is also possible to use a support whose surface has been subjected to a conductive treatment. When an electrically insulating support is used, it is more preferable to subject the surface opposite to the side on which the photoconductive layer is formed to a conductive treatment.

The electroconductive support 11 may be in the form of a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness thereof forms the electrophotographic light-receiving member 10 as desired. When the flexibility of the electrophotographic light-receiving member 10 is required, the thickness thereof should be as thin as possible within a range where the function of the conductive support 11 can be sufficiently exerted. You can However, it is usually required to be 10 μm or more in terms of manufacturing and handling of the conductive support 11, or from the viewpoint of mechanical strength.

In particular, when image recording is performed using coherent light such as laser light, the surface of the conductive support 11 is used for the purpose of eliminating image defects due to so-called interference fringe patterns that appear in visible images. You may provide unevenness in. Such irregularities are disclosed in JP-A-60-168156 and 60-178457.
It is formed by the known method described in Japanese Patent Publication No. 60-225854. As another method of eliminating the image defect due to the interference fringe pattern, the surface of the conductive support 11 may be provided with a concavo-convex shape formed by a plurality of spherical trace depressions.
That is, the surface of the conductive support 11 is provided with irregularities due to the spherical trace depressions that are smaller than the resolution required for the electrophotographic light-receiving member. Such unevenness can be formed by the method described in JP-A-61-231561.

Photoconductive layer 12 in the present invention (photoconductive layer second region 15 when composed of two regions, and so on)
Is composed of a non-single-crystal material containing silicon atoms as a base material and containing carbon atoms and hydrogen atoms, and has desired photoconductive characteristics, in particular, charge retention characteristics, charge generation characteristics, and charge transport characteristics.

The carbon atoms contained in the photoconductive layer 12 form a distribution, and the distribution is nonuniform in the thickness direction of the layer, and the carbon atoms are contained on the conductive support 11 side at each point in the film thickness direction. The ratio is high, and the distribution is such that it becomes lower as the distance from the conductive support decreases. When the content of carbon atoms is less than 0.5 atom% on the surface on the side where the conductive support 11 is provided or near the surface, if the content is less than 0.5 atom%, the adhesion with the conductive support 11 is improved and charge injection is prevented. The function deteriorates, and the effect of improving the charging ability due to the decrease in electrostatic capacity disappears. Also
If it exceeds 50 atomic%, a residual potential will be generated. Therefore, practically 0 .. It is 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 12 to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, in particular, photoconductivity and charge retention characteristics. This is because it is essential for improvement. In particular, since the inclusion of carbon atoms requires more hydrogen atoms to maintain the film quality, it is desirable to adjust the amount of hydrogen atoms contained according to the carbon content. Therefore, the content of hydrogen atoms on the surface of the conductive support 11 side or in the vicinity of the surface is preferably 1 to 40 atom%, more preferably 5 to 35 atom%, and optimally 10 to 30 atom%.

In the present invention, the deposition film formation rate of the photoconductive layer 12 is changed in the layer thickness direction so that it is faster on the side of the conductive support 11 and slower on the side of the surface layer 13 so that the stress on the deposited film is further reduced. It is possible to alleviate more effectively, improve the denseness of the deposited film, further improve the image characteristics such as halftone unevenness, and significantly suppress the peeling of the deposited film and the occurrence of minute defects. it can. Furthermore, electric characteristics such as charging ability can be further improved.

In addition, this effect is obtained by controlling the deposition film formation rate on the surface on the surface layer 13 side or in the vicinity of the surface by the conductive support 1.
30 to the deposition rate at the surface on the 1st side or near the surface
It becomes more prominent at 90%. When it is lower than 30%, the stress of the deposited film is not sufficiently relaxed, and the effect of suppressing the peeling of the deposited film and defects is insufficient, and
If it exceeds 90%, the densification of the deposited film and the relaxation of the stress of the deposited film are not sufficient, and the image characteristics such as uneven halftone and the electrical characteristics such as charging ability are not sufficiently improved.

Further, it is effective that the photoconductive layer 12 of the present invention contains a fluorine atom. Fluorine atom is the photoconductive layer 12
Suppresses the aggregation of carbon atoms and hydrogen atoms contained in,
It has an effect of reducing the localized level density in the band gap, and further improves ghost and uneven halftone. If the content of fluorine atoms in the photoconductive layer 12 is less than 1 atomic ppm, the effect of improving the ghost and halftone unevenness due to the fluorine atoms will not be sufficiently exerted, and if it exceeds 95 atomic ppm, the film quality will be deteriorated. The ghost phenomenon comes to occur. Therefore, it is desirable that the content of fluorine atoms is practically 1 to 95 atomic ppm, more preferably 3 to 80 atomic ppm, and most preferably 5 to 50 atomic ppm.

In particular, when the photoconductive layer 12 contains carbon atoms within the above range, the content of fluorine atoms is set within the above range, whereby the photoconductive characteristics, image characteristics and durability are remarkably improved. It was confirmed to do.

Further, in the present invention, it is effective that at least fluorine atoms contained in the photoconductive layer 12 are nonuniformly distributed in the layer thickness direction. By unevenly distributing fluorine atoms in the layer thickness direction, changes in internal stress on the side of the conductive support 11 and the surface layer 13 caused by changes in the content of carbon atoms in the layer thickness direction can be relaxed. Therefore, 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 electrophotographic light-receiving member 10 change according to the temperature change of the use environment, and it is possible to improve the charging ability and the image density unevenness between copy images. ..

In the present invention, the photoconductive layer 1 is also used.
It is also possible to contain oxygen atoms in 2, and in this case, the synergistic effect with fluorine atoms more effectively relieves the stress of the deposited film and suppresses structural defects of the film. Therefore, the potential shift which is a problem in the A-SiC based photoconductive layer is improved.

The oxygen atom content in the photoconductive layer is 10 atom pp.
When it is less than m, it is not possible to sufficiently improve the adhesion of the film and suppress the occurrence of abnormal growth, and the potential shift becomes large. If it exceeds 5000 atomic ppm, the electrical characteristics will not be sufficient to support the speeding up of electrophotography.
Therefore, the content of oxygen atoms is 10 to 5000 atomic ppm
Is preferred.

Further, in the present invention, at least the oxygen atoms contained in the photoconductive layer 12 are non-uniformly distributed in the layer thickness direction, whereby the stress of the deposited film can be alleviated more effectively, It is possible to significantly suppress structural defects in the film. Therefore, deterioration of the photoconductive layer due to long-term use is suppressed, and electrophotographic properties such as sensitivity, residual potential, and potential shift after long-term use can be significantly improved.

In the present invention, the photoconductive layer 12 is produced 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, for example, glow discharge method (AC discharge CVD such as low frequency CVD method, high frequency CVD method or microwave CVD method)
Method, or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method
And various thin film deposition methods such as thermal CVD. These thin film deposition methods have desired characteristics, although they are appropriately selected depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and characteristics required for the electrophotographic light-receiving member to be manufactured. The glow discharge method, the sputtering method, and the ion plating method are preferable because the control of the conditions for manufacturing the electrophotographic light-receiving member is relatively easy. Then, these methods may be used together in the same apparatus system to perform thin film deposition. For example, in order to form a photoconductive layer of A-SiC (H) by the glow discharge method, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a carbon atom (C) are supplied. A raw material gas for C supply capable of supplying hydrogen and a raw material gas for H supply capable of supplying hydrogen atoms (H) are introduced in a desired gas state into a reaction vessel capable of reducing the pressure inside, and then introduced into the reaction vessel. A glow discharge is caused to occur, and a layer made of A-SiC (H) may be formed on the surface of a predetermined conductive support which is installed in a predetermined position in advance.

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
Silicon hydrides (silanes) in a gas state such as ₈ , Si ₄ H ₁₀ or the like that can be gasified are mentioned as being effectively used. Above all, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. The H ₂ depending on the raw material gas for these Si supply need, He, Ar, may be used as diluted with a gas Ne or the like.

In the present invention, as the raw material for introducing carbon atoms, it is desirable to adopt a gaseous substance at room temperature and atmospheric pressure, or at least a substance that can be easily gasified under the layer forming conditions.

The raw material for introducing carbon atoms (C) includes C and H as constituent atoms, for example, saturated hydrocarbon having 1 to 5 carbon atoms, ethylene hydrocarbon having 2 to 4 carbon atoms, and 2 carbon atoms. ~ 3 acetylene hydrocarbons and the like. Specifically, the saturated hydrocarbon is methane, ethane, propane, n-butane, pentane and the like, and the ethylene hydrocarbon is ethylene, propylene, 1-butene, 2
Examples of butene, isobutylene, pentene and acetylene hydrocarbons include acetylene, methylacetylene and butyne.

Further, as the source gas containing Si and C as constituent atoms, alkyl silicide such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be cited.

In addition to this, in addition to the introduction of carbon atoms (C), it is also possible to introduce fluorine atoms, so that CF ₄ , C ₂
Fluorocarbon compounds such as F ₆ , C ₃ F ₈ and C ₄ F ₁₀ , CHF ₃
Fluorine-substituted hydrocarbons such as

In order to structurally introduce hydrogen atoms (H) into the photoconductive layer 12, in addition to the above, H ₂ or SiH ₄ ,
Si hydrides such as Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ , and S
It can also be carried out by causing silicon or a silicon compound for supplying i to coexist in the reaction vessel to cause discharge.

Effective as the fluorine supply gas used in the present invention is, for example, a gaseous or gasifiable fluorine compound such as fluorine gas, a fluoride, an interhalogen compound containing fluorine, a silane derivative substituted with fluorine, or the like. Are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a fluorine atom, which contains silicon atoms and fluorine atoms as constituent elements, can be cited as an effective one. Specific examples of the fluorine compound that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF and Cl.
Interhalogen compounds such as F, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned.

As a silicon compound containing a fluorine atom, a so-called silane derivative substituted with a fluorine atom, specifically,
Silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be mentioned as preferable ones. When such a silicon compound containing a fluorine atom is used to form the characteristic electrophotographic light-receiving member of the present invention by glow discharge or the like, a silicon hydride gas as a Si supply gas is not used. However, nc-SiC containing a fluorine atom is provided on the predetermined conductive support 11.
The photoconductive layer 12 composed of (H, F) can be formed, but in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the photoconductive layer 12 to be formed, these gases are used. Further, it is preferable to form a layer by mixing a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms. 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 silicon compounds containing fluorine are effectively used as the fluorine atom supplying gas.
Fluorine-substituted silicon hydrides such as HF, SiH ₃ F, SiH ₂ F ₂ and SiHF _{3, and the} like in a gas state or a gasifiable substance can also be mentioned as effective raw material for forming the photoconductive layer. Among these substances, the fluorinated compounds containing hydrogen atoms are introduced with hydrogen atoms, which are extremely effective for controlling electrical or photoelectrical 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 fluorine atom supply gas.

In the present invention, the starting material effectively used as a gas for introducing oxygen atoms (O) is
For example, oxygen, ozone, nitric oxide, nitrogen dioxide, nitrogen monoxide, nitrogen trioxide, nitrogen trioxide, nitrogen pentaoxide, etc. can be mentioned.

In addition to the above, in addition to the introduction of carbon atom (C), the introduction of oxygen atom (O) is also possible.
O, CO _2, etc. can be mentioned.

In order to control the amount of hydrogen atoms and / or fluorine atoms contained in the photoconductive layer 12, for example, the temperature of the conductive support 11 and the raw material used for containing hydrogen atoms or fluorine atoms are used. It is sufficient to control the introduction amount into the reaction container, the discharge power, and the like. Further, in the present invention, it is preferable that the photoconductive layer 12 contains an atom (M) that controls conductivity, if necessary. Atoms (M) for controlling conductivity may be contained in the photoconductive layer 12 in a uniformly distributed state, or may be contained in a nonuniformly distributed state in the layer thickness direction. May be.

Examples of the atom (M) for controlling the conductivity include so-called impurities in the field of semiconductors, which are elements belonging to Group 3B of the periodic table (hereinafter referred to as “Group 3B”) that give p-type conductivity. Or an element belonging to Group 5B of the periodic table (hereinafter abbreviated as “Group 5B element”) that gives n-type conductivity.
As the Group 3B element, specifically, B, Al, Ga,
There are In, Tl, etc., and B, Al, Ga are particularly preferable. As the Group 5B element, specifically, P, As, S
b, Bi and the like, and P and As are particularly preferable.

The content of atoms (M) controlling the conductivity contained in the photoconductive layer 12 is preferably 1 × 10 ^−3.
~ 5 x 10 ⁴ atomic ppm, more preferably 1 x 10 ^-2 to 1 x
10 ⁴ atom ppm, optimally 1 × 10 ^{-1 to} 5 × 10 ³ atom ppm
Is desirable. In particular, when the content of carbon atoms (C) in the photoconductive layer 12 is 1 × 10 ³ atomic ppm or less, the content of atoms (M) contained in the photoconductive layer 12 is preferably 1 × 10 ^−3. desirable to the to 1 × 10 ³ atomic ppm, the content of the case where the carbon atom content exceeds 1 × 10 ³ atom ppm, atom (M), preferably 1 × 10
^{-1 to} 5 × 10 ⁴ atomic ppm is preferable.

Atoms for controlling conductivity in the photoconductive layer 12,
For example, in order to structurally introduce a Group 3B element or a Group 5B element, a reaction vessel in a gas state of a raw material for introducing a Group 3B element or a raw material for introducing a Group 5B element during layer formation It may be introduced together with another gas for forming the photoconductive layer 12. As a raw material for introducing a Group 3B element or a raw material for introducing a Group 5B element, a gaseous substance at room temperature and atmospheric pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. Is desirable.

As the raw material for introducing the Group 3B element,
Specifically, for example, for introducing a boron atom, B
₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ ,
Examples thereof include borohydrides such as B ₆ H ₁₄ and borohalides such as BF ₃ , BCl ₃ and BBr ₃ . Other raw materials for introducing the Group 3B element include AlCl ₃ and GaC.
Examples include l ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like.

As the raw material for introducing the Group 5B element, those effectively used in the present invention include phosphorus hydrides such as PH ₃ and P ₂ H ₄ and PH ₄ for introducing phosphorus atoms.
I, PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PB
Examples thereof include phosphorus halides such as r ₅ and PI ₃ . As other raw materials for introducing a Group 5B element, AsH ₃ , As
_{F 3, AsCl 3, AsBr 3} , AsF 5, SbH 3, Sb
F ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , Bi
Examples thereof include Cl ₃ and BiBr ₃ .

The atom (M) that controls the conductivity of these
Raw materials for introduction are H ₂ , He, A
You may dilute with gas, such as r and Ne, and may use it.

Further, in the present invention, the photoconductive layer 12 contains at least one element selected from Group 1A, Group 2A, Group 6A, and Group 8 of the periodic table in an amount of 0.1 to 10000 ppm. Good. The element may be evenly distributed in the photoconductive layer 12, or may be uniformly distributed in the photoconductive layer 12, but may be unevenly distributed in the layer thickness direction. There is no problem even if there is a portion containing it in the state of being.

As the Group 1A element, specifically, Li,
Na and K can be mentioned, and as the Group 2A element,
Be, Mg, Ca, Sr, Ba can be mentioned.
Further, as the Group 6A element, Cr, Mo, W can be cited, and as the Group 8 element, Fe, Co, Ni, etc. can be cited.

In the present invention, the layer thickness of the photoconductive layer 12 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 5 to 50 μm.
It is more preferably 10 to 40 μm, and most preferably 15 to 30 μm.

A having properties capable of achieving the objects of the present invention
To form the photoconductive layer 12 made of —SiC (H),
It is necessary to appropriately set the surface temperature of the conductive support 11 and the gas pressure in the reaction vessel as desired.

The surface temperature (Ts) of the conductive support 11 is
The optimum range is appropriately selected according to the layer design, but in the usual case, 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 likewise appropriately selected according to the layer design, but in the usual case, it is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to} 3 Tor.
rr, optimally 1 × 10 ^-4 to 1 Torr.

In the present invention, the layer production factors include the numerical range of the surface temperature and the gas pressure of the conductive support 11 described above, but these factors are not usually independently determined separately. It is desirable to determine optimal values for these factors based on their mutual and organic relevance to form photoconductive layer 12 with the desired properties.

In the present invention, at least an aluminum atom is provided on the electroconductive support 11 side of the photoconductive layer 12.
It is desirable to have a layer region in which silicon atoms, carbon atoms and hydrogen atoms are contained in a non-uniform distribution state in the layer thickness direction.

In the present invention, the photoconductive layer 12 may be composed of two regions, a photoconductive layer second region 15 and a photoconductive layer first region 16. In that case, the photoconductive layer second region 15 has the same composition as the photoconductive layer 12 described above, and is formed on the conductive support 11 by the method described above. The photoconductive layer first region 16 is made of A-Si (H) containing silicon atoms and hydrogen atoms as a constituent element, and has desired photoconductive characteristics, particularly charge generation characteristics and charge transport characteristics.

The first region 16 of the photoconductive layer is a silicon atom,
It is a non-single crystalline material consisting of hydrogen atoms, with 1 to 40 hydrogen atoms.
It is formed by containing atomic%. This photoconductive layer first region 16
Is provided to efficiently generate photocarriers, enhance absorption of long-wavelength light, and improve sensitivity. Further, as another effect, since the traveling property of the carrier having the electric polarity opposite to the charging polarity is better than that of the second region 15 of the photoconductive layer, an unexpected effect that the ghost is reduced can be obtained.

The above-mentioned photoconductive layer 12 (photoconductive layer second region 1)
5) Similarly, the photoconductive layer first region 16 is also 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, for example, in order to form the A-Si (H) photoconductive layer first region 16 by a glow discharge method, basically, a raw material gas for supplying Si, which can supply silicon atoms (Si), can be used. And a raw material gas for supplying H capable of supplying hydrogen atoms (H) in a desired gas state in a reaction vessel capable of reducing the pressure inside thereof, to cause glow discharge in the reaction vessel, and predetermined The photoconductive layer second on the surface of a predetermined support installed at the position
A layer made of A-Si (H) may be formed on the region 15.

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
Silicon hydrides (silanes) in a gas state such as ₈ , Si ₄ H ₁₀ or the like that can be gasified are mentioned as being effectively used. Above all, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. The H ₂ depending on the raw material gas for these Si supply need, He, Ar, may be used as diluted with a gas Ne or the like.

In order to more easily control the introduction ratio of hydrogen atoms introduced into the photoconductive layer first region 16 to be formed, hydrogen gas or a silicon compound gas containing hydrogen atoms is added to these gases. Also, it is preferable to mix a desired amount 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 order to structurally introduce hydrogen atoms (H) into the first region 16 of the photoconductive layer, in addition to the above, H ₂ , or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si _{4 are used.} It can also be performed by causing silicon hydride such as H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the reaction vessel to cause discharge.

In order to control the amount of hydrogen atoms contained in the first region 16 of the photoconductive layer, for example, the temperature of the conductive support 11 and the inside of the reaction vessel of the raw material used for containing the hydrogen atoms are controlled. It is sufficient to control the amount of introduction into, the discharge power, and the like.

Further, in the present invention, the atom (M) for controlling the conductivity is also included in the first region 16 of the photoconductive layer, if necessary.
Is preferably contained. The conductivity-controlling atoms (M) may be contained in the photoconductive layer first region 16 in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. There is no problem even if there is a part that does.

The content of atoms (M) controlling the conductivity contained in the first region 16 of the photoconductive layer is preferably 1
× 10 ^{-3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ^-2 to 1 × 1
It is desirable that the concentration is 0 ⁴ atomic ppm, optimally 1 × 10 ^{-1 to} 5 × 10 ³ atomic ppm. To structurally introduce conductivity-controlling atoms into the photoconductive layer first region 16, the above-described photoconductive layer 12 is used.
The method described in the method of forming a sheet is used.

Further, the first region 16 of the photoconductive layer contains 0.1 to 10000 ppm of at least one element selected from Group 1A, Group 2A, Group 6A and Group 8 of the periodic table. May be. The element is the photoconductive layer first region 16
It may be evenly distributed in the inside, or may be contained evenly, but there may be a part in which it is contained in a state of being unevenly distributed in the layer thickness direction.

In the present invention, the layer thickness of the first region 16 of the photoconductive layer is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 0.
5-15 μm, more preferably 1-10 μm, optimally 1-5 μm
Is desirable.

A having characteristics capable of achieving the object of the present invention
In order to form the photoconductive layer first region 16 made of —Si (H), it is necessary to appropriately set the surface temperature of the conductive support 11 and the gas pressure in the reaction vessel as desired.

The surface temperature (Ts) of the conductive support 11 is
The optimum range is appropriately selected according to the layer design, but in the usual case, 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.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 1 × 10 ⁻⁵ to 10 Torr, more preferably 5 × 10 ^{−5 to} 3 Torr. T
Orr, optimally 1 × 10 ^-4 to 1 Torr is desirable.

In the present invention, the layer production factors include the numerical range of the surface temperature and the gas pressure of the conductive support 11 described above, but these factors are not usually independently determined separately. It is desirable to determine optimum values for these factors based on their mutual and organic relevance to form the photoconductive layer first region 16 having the desired characteristics.

In the electrophotographic light-receiving member 10 of the present invention, the photoconductive layer 12 is provided between the photoconductive layer 12 and the surface layer 13.
Is composed of two regions, the photoconductive layer first region 1
Between 6 and the surface layer 13, a layer region whose composition is continuously changed may be provided. By providing the layer region, the adhesion between the layers can be further improved.

The surface layer 13 in the present invention contains a silicon atom, a carbon atom, a nitrogen atom and an oxygen atom as constituent elements at the same time, and further contains a hydrogen atom and a halogen atom (hereinafter referred to as "nc- SiC, O, N
(Denoted as (H, X)).

The carbon atoms, oxygen atoms and nitrogen atoms contained in the surface layer 13 may be contained in the layer in a state of being uniformly distributed, or may be nonuniform in the layer thickness direction. It does not matter even if there is a portion that is contained in the state of being distributed in.

Carbon atoms, oxygen atoms and nitrogen atoms contained in the entire surface region of the surface layer 13 have effects of remarkably high dark resistance and high hardness when they are contained at the same time. The sum of the contents of carbon atoms, oxygen atoms and nitrogen atoms contained in the surface layer 13 is preferably 40 to 90 atom% with respect to the sum of the contents of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. , More preferably 45 to 85 atom%, most preferably 50 to
It is preferably set to 80 atom%. In order to further exert the effect of the present invention, the total content of oxygen atoms and nitrogen atoms is preferably 10 atom% or less.

The hydrogen atoms and halogen atoms contained in the surface layer 13 in the present invention are nc-SiC, O,
The dangling bonds existing in N (H, X) are compensated, the film quality is improved, and the carriers trapped at the interface between the photoconductive layer 12 and the surface layer 13 are reduced, so that the image deletion is improved. .. Further, since the halogen atom improves the water repellency of the surface layer 13, the high humidity flow due to the adsorption of water vapor is also reduced. The content of halogen atoms in the surface layer 13 is preferably 20 atom% or less, and the sum of the content of hydrogen atoms and halogen atoms is preferably 30 to 70 atom%, more preferably 35 to 65 atom. %, Most preferably 40 to 60 atomic%.

In the present invention, the starting materials that are effectively used as the gas for introducing oxygen atoms (O) are those that are gaseous at room temperature and atmospheric pressure or can be easily gasified under at least the layer forming conditions. It is desirable to be adopted.
For example, oxygen (O _2), ozone (O _3), and the like.

In the present invention, the starting material effectively used as a gas for introducing a nitrogen atom (N) is one which is gaseous at room temperature and atmospheric pressure or can be easily gasified under at least the layer forming conditions. It is desirable to be adopted.
For example, nitrogen (N _2), ammonia (NH _3), and the like.

Further, as a starting material capable of simultaneously introducing an oxygen atom and a nitrogen atom, nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂₎ O ₃ ), nitrogen trioxide (N ₃ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), and the like.

In addition to these, compounds such as CO and CO ₂ can also be mentioned as starting materials because oxygen atoms can be introduced in addition to carbon atoms.

Effective halogen-supplying gas used in the present invention is, for example, a gaseous or gasifiable fluorine compound such as a halogen gas, a halide, an interhalogen compound, and a silane derivative substituted with a halogen atom. Are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be cited as an effective one.

The halogen compound which can be preferably used in the present invention is specifically fluorine gas (F ₂ ), BrF,
Interhalogen compounds such as ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned.

As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom, specifically, silicon fluoride such as SiF ₄ and Si ₂ F ₆ can be mentioned as a preferable example. When such a silicon compound containing a halogen atom is adopted to form the characteristic electrophotographic light-receiving member of the present invention by glow discharge or the like, a silicon hydride gas as a Si supply gas is not used. However, nc-SiC, O, N containing a halogen atom
The surface layer 13 made of (H, X) can be formed, but in order to more easily control the introduction ratio of hydrogen atoms introduced into the formed surface layer 13, hydrogen is added to these gases. It is preferable to mix a gas or a gas of a silicon compound containing a hydrogen atom in a desired amount 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 halide or silicon compound containing halogen is effectively used as the gas for supplying halogen atoms, but in addition, HF, SiH ₃ F, SiH ₂ F ₂ , SiH
Halogen-substituted silicon hydride such as F _{3 and the} like, and substances in a gas state or capable of being gasified can also be mentioned as effective raw material for forming the surface layer. Among these substances, a halide containing a hydrogen atom is introduced at the same time as the introduction of the halogen atom into the layer during the formation of the surface layer, since a hydrogen atom extremely effective in controlling the electrical or photoelectric properties is also introduced, In the present invention, it is used as a suitable gas for supplying halogen atoms.

Further, in the present invention, the surface layer 13 also includes the above-mentioned groups 1A, 2A, 6A and 8A of the periodic table.
0.1-10000 pp of at least one element selected from the group
You may contain about m. These elements are included in the surface layer 1
3 may be evenly distributed evenly, or even if it is evenly contained, there may be a part that is unevenly distributed in the layer thickness direction. ..

As the substance that can be the gas for supplying Si and the raw material for introducing carbon atoms used in the present invention, the same substances as those mentioned above when forming the photoconductive layer can be used. In the present invention, the layer thickness of the surface layer 13 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, and most preferably. It is desirable that the thickness is 0.1 to 10 μm.

In the present invention, nc-SiC, O, N
To form the surface layer 13 composed of (H, X), a vacuum deposition method similar to the method of forming the photoconductive layer 12 described above is adopted.

In order to form the surface layer 13 having the characteristics capable of achieving the object of the present invention, the surface temperature of the conductive support 11 and the gas pressure in the reaction vessel are important factors that influence the characteristics of the surface layer. Is.

The surface temperature of the conductive support 11 is 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 Torr, more preferably 5 × 10 ^{−5 to} 3 Torr, most preferably 1 × 10 ⁻⁴ to 1 Torr is preferred.

In the present invention, the important factors for forming the surface layer 13 include the above-mentioned surface temperature of the conductive support 11 and the numerical ranges of gas pressure, but these factors are usually independently and separately. It is not determinable, but it is desirable to determine the optimum values of these factors on the basis of mutual and organic relationships to form the surface layer 13 having the desired properties.

The apparatus and method for forming the deposited film by the high frequency plasma CVD method and the microwave plasma CVD method will be described in detail below.

FIG. 4 shows high frequency plasma CVD (hereinafter referred to as "RF
It is a schematic block diagram which shows an example of the manufacturing apparatus of the photoreceptor member for electrophotography by the method (it describes with -PCVD). The configuration of the device is as follows.

The apparatus is roughly classified into a deposition apparatus 4100,
It comprises a source gas supply device 4200 and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 4111. A conductive cylindrical support 4112 and a heater 411 for heating the support are provided in the reaction vessel 4111 in the deposition apparatus 4100.
3. The source gas introduction pipe 4114 is installed, and the high frequency matching box 4115 is further connected.

The source gas supply device 4200 is composed of SiH ₄ ,
Cylinders 4221-4226 of raw material gases such as H ₂ , CH ₄ , NO, NH ₃ , SiF ₄ and valves 4231-4236, 4
241 to 4246, 4251 to 4256 and mass flow controllers 4211 to 4216, and a cylinder of each source gas is a reaction vessel 41 via a valve 4260.
11 is connected to the gas introduction pipe 4114.

The deposited film can be formed using the apparatus, for example, as follows.

First, a cylindrical support 4112 is installed in the reaction container 4111, and the reaction container 4111 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the cylindrical support 411 is heated by the heater 4113 for heating the support.
The temperature of 2 is controlled to a predetermined temperature of 20 to 500 ° C.

A source gas for forming a deposited film is supplied to the reaction vessel 411.
The gas cylinder valve 4231-
4236, make sure that the leak valve 4117 of the reaction vessel is closed, and check the inflow valves 4241-42.
46, outflow valves 4251 to 4256, auxiliary valve 42
After confirming that 60 is open, first open the main valve 4118 to open the reaction vessel 4111 and the gas pipe 41.
Evacuate 16.

Next, the vacuum gauge 4119 reads about 5 × 10 ^-5.
Auxiliary valve 4260, outflow valve 4 when Torr is reached
251 to 4256 are closed. Then, the gas cylinder 422
Each gas is introduced from 1 to 4226 by opening the valves 4231 to 4236, and each gas pressure is adjusted to ² Kg / cm ² by the pressure regulators 4261 to 4266. Next inflow valve 4
The valves 241 to 4246 are gradually opened to introduce the respective gases into the mass flow controllers 4211 to 4216.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 4112.

When the cylindrical support 4112 reaches a predetermined temperature, one of the outflow valves 4251 to 4256 connected to a desired gas cylinder, and the auxiliary valve 4
260 is gradually opened, and a desired gas is supplied from the gas cylinders 4221 to 4226 through the gas introduction pipe 4114 to the reaction vessel 4.
Introduced into 111. Next, mass flow controller 4
211-4216 are adjusted so that each source gas has a predetermined flow rate. At that time, the vacuum gauge 4119 is adjusted so that the pressure inside the reaction vessel 4111 becomes a predetermined pressure of 1 Torr or less.
The opening of the main valve 4118 is adjusted while watching. When the internal pressure is stable, the RF power source (not shown) is set to a predetermined power, and the RF power is introduced into the reaction vessel 4111 through the high frequency matching box 4115 to cause the RF glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 4112. After the desired film thickness is formed, the supply of RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a layer having a desired multi-layer structure is formed.

It goes without saying that all the outflow valves except for the necessary gas are closed when forming each layer. In addition, each gas is a reaction container 4111.
Inside, outflow valves 4251 to 4256 to reaction vessel 411
In order to avoid remaining in the pipe reaching 1, the outflow valves 4251 to 4256 are closed, the auxiliary valve 4260 is opened, the main valve 4118 is fully opened, and the system is temporarily evacuated to a high vacuum. To do.

In order to make the film formation uniform, the cylindrical support 4112 may be rotated at a predetermined speed by a driving device (not shown) during the film formation.

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

The heating method for the cylindrical support may be carried out by a heating element having a vacuum specification. Specific examples of the heating element having such a vacuum specification include a wound heater of a sheathed heater, a plate heater, Examples thereof include an electric resistance heating element such as a ceramic heater, a heat radiation lamp heating element such as a halogen lamp and an infrared lamp, and a heating element by a heat exchange means using a liquid, a gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a method such as providing a container dedicated to heating in addition to the reaction container 4111, heating the cylindrical support 4112, and then transporting the cylindrical support in the reaction container 4111 in a vacuum is used. ..

Next, a method for manufacturing the electrophotographic light-receiving member formed by the microwave plasma CVD (hereinafter referred to as “μW-PCVD”) method will be described.

FIGS. 5A and 5B are schematic structural views showing an example of a deposition apparatus 5100 for forming a deposition film for an electrophotographic light receiving member by the μW-PCVD method. ) Shows a side section, (b) shows a XX 'cross section. FIG. 6 is an explanatory diagram of the entire manufacturing apparatus of the electrophotographic light-receiving member by the μW-PCVD method.

By exchanging the deposition apparatus 5100 by the μW-PCVD method shown in FIG. 5 with the deposition apparatus 4100 shown in FIG. 4 and connecting it to the source gas supply apparatus 4200,
By the μW-PCVD method shown in FIG. 6, an electrophotographic light-receiving member manufacturing apparatus having the following configuration can be obtained.

The apparatus 5100 is composed of a reaction vessel 5111 having a vacuum airtight structure and capable of reducing the pressure, a source gas supply apparatus 5200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel. .. The reaction vessel 5111 efficiently transmits microwave power into the reaction vessel, and
A microwave power source (not shown) is passed through a microwave introduction window 5112, a stub tuner (not shown) and an isolator (not shown) formed of a material capable of maintaining vacuum airtightness (eg, quartz glass, alumina ceramics, etc.). ), A microwave waveguide 5113, a cylindrical support 5115 on which a deposited film is to be formed, a support heating heater 5116, a source gas introduction pipe 5117, and an external electric bias for controlling the plasma potential. An electrode 5118 for giving is provided, and the inside of the reaction vessel 5111 can be exhausted through an exhaust pipe 5121 by an exhaust device (not shown) (for example, a diffusion pump). The source gas supply device 4200 uses SiH ₄ , H ₂ , CH ₄ , and N.
Cylinders 4221-4 of raw material gas such as O, NH ₃ , SiF ₄
226 and valves 4231-4236, 4241-424
6, 4251 to 4256, mass flow controllers 4211 to 4216, and the like, and each source gas cylinder is connected to a gas introduction pipe 5117 in a reaction vessel 5111 via a valve 4260. In addition, the cylindrical support 5
The space surrounded by 115 forms a discharge space 5130.

The formation of the deposited film by the apparatus by the μW-PCVD method can be performed as follows.

First, a cylindrical support 5115 is installed in the reaction vessel 5111, the support 5115 is rotated by a support rotation motor 5120, and the inside of the reaction vessel 5111 is exhausted through an exhaust pipe 5121 by an exhaust device (not shown). Evacuate and adjust the pressure in the reaction vessel 5111 to 1 × 10 ⁻⁵ Torr or less. Then, the temperature of the cylindrical support 5115 is heated and maintained at a predetermined temperature of 20 to 500 ° C. by the support heating heater 5116.

A source gas for forming a deposited film is supplied to the reaction vessel 511.
1 for gas cylinder valves 4231-4
236, make sure that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valves 4241-42.
46, outflow valves 4251 to 4256, auxiliary valve 42
After confirming that 60 is open, first open the main valve (not shown) to open the reaction vessel 5111 and the gas pipe 51.
The inside of 22 is exhausted.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10 ^-5 T
Auxiliary valve 4260 and outflow valve 4 when orr is reached
251 to 4256 are closed. Then, the gas cylinder 422
Each gas is introduced from 1 to 4226 by opening the valves 4231 to 4236, and each gas pressure is adjusted to ² Kg / cm ² by the pressure regulators 4261 to 4266. Then the inflow valve 4241
~ 4246 is gradually opened to introduce each gas into the mass flow controllers 4211-4216.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 5115.

When the cylindrical support 5115 reaches a predetermined temperature, one of the outflow valves 4251 to 4256 connected to a desired gas cylinder, and the auxiliary valve 4
260 is gradually opened, and a desired gas is supplied from the gas cylinders 4221 to 4226 through the gas introduction pipe 5114 to the reaction vessel 5.
It is introduced into the discharge space 5130 in 111. Next, the mass flow controllers 4211 to 4216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the pressure inside the reaction vessel 5111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable, a microwave power source (not shown) generates a microwave having a frequency of 500 MHz or higher, preferably 2.45 GHz, and introduces microwave energy into the discharge space 5130 through the microwave introduction window 5112, Causes microwave glow discharge. Simultaneously with this, the power source 5119 to the electrode 511
An electric bias such as a direct current is applied to 8. Thus, the source gas introduced into the discharge space 5130 is excited by microwave energy and dissociates, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 5115. At this time, the cylindrical support 5115 is rotated at a desired rotation speed by the support rotation motor 5120 in order to make the layer formation uniform.

After the desired film thickness is formed, the supply of microwave power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction container, and the formation of the deposited film is completed.

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

Needless to say, all the outflow valves except for the necessary gas are closed when forming each layer. In addition, each gas is used in the reaction vessel 5111.
Inside, outflow valves 4251 to 4256 to reaction vessel 511
In order to avoid remaining in the pipe up to 1, the outflow valves 4251 to 4256 are closed, the auxiliary valve 4260 is opened, the main valve is fully opened, and the system is temporarily evacuated to a high vacuum as needed. ..

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

The cylindrical support 5115 may be heated by a heating element having a vacuum specification. Specific examples of such a heating element having a vacuum specification include a winding heater of a sheath heater and a plate heater. Examples thereof include an electric resistance heating element such as a ceramic heater, a heat radiation lamp heating element such as a halogen lamp and an infrared lamp, and a heating element by a heat exchange means using liquid, gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a method such as providing a container for heating only in addition to the reaction container 5111, heating the cylindrical support 5115, and then transporting the cylindrical support in the reaction container 5111 in a vacuum is used. ..

[0152] In .mu.W-PCVD method, the pressure in the discharge space, preferably 1 × 10 ^{- 3} Torr over 1 × 10 ^-1 To
rr or less, more preferably 3 × 10 ⁻³ Torr or more and 5 × 10 ⁻² Torr or less, and most preferably 5 × 10 ⁻³ Torr or more and 3 × 10 ⁻² Torr or less.

The pressure outside the discharge space may be lower than the pressure inside the discharge space, but the pressure inside the discharge space is 1 × 10 ^-1 Torr.
Below, particularly, at 5 × 10 ⁻² Torr or less, when the pressure inside the discharge space is three times or more the pressure outside the discharge space, the effect of improving the characteristics of the deposited film is particularly large.

As a method of introducing the microwave into the reaction container, a method using a waveguide 5113 can be mentioned, and a method of introducing the microwave into the reaction container through one or a plurality of microwave introduction windows 5112 can be mentioned. Examples of the material of the microwave introduction window 5112 include alumina (Al ₂ O ₃ ), aluminum nitride, boron nitride, silicon nitride, silicon carbide, silicon oxide, beryllium oxide, Teflon (trade name), polystyrene, etc. Fewer materials are commonly used.

The electric field generated between the electrode 5118 and the cylindrical support 5115 is preferably a DC electric field, and the direction of the electric field is preferably directed from the electrode 5118 to the cylindrical support 5115. The average magnitude of the DC voltage applied to the electrode 5118 for generating an electric field is 15 V or more and 300 V or less, preferably 30 V or more and 200 V or less. The DC voltage waveform is not particularly limited, and various waveforms are effective in the present invention. In other words, it does not matter in which case the direction of the voltage does not change with time. For example, a constant voltage whose magnitude does not change with time as well as a pulsed voltage,
Also, a pulsating voltage whose magnitude changes depending on the time rectified by the rectifier is effective.

It is also effective to apply an AC voltage. There is no problem with the alternating current frequency,
Practically 50 Hz or 60 Hz at low frequencies, 13.5 at high frequencies
6MHz is suitable. The AC waveform may be a sine wave, a rectangular wave, or any other waveform, but a sine wave is practically suitable. However, at this time, the voltage refers to an actual value in any case.

The size and shape of the electrode 5118 may be any as long as the discharge is not disturbed.
A cylindrical shape of 0.1 cm or more and 5 cm or less is preferable. At this time,
The length of the electrode can be set without particular limitation as long as the electric field is uniformly applied to the support.

The electrode 5118 may be made of any material as long as it has a conductive surface. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, T.
Metals such as e, V, Ti, Pt, Pd, and Fe or alloys thereof, or glass, ceramic, plastic whose surface is subjected to a conductive treatment are usually used.

[0159]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Using the apparatus for manufacturing a light receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 1
An electrophotographic light-receiving member was produced under the production conditions shown in. In this example, in order to change the change pattern of carbon content in the photoconductive layer as shown in FIG. 13, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer was changed linearly. At the same time, in order to change the change pattern of the deposited film formation rate of the photoconductive layer as shown in FIG. 7, the flow rate of SiH ₄ introduced during the formation of the photoconductive layer was changed linearly. At this time, the carbon content on the surface of the photoconductive layer on the side of the conductive support should be about 30 atom%, and on the surface layer side relative to the deposition film forming rate (R1) on the side of the photoconductive layer on the conductive support. Deposited film formation rate (R2)
The ratio R2 / R1 was about 50%.

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 ratio by Auger spectroscopy. .. To measure the deposition film formation rate, a deposition film sample was prepared in advance with the SiH ₄ flow rate in the photoconductive layer being constant, and the thickness of the deposition film was measured by the stylus method to obtain the deposition film formation rate.

[0162]

[Table 1] Canon electrophotographic photocopier NP
-6650 was installed in an electrophotographic apparatus modified for experiments, and electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness were evaluated. Each item is
The following method evaluated.

Charging Ability, Sensitivity, Residual Potential: Charging Ability: Electrophotographic photoreceptive member is installed in experimental equipment, high voltage of +6 kV is applied to the charger, corona charging is performed, and electrophotographic is performed by a surface electrometer The dark surface potential of the light receiving member is measured.

Sensitivity: The photoreceptive member for electrophotography is charged to a constant dark surface potential. Then, the light image is immediately irradiated.
The light image uses a xenon lamp light source and a filter
Irradiation was performed with light excluding light in the wavelength range of 550 nm or less. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface potential meter. The exposure amount is adjusted so that the light surface potential becomes a predetermined potential, and the exposure amount at this time is taken as the sensitivity.

Residual potential: The photoreceptive member for electrophotography is charged to a constant dark part surface potential, and immediately irradiated with a constant intensity of relatively strong light. The light image was emitted by using a xenon lamp light source and excluding light in the wavelength range of 550 nm or less using a filter. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface potential meter.

White spots, halftone unevenness: White spots: Canon full surface black chart (part number: FY9
-9073) was placed on a document table, and white spots having a diameter of 0.2 mm or less within the same area of a copy image obtained by copying were evaluated.

Halftone unevenness: put a Canon halftone chart (part number: FY9-9042) on the platen,
The image density at 100 points was measured with a circular area of 0.05 mm on the copy image obtained when copying was made as one unit, and the variation in the image density was evaluated.

In each case, ⊚ indicates particularly good, ∘ indicates good, Δ indicates no practical problem, and x indicates practical problem.

Next, the produced electrophotographic light-receiving member was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for experiments, and an accelerated durability test equivalent to 3 million sheets was conducted. An evaluation was made. The results are shown in Table 4.

Example 2 As in Example 1, under the manufacturing conditions shown in Table 2, a photoconductive layer second region, a photoconductive layer first region, and a surface layer were deposited in this order on a conductive support. Formation was carried out to produce a light receiving member for electrophotography. The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0171]

[Table 2] Comparative Example 1 Under the production conditions shown in Table 3 in the same manner as in Example 1, 3 of the conductive support, the second photoconductive layer, the first photoconductive layer and the surface layer were prepared.
A so-called function-separated type electrophotographic light-receiving member having a layered structure was produced. The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0172]

[Table 3]

[0173]

[Table 4] From these results, by forming the electrophotographic light-receiving member 10 by the method of the present invention, the charging ability and sensitivity are improved, and the residual potential is suppressed low. Further, it can be seen that the halftone unevenness shows excellent characteristics. Further, according to the present invention, it can be seen that there is no problem in electrical and image characteristics even after the endurance.

Example 3 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, except that the microwave glow discharge method was used, the same procedure as in Example 1 was carried out under the conditions shown in Table 5 A light receiving member for photography was produced. When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, the same results as in Example 1 were obtained.

[0175]

[Table 5] Example 4 Similar to Example 3, under the production conditions shown in Table 6, a deposited film was formed on the conductive support in the order of the photoconductive layer second region, the photoconductive layer first region, and the surface layer. A light receiving member for electrophotography was produced. Example 1 was applied to the produced electrophotographic light-receiving member.
The same evaluation as in Example 1 was performed, and the same results as in Example 1 were obtained.

[0176]

[Table 6] Comparative Example 2 Under the production conditions shown in Table 7 in the same manner as in Example 3, 3 of the conductive support, the second photoconductive layer, the first photoconductive layer and the surface layer were prepared.
A so-called function-separated type electrophotographic light-receiving member having a layered structure was produced. When the manufactured electrophotographic light-receiving member was evaluated in the same manner as in Example 1, the same results as in Comparative Example 1 were obtained.

[0177]

[Table 7] Example 5 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, by the RF glow discharge method according to the procedure detailed above, Table 8
An electrophotographic light-receiving member 10 was produced under the production conditions shown in. In this example, in order to change the change pattern of the deposited film formation rate of the photoconductive layer 12 as shown in FIGS. 7 to 10, the flow rate of SiH ₄ introduced during the formation of the photoconductive layer 12 was changed and four kinds of electrons were changed. A photographic light-receiving member 10 was produced. In any pattern, the ratio R2 of the deposition film formation rate R
/ R1 was set to about 50%. At this time, the change pattern of the carbon content in the photoconductive layer 12 was changed as shown in FIG. 13 so that the carbon content on the surface of the photoconductive layer 12 on the side of the conductive support was 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 ratio by Auger spectroscopy. .. To measure the deposition film formation rate, a deposition film sample was prepared in advance with the SiH ₄ flow rate in the photoconductive layer being constant, and the thickness of the deposition film was measured by the stylus method to obtain the deposition film formation rate.

The produced electrophotographic light-receiving member 10 was installed in an electrophotographic apparatus obtained by modifying a Canon copying machine NP-6650 for experiments, and the charging ability, sensitivity, residual potential, white spot,
The electrophotographic characteristics such as halftone unevenness were evaluated in the same manner as in Example 1.

[0180]

[Table 8] Comparative Example 3 Two types of electrophotographic light-receiving members were produced in the same manner as in Example 5 except that the change pattern of the deposition rate of the photoconductive layer was changed as shown in FIGS. 11 and 12. At this time, the ratio R2 / R1 of the deposited film formation rate R is 100% in FIG.
Was 120%. The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 5.

Table 9 shows the evaluation results of Example 5 and Comparative Example 3. From these results, it was found that the change pattern of the deposited film formation rate of the photoconductive layer of the present invention provided better results in electrical and image characteristics than in Comparative Example 3.

[0182]

[Table 9] Example 6 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 1
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this embodiment, SiH ₄ introduced at the time of forming the photoconductive layer second region 15 in order to change the change pattern of the deposition film formation rate of the photoconductive layer second region 15 as shown in FIGS.
Of the four types of electrophotographic light-receiving members 10 by changing the flow rate of the
Was produced. In any pattern, the ratio R2 / R1 of the deposition film formation rate R was set to about 50%. At this time, the change pattern of the carbon content in the second region 15 of the photoconductive layer was changed as shown in FIG. 13 so that the carbon content on the surface of the photoconductive layer second region 15 on the side of the conductive support was about 10 atomic%. So that

The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 5.

[0184]

[Table 10] Comparative Example 4 Two kinds of electrophotographic light-receiving members were produced in the same manner as in Example 6 except that the change pattern of the deposited film formation rate in the second region of the photoconductive layer was changed as shown in FIGS. 11 and 12. .. At this time, the ratio R2 / R1 of the deposition film formation rate R is 100 in FIG.
% And 120% in FIG.

The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 5.

Table 11 shows the evaluation results of Example 6 and Comparative Example 4.
Shown in. From these results, it was found that the change pattern of the deposition film formation rate in the second region of the photoconductive layer of the present invention provided better results in electrical and image characteristics than in Comparative Example 4.

[0187]

[Table 11] Example 7 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 6, a mirror-finished aluminum member having a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, an electrophotographic light-receiving member was produced under the production conditions shown in Table 12 by the microwave glow discharge method according to the procedure detailed above. In Table 12, four kinds of electrophotographic light-receiving members 10 were produced by changing the change pattern of the deposited film formation rate of the photoconductive layer 12 as shown in FIGS.

Example 5 was applied to the produced electrophotographic light-receiving member.
The same evaluation as in Example 5 was performed, and the same results as in Example 5 were obtained.

[0189]

[Table 12] Comparative Example 5 Two types of electrophotographic light-receiving members were produced in the same manner as in Example 7 except that the change pattern of the deposition rate of the photoconductive layer was changed as shown in FIGS. 11 and 12. At this time, the ratio R2 / R1 of the deposited film formation rate R is 100% in FIG.
Was 120%. The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 7.

The evaluation result of Comparative Example 5 was exactly the same as the evaluation result of Comparative Example 3.

Example 8 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 1
An electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this example, in order to change the change pattern of the carbon content in the photoconductive layer 12 as shown in FIGS. 13 to 15, the flow rate of CH ₄ introduced during the formation of the photoconductive layer 12 was changed,
Three types of electrophotographic light-receiving members 10 were produced. In any pattern, the conductive support 11 of the photoconductive layer 12
The carbon content on the side surface was set to about 10 atomic%.
Further, the change pattern of the deposited film forming rate of the photoconductive layer 12 at this time was changed as shown in FIG. 7 so that the ratio R1 / R1 of the deposited film forming rate R was about 50%. The carbon content and the deposition film formation rate were measured in the same manner as above.

The produced electrophotographic light-receiving member 10 was set in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for experiments, and the charging ability, sensitivity, residual potential, white spot,
The electrophotographic characteristics such as halftone unevenness were evaluated in the same manner as in Example 1. Further, an accelerated durability test of about 3 million sheets was performed, and the same evaluation was performed for each electrophotographic characteristic.

[0193]

[Table 13] Comparative Example 6 Two types of electrophotographic light-receiving members were produced in the same manner as in Example 8 except that the carbon content change pattern of the photoconductive layer 12 was changed as shown in FIGS. 16 and 17.

The light-receiving member for electrophotography thus obtained was evaluated in the same manner as in Example 8.

Table 14 shows the evaluation results of Example 8 and Comparative Example 6.
Shown in. From these results, it was found that, in the variation pattern of the carbon content of the photoconductive layer 12 of the present invention, good electrical and image characteristics were obtained as compared with Comparative Example 6.

[0196]

[Table 14] Example 9 Similar to Example 8, under the conditions shown in Table 15, a deposited film was formed on the conductive support in the order of the photoconductive layer second region, the photoconductive layer first region, and the surface layer. A light receiving member for electrophotography was produced. The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 8. The results are shown in Table 16.

[0197]

[Table 15] Comparative Example 7 Two kinds of electrophotographic light-receiving members were produced in the same manner as in Example 9 except that the carbon content change pattern of the photoconductive layer second region 15 was changed as shown in FIGS. 16 and 17. ..

The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 9.

Table 16 shows the evaluation results of Example 9 and Comparative Example 7.
Shown in. From these results, the second region 1 of the photoconductive layer of the present invention
It was found that in the carbon content change pattern of No. 5, good results were obtained in both electrical and image characteristics as compared with Comparative Example 7.

[0200]

[Table 16] Example 10 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 6, a mirror-finished aluminum member having a diameter of 108 mm and a length of 3
An electrophotographic light-receiving member for electrophotography was produced in the same manner as in Example 8 except that the production was carried out by the microwave glow discharge method under the production conditions shown in Table 17 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm. did. In Table 15, the change pattern of the carbon content of the photoconductive layer 12 was changed as shown in FIGS. 13 to 15 in the same manner as in Example 8 to prepare three types of electrophotographic light-receiving members 10.

Example 8 was applied to the produced electrophotographic light-receiving member.
The same evaluation as in Example 8 was performed, and the same results as in Example 8 were obtained.

[0202]

[Table 17] Comparative Example 8 Two kinds of electrophotographic light-receiving members were produced in the same manner as in Example 10 except that the carbon content change pattern of the photoconductive layer 12 was changed as shown in FIGS. 16 and 17.

The electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 10. The evaluation result of Comparative Example 8 was exactly the same as the evaluation result of Comparative Example 6.

Example 11 Using the apparatus for manufacturing a light receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 1
An electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this embodiment, the change pattern of the deposited film formation rate of the photoconductive layer 12 is changed as shown in FIG.
In order to change the ratio R2 / R1 of the deposited film formation rate of
The flow rate of SiH ₄ introduced when forming the photoconductive layer 12 was changed. At this time, the change pattern of the carbon content in the photoconductive layer second region 15 was changed as shown in FIG. 13, and the carbon content in the surface of the photoconductive layer second region 15 on the side of the conductive support was about 10 atomic%. So that

[0205]

[Table 18] The produced electrophotographic light-receiving member 10 is installed in an electrophotographic apparatus which is a Canon copying machine NP-6650 modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness are set. Was evaluated in the same manner as in Example 1. Further, an accelerated durability test of about 3 million sheets was performed, and the same evaluation was performed for each electrophotographic characteristic.

Table 19 shows the evaluation results. from this result,
The ratio R2 / R1 of the deposited film formation rate of the photoconductive layer 12 is 30 to
It has been found that an excellent result can be obtained by setting it to 90%.

[0207]

[Table 19] Example 12 Using a manufacturing apparatus for a light receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 2
An electrophotographic light-receiving member was produced in the same manner as in Example 11 except that the production conditions were 0.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 1 was performed, the same results as in Example 11 were obtained.

[0209]

[Table 20] Example 13 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
An electrophotographic light-receiving member was produced in the same manner as in Example 11 except that the production was performed under the production conditions shown in Table 21 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method. did.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 1 was performed, the same results as in Example 11 were obtained.

[0211]

[Table 21] Example 14 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 2
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this example, the change pattern of the carbon content in the photoconductive layer 12 was changed as shown in FIG.
In order to change the carbon content on the surface of the electroconductive support 11 side, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer 12 was changed. At this time, the change pattern of the deposited film forming rate of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposited film forming rate was set to about 85%.

[0212]

[Table 22] The produced electrophotographic light-receiving member 10 is installed in an electrophotographic apparatus which is a Canon copying machine NP-6650 modified for experiments, and the electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness are set. Was evaluated in the same manner as in Example 1, and the number of spherical projections generated on the surface of the electrophotographic light-receiving member was evaluated. The number of spherical projections generated was evaluated according to the following method.

The entire surface of the manufactured electrophotographic light-receiving member was observed with an optical microscope, and the diameter was 20 μm within an area of 100 cm ^2.
The number of the spherical protrusions was checked. Results were obtained for each electrophotographic light-receiving member, and the layer pair was compared with 100% having the largest number of spherical projections. The results are classified as follows.

⊚ is less than 60%, ◯ is less than 80% to 60% or more, and Δ is 100 to 80% or more.

Table 23 shows the evaluation results. from this result,
When the carbon content of the photoconductive layer 12 on the side of the conductive support 11 is 0.5 to 50 atom%, the characteristics are improved, and further 1 to 30 atom%, an extremely good result is obtained.

[0216]

[Table 23] Example 15 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 2
An electrophotographic light-receiving member was produced in the same manner as in Example 14 except that the production conditions shown in 4 were used.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 4 was performed, the same results as in Example 14 were obtained.

[0218]

[Table 24] Example 16 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, the mirror-finished aluminum member has a diameter of 108 mm and a length of 3 mm.
An electrophotographic light-receiving member for electrophotography was produced in the same manner as in Example 14 except that the production was performed under the production conditions shown in Table 25 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method. did.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 4 was performed, the same results as in Example 14 were obtained.

[0220]

[Table 25] Example 17 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 2
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this embodiment, the fluorine content in the photoconductive layer 12 is shown in FIG.
8, the flow rate of SiF ₄ introduced at the time of forming the photoconductive layer 12 was changed to be constant in the layer thickness direction, and electrophotographic light receiving members having different fluorine contents were produced. At this time, the change pattern of the deposition film formation rate of the photoconductive layer 12 is changed as shown in FIG. 7, and the deposition film formation rate ratio R2 /
R1 was set to about 85%. Further, the change pattern of the carbon atom content in the photoconductive layer 12 is changed as shown in FIG. 13 so that the carbon atom content on the surface of the photoconductive layer 12 on the side of the conductive support 11 becomes about 30 atom%. I chose

The fluorine content in the photoconductive layer 12 is SI
It was performed by elemental analysis by MS (CAMECA, IMS-3F).

[0222]

[Table 26] The produced electrophotographic light-receiving member 10 was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for experiments, and electrophotographic characteristics such as white spots and halftone unevenness were evaluated in the same manner as in Example 1. Then, the ghost was evaluated. The evaluation of the ghost was based on the following method.

A Canon ghost test chart (part number: FY9-9040) to which a black circle having a reflection density of 1.1 and φ5 mm is attached is placed at the leading edge of the image on the platen, and a Canon halftone chart is overlaid thereon. The difference between the reflection density of φ5 mm of the ghost chart and the reflection density of the halftone portion observed on the halftone copy in the copy image when placed was measured. The one with the largest difference was set as 100% for relative comparison. The results are classified as follows.

⊚ is less than 60%, ◯ is less than 80% to 60% or more, and Δ is 100 to 80% or more.

Further, an accelerated durability test of about 3 million sheets was carried out, and the same evaluation was carried out for each electrophotographic characteristic.

Table 27 shows the evaluation results. From these results, by setting the fluorine content of the photoconductive layer 12 in the range of 95 atomic ppm or less, it is possible to produce a photoreceptive member for electrophotography which is also excellent in image characteristics and durability. It was shown to be.

[0227]

[Table 27] Example 18 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 2
An electrophotographic light-receiving member was produced in the same manner as in Example 17, except that the production conditions shown in 8 were used.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 7 was performed, the same results as in Example 17 were obtained.

[0229]

[Table 28] Example 19 Using a manufacturing apparatus for a light-receiving member for electrophotography shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
An electrophotographic light-receiving member for electrophotography was produced in the same manner as in Example 17 except that the production was carried out by the microwave glow discharge method under the production conditions shown in Table 29 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm. did.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 7 was performed, the same results as in Example 17 were obtained.

[0231]

[Table 29] Example 20 Using the apparatus for manufacturing a light receiving member for electrophotography shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 3
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this embodiment, the fluorine content in the photoconductive layer 12 is shown in FIG.
8 to 22, in order to change in the layer thickness direction, the flow rate of SiF ₄ introduced when forming the photoconductive layer 12 is changed,
Five types of electrophotographic light-receiving members 10 were produced. At this time, the fluorine content in the photoconductive layer 12 was changed within the range of 1 to 95 atomic ppm. Further, a sample was prepared at the same time in which the photoconductive layer 12 did not contain fluorine atoms. At this time, the change pattern of the deposited film forming rate of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposited film forming rate was set to about 85%. Further, the change pattern of the carbon atom content in the photoconductive layer 12 is changed as shown in FIG. 13 so that the carbon atom content on the surface of the photoconductive layer 12 on the side of the conductive support 11 becomes about 30 atom%. I chose

The fluorine content in the photoconductive layer 12 is SI
It was performed by elemental analysis by MS (CAMECA, IMS-3F).

[0233]

[Table 30] The six types of electrophotographic light-receiving members 10 thus prepared were installed in an electrophotographic apparatus modified from a Canon copying machine NP-6650 for experiments, and the charging ability, sensitivity, residual potential, white spots, halftone unevenness, and ghost were set. The electrophotographic characteristics such as the above were evaluated in the same manner as in Examples 1 and 17, and further the temperature characteristics and the image density unevenness were evaluated. The following methods were used to evaluate the temperature characteristics and the image density unevenness.

Temperature characteristics: The surface temperature of the manufactured electrophotographic light-receiving member 10 was changed to 30 to 45 ° C., and +6 k was applied to the charger.
A high voltage of V is applied, corona charging is performed, and the surface potential of the dark part is measured by a surface potential meter. A change in the surface temperature of the dark portion with respect to the surface temperature of the electrophotographic light-receiving member 10 is approximated by a straight line, and the inclination thereof is expressed as a "temperature characteristic" in the unit of [V / deg].

The evaluations are as follows: ⊚: "especially good", ○
Indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

Image density unevenness: A circular area having a diameter of 0.05 mm on each copy image obtained when a Canon halftone chart (part number: FY9-9042) was placed on a platen and 200 sheets were continuously copied. 100 as one unit
The image density of the points is measured, and the average of the image densities is calculated.
The evaluation was performed on the average variation of the image density among the obtained 200 images.

The evaluations are as follows: ⊚: "especially good", ○
Indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

Further, an accelerated durability test of about 3 million sheets was performed, and the same evaluation was performed for each electrophotographic characteristic.

Table 31 shows the evaluation results. From these results, it was confirmed that by containing a fluorine atom in the photoconductive layer 12 and further changing the fluorine content in the layer thickness direction, it was very effective in terms of image characteristics and durability.

[0240]

[Table 31] Example 21 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, the mirror-finished aluminum member has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 3
An electrophotographic light-receiving member was produced in the same manner as in Example 20 except that the production conditions shown in 2 were used.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as 0 was performed, the same results as in Example 20 were obtained.

[0242]

[Table 32] Example 22 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
An electrophotographic light-receiving member was produced in the same manner as in Example 20 except that the production was carried out under the production conditions shown in Table 33 by the microwave glow discharge method on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm. did.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as 0 was performed, the same results as in Example 20 were obtained.

[0244]

[Table 33] Example 23 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 3
An electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this example, the oxygen content in the photoconductive layer 12 is shown in FIG.
3, the oxygen content was changed as shown in Table 35 by changing the flow rate of CO ₂ introduced at the time of forming the photoconductive layer 12 to manufacture the electrophotographic light-receiving members 10. At this time, the change pattern of the deposited film forming rate of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposited film forming rate was set to about 85%.
Further, the change pattern of the carbon atom content in the photoconductive layer 12 is changed as shown in FIG. 13 so that the carbon atom content on the surface of the photoconductive layer 12 on the side of the conductive support 11 becomes about 30 atom%. I chose

The oxygen content in the photoconductive layer 12 is SI
It was performed by elemental analysis by MS (CAMECA, IMS-3F).

[0246]

[Table 34] The produced electrophotographic light-receiving member 10 was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for experiments, and the electrophotographic characteristics such as charging ability, sensitivity and residual potential were the same as in Example 1. The evaluation was performed and further the potential shift was evaluated. The evaluation of the potential shift was according to the following method.

The electrophotographic light-receiving member 10 thus prepared was placed in an experimental apparatus, a high voltage of +6 kV was applied to the charger, corona charging was performed, and the surface of the dark portion of the electrophotographic light-receiving member 10 was measured by a surface electrometer. Measure the potential. At this time, the dark surface temperature potential when the voltage starts to be applied to the charger is set to Vd0, and 2
The surface potential of the dark area after the minute is set to Vd. Then, the difference between Vd0 and Vd is used as the potential shift amount.

The evaluation is as follows: ⊚: "especially good", ○
Indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

The evaluation results are shown in Table 35. From these results, it was confirmed that when the photoconductive layer 12 contains a fluorine atom and further contains an oxygen atom in the range of 10 to 5000 ppm, it is very effective in improving electrophotographic characteristics such as potential shift. Was done.

[0250]

[Table 35] Example 24 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 3
An electrophotographic light-receiving member was produced in the same manner as in Example 23 except that the production conditions shown in 6 were used.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 3 was performed, the same results as in Example 23 were obtained.

[0252]

[Table 36] Example 25 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
An electrophotographic light-receiving member for electrophotography was produced in the same manner as in Example 23 except that the production was performed under the production conditions shown in Table 37 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method. did.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 3 was performed, the same results as in Example 23 were obtained.

[0254]

[Table 37] Example 26 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, the mirror-finished aluminum member has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 3
An electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this example, the oxygen content in the photoconductive layer 12 is shown in FIG.
3 to 27, the flow rate of CO ₂ introduced at the time of forming the photoconductive layer 12 is changed to change the layer thickness direction.
A variety of electrophotographic light-receiving members 10 were produced. At this time, the oxygen content in the photoconductive layer 12 is 10 to 800 atom pp.
It was changed within the range of m. Further, a sample was prepared at the same time in which the photoconductive layer 12 did not contain oxygen atoms. At this time,
The change pattern of the deposited film forming rate of the photoconductive layer 12 was changed as shown in FIG. 7, and the deposited film forming rate ratio R2 / R1 was set to about 85%. Further, the change pattern of the carbon atom content in the photoconductive layer 12 is changed as shown in FIG.
The carbon atom content on the surface of the photoconductive layer 12 on the electroconductive support 11 side was set to about 30 atom%.

The oxygen content in the photoconductive layer 12 is SI
It was performed by elemental analysis by MS (CAMECA, IMS-3F).

[0256]

[Table 38] The six types of electrophotographic light-receiving members 10 thus prepared were installed in an electrophotographic apparatus modified from a Canon copying machine NP-6650 for experiments, and the charging ability, sensitivity, residual potential, white spots, halftone unevenness, and ghost were set. The electrophotographic characteristics such as potential shift were evaluated in the same manner as in Examples 1, 17 and 23.

Further, an accelerated durability test of about 3 million sheets was carried out, and the same evaluation was carried out for each electrophotographic characteristic.

Table 39 shows the evaluation results. From these results, it has been clarified that the durability in electrophotographic characteristics is improved by containing oxygen atoms in the photoconductive layer 12 and more preferably changing the concentration thereof in the layer thickness direction.

[0259]

[Table 39] Example 27 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 4
An electrophotographic light-receiving member was produced in the same manner as in Example 26 except that the production conditions were 0.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 6 was performed, the same results as in Example 26 were obtained.

[0261]

[Table 40] Example 28 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, the mirror-finished aluminum member has a diameter of 108 mm and a length of 3
A light-receiving member for electrophotography was produced in the same manner as in Example 26 except that the production was performed under the production conditions shown in Table 41 on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method. did.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as in Example 6 was performed, the same results as in Example 26 were obtained.

[0263]

[Table 41] Example 29 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 4
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this example, carbon atoms contained in the surface layer 13,
Oxygen atom, silicon atom and the sum of the content of nitrogen atom, carbon atom, oxygen atom, from 40 atomic% to the sum of the content of nitrogen atoms to 90 atomic%, the power to be introduced at the surface layer 13 formed, CH ₄ flow rate , CO ₂ flow rate, and NH ₃ flow rate were changed.

[0264]

[Table 42] The produced electrophotographic light-receiving member 10 was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for experiments, and the electrophotographic characteristics such as charging ability, sensitivity and residual potential were the same as in Example 1. Evaluation is performed and further image deletion, 30
Image evaluation was performed before and after the accelerated durability test equivalent to 0,000 sheets. Image deletion and image evaluation were according to the following methods.

Image deletion: A Canon test chart (part number: FY9-9058) consisting of all characters on a white background is placed on a document table and exposed at an exposure amount twice the normal exposure amount.
Make a copy. The image thus obtained was observed, and whether the thin lines on the image were connected without interruption was evaluated according to the following four grades. However, at this time, when there was unevenness on the image, evaluation was made on the worst part in the entire image area.

The evaluations are as follows: ⊚ is “good”, ◯ is “partially discontinued”, Δ is “interrupted but legible as a character and practically no problem”, and × is “disrupted with many characters” It is difficult to read, and there is a problem in practical use. "

Image evaluation: Five-level limit samples were prepared for each of white spots and scratches, and the total evaluation results were classified into the following four levels. ⊚ indicates “particularly good”, ◯ indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

Comparative Example 9 For electrophotography in the same manner as in Example 29 except that the total content of carbon atom, oxygen atom and nitrogen atom contained in the surface layer was set to less than 40 atom% and more than 90 atom%. A light receiving member was prepared and evaluated in the same manner.

Comparative Example 10 Except that CH ₄ was not used at the time of forming the surface layer, NO was used instead of CO ₂ , and the total content of oxygen atoms and nitrogen atoms contained in the surface layer was 60 atomic%. An electrophotographic light-receiving member was produced in the same manner as in Example 29, and evaluated in the same manner.

Comparative Example 11 An electrophotographic process was performed in the same manner as in Example 29 except that CO ₂ was not used when forming the surface layer and the total content of carbon atoms and nitrogen atoms contained in the surface layer was set to 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

Comparative Example 12 Electrophotography was carried out in the same manner as in Example 29 except that NH ₃ was not used when forming the surface layer, and the total content of carbon atoms and oxygen atoms contained in the surface layer was 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

The results of Example 29 and Comparative Examples 9 to 12 are shown in Table 43 together. From these results, the total content of carbon atoms, oxygen atoms and nitrogen atoms in the surface layer according to the present invention is 40 to 90 relative to the total content of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. A marked improvement in electrophotographic properties and durability was observed at atomic%, and extremely good results were obtained by adjusting the sum of the content of oxygen atoms and nitrogen atoms to 10 atomic% or less.

[0273]

[Table 43] Example 30 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, the mirror-finished aluminum member has a diameter of 108 mm and a length of 3 mm.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 4
An electrophotographic light-receiving member was produced in the same manner as in Example 29 except that the production conditions shown in 4 were used. The obtained electrophotographic light-receiving member was evaluated in the same manner as in Example 29.

[0274]

[Table 44] Comparative Example 13 An electrophotographic light-receiving member was prepared in the same manner as in Example 30, except that the total content of carbon atom, oxygen atom and nitrogen atom contained in the surface layer was less than 40 atom% and more than 90 atom%. Was prepared and evaluated in the same manner.

Comparative Example 14 Except that CH ₄ was not used at the time of forming the surface layer, and NO was used instead of CO _{2 so that} the total content of oxygen atoms and nitrogen atoms contained in the surface layer was 60 atomic%. An electrophotographic light-receiving member was produced in the same manner as in Example 30, and evaluated in the same manner.

Comparative Example 15 An electrophotography was carried out in the same manner as in Example 30 except that CO ₂ was not used when forming the surface layer and the total content of carbon atoms and nitrogen atoms contained in the surface layer was set to 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

Comparative Example 16 Electrophotography was carried out in the same manner as in Example 30 except that NH ₃ was not used at the time of forming the surface layer and the total content of carbon atoms and oxygen atoms contained in the surface layer was changed to 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

The same results as in Example 29 were obtained for Example 30 and for Comparative Examples 13 to 16 and Comparative Examples 9 to 12.

Example 31 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 6, on a cylindrical conductive support 11 made of mirror-finished aluminum and having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm. Further, a light-receiving member for electrophotography was produced by the same method as in Example 29 except that the production conditions shown in Table 45 were used and the microwave glow discharge method was used.

[0280]

[Table 45] Comparative Example 17 An electrophotographic light-receiving member for electrophotography was performed in the same manner as in Example 31 except that the total content of carbon atoms, oxygen atoms and nitrogen atoms contained in the surface layer was less than 40 atom% and more than 90 atom%. Was prepared and evaluated in the same manner.

Comparative Example 18 Except that CH ₄ was not used at the time of forming the surface layer, and NO was used instead of CO _{2 so that} the total content of oxygen atoms and nitrogen atoms contained in the surface layer was 60 atomic%. An electrophotographic light-receiving member was produced in the same manner as in Example 31, and evaluated in the same manner.

Comparative Example 19 An electrophotographic process was performed in the same manner as in Example 31 except that CO ₂ was not used when forming the surface layer and the total content of carbon atoms and nitrogen atoms contained in the surface layer was set to 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

Comparative Example 20 An electrophotographic process was performed in the same manner as in Example 31 except that NH ₃ was not used when forming the surface layer and the total content of carbon atoms and oxygen atoms contained in the surface layer was changed to 60 atom%. A light-receiving member for use was prepared and evaluated in the same manner.

The same results as in Example 29 were obtained for Example 31 and in Comparative Examples 9-12 for Comparative Examples 17-20.

Example 32 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, a mirror-finished aluminum member having a diameter of 108 mm and a length of 3 was formed.
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 4
The electrophotographic light-receiving member 10 was produced under the production conditions shown in FIG. In this embodiment, the surface layer contains 20 atomic% or less of fluorine atoms and the total content of hydrogen atoms and fluorine atoms is changed in the range of 30 to 70 atomic%. Electrophotographic light-receiving members were produced by changing the power, H ₂ and / or SiF ₄ flow rate introduced during formation.

The produced electrophotographic light-receiving member was placed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6650 for an experiment, and in the same manner as in Example 29, the residual potential, the sensitivity, and the image deletion were 3%. The items were evaluated.

[0287]

[Table 46] Comparative Example 21 An electrophotographic light-receiving member was produced in the same manner as in Example 32, except that the total content of hydrogen atoms and fluorine atoms contained in the surface layer was less than 30 atom% and more than 70 atom%. , And evaluated in the same manner.

Comparative Example 22 An electrophotographic light-receiving member was prepared and evaluated in the same manner as in Example 32 except that the content of fluorine atoms contained in the surface layer was increased to more than 20 atom%.

Comparative Example 23 Example 3 except that SiF ₄ was not used when forming the surface layer.
A light-receiving member for electrophotography was prepared in the same manner as in 2, and evaluated in the same manner.

The results of Example 32 and Comparative Examples 21 to 23 are shown in Table 47 together. As is clear from Table 47, the residual potential is controlled by setting the sum of the content of hydrogen atoms and fluorine atoms in the surface layer to 30 to 70 atom% and the content of fluorine atoms in the range of 20 atom% or less. It was found that both the sensitivity and the sensitivity showed good results and that the image deletion at the strong exposure could be significantly suppressed.

[0291]

[Table 47] Example 33 Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, it was made of mirror-finished aluminum and had a diameter of 108 mm and a length of 3
On the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure detailed above, by the RF glow discharge method, Table 4
An electrophotographic light-receiving member was produced in the same manner as in Example 32 except that the production conditions shown in 8 were used. The obtained electrophotographic light receiving member was evaluated in the same manner as in Example 32.

[0292]

[Table 48] Comparative Example 24 An electrophotographic light-receiving member was produced in the same manner as in Example 33 except that the total content of hydrogen atoms and fluorine atoms contained in the surface layer was less than 30 atom% and more than 70 atom%. , And evaluated in the same manner.

Comparative Example 25 An electrophotographic light-receiving member was prepared and evaluated in the same manner as in Example 33 except that the content of fluorine atoms in the surface layer was increased to more than 20 atom%.

Comparative Example 26 Example 3 except that SiF ₄ was not used when forming the surface layer.
An electrophotographic light-receiving member was produced in the same manner as in 3, and evaluated in the same manner.

The same results were obtained as in Example 32 for Example 33 and for Comparative Examples 24 to 26 and Comparative Examples 21 to 23.

Example 34 Using the apparatus for manufacturing a light receiving member for electrophotography shown in FIG. 6, it is made of mirror-finished aluminum and has a diameter of 108 mm and a length of 3 mm.
An electrophotographic light-receiving member was produced in the same manner as in Example 32 except that the production was performed under the production conditions shown in Table 49 by the microwave glow discharge method on the cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm. did. The obtained electrophotographic light receiving member was evaluated in the same manner as in Example 32.

[0297]

[Table 49] Comparative Example 27 An electrophotographic light-receiving member was produced in the same manner as in Example 34, except that the total content of hydrogen atoms and fluorine atoms contained in the surface layer was less than 30 atom% and more than 70 atom%. , And evaluated in the same manner.

Comparative Example 28 An electrophotographic light-receiving member was prepared and evaluated in the same manner as in Example 34 except that the content of fluorine atoms contained in the surface layer was more than 20 atom%.

Comparative Example 29 Example 3 except that SiF ₄ was not used when forming the surface layer.
An electrophotographic light-receiving member was produced in the same manner as in 4, and evaluated in the same manner.

Similar results were obtained as in Example 32 for Example 34 and Comparative Examples 21-23 for Comparative Examples 27-29.

[0301]

EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to solve various problems in the conventional photoreceptive member for electrophotography composed of A-Si, and in particular, extremely excellent electric characteristics and optical characteristics. It is possible to form a photoreceptive member for electrophotography, which exhibits photoconductive properties, image properties, durability and use environment properties. Particularly in the present invention, the carbon atoms contained in the photoconductive layer are continuously reduced from the side of the conductive support toward the side of the surface layer, whereby the generation of charges (photocarriers) and the transport of the generated charges are carried out. The important function for the electrophotographic light-receiving member can be smoothly maintained, and an electrophotographic light-receiving member having excellent photosensitivity can be produced. In addition, since the photoconductive layer contains carbon atoms, the dielectric constant of the photoreceptive layer including the photoconductive layer and the surface layer can be reduced, so that the capacitance per layer thickness can be reduced. It is possible to achieve high chargeability, a remarkable improvement in photosensitivity, further improvement in withstand voltage against high voltage, and improvement in durability.

Further, by increasing the deposition film formation rate of the photoconductive layer on the support side and slowing it on the surface layer side, the content of carbon atoms in the photoconductive layer changes in the layer thickness direction. The stress of the inside is effectively relieved, and the denseness of the deposited film is improved by the synergistic effect of the change of the deposited film formation rate and the change of the carbon content, so that the uniformity of the deposited film is improved and The number of defects is reduced. As a result, image characteristics such as uneven halftone can be improved, and injection of charges from the surface layer side can be prevented more effectively, and higher charging ability can be obtained.
Furthermore, peeling of the deposited film and generation of minute defects can be significantly suppressed.

Further, the photoconductive layer is composed of two regions, that is, the second region of the photoconductive layer and the first region of the photoconductive layer, and the layer thickness of the first region of the photoconductive layer is 0.5 to 50 μm. The ghost is improved because the sensitivity of wavelength light is improved and the traveling property of carriers opposite to the charging polarity is improved. Further, by providing the surface layer according to the present invention, the water repellency is enhanced and the moisture resistance is improved. 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 the charging ability, operating environment characteristics, durability and electrical withstand voltage Can be improved. In addition, the absorption of light in the surface layer is reduced, which can improve the sensitivity, and the accumulation of carriers between the photoconductive layer and the surface layer is reduced, so that the chargeability is maintained at a high level. It is possible to provide an electrophotographic light-receiving member capable of suppressing image deletion as it is.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram for explaining a layer configuration of a preferred embodiment of a light receiving member for electrophotography according to the present invention.

FIG. 2 is a schematic configuration diagram for explaining a layer configuration of another preferred embodiment of the electrophotographic light-receiving member according to the present invention.

FIG. 3 is a schematic configuration diagram showing an example of a layer configuration of a conventional electrophotographic light-receiving member.

FIG. 4 shows an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, RF
It is a schematic explanatory view of a manufacturing apparatus of a light receiving member for electrophotography by a glow discharge method.

FIG. 5 shows an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography according to the present invention.
It is a schematic explanatory drawing of the deposition apparatus part of the manufacturing apparatus of the electrophotographic light-receiving member by the glow discharge method, (a) is a side sectional view of an apparatus, (b) is a transverse sectional view in XX '. is there.

6 shows an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography according to the present invention, and FIG.
FIG. 6 is a schematic explanatory view in which the deposition apparatus of the apparatus for manufacturing the electrophotographic light-receiving member by the RF glow discharge method of FIG.

FIG. 7: Photoconductive layer in the present invention (photoconductive layer second region)
3 is a graph showing a change pattern of the deposited film formation rate of FIG.

FIG. 8 is a photoconductive layer in the present invention (photoconductive layer second region).
3 is a graph showing a change pattern of the deposited film formation rate of FIG.

FIG. 9 is a photoconductive layer in the present invention (photoconductive layer second region).
3 is a graph showing a change pattern of the deposited film formation rate of FIG.

FIG. 10 is a graph showing a change pattern of a deposition film formation rate of a photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 11 is a graph showing a change pattern of a deposition film formation rate of a photoconductive layer (photoconductive layer second region) outside the present invention.

FIG. 12 is a graph showing a change pattern of a deposition film formation rate of a photoconductive layer (photoconductive layer second region) outside the present invention.

FIG. 13 is a graph showing a change pattern of carbon content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 14 is a graph showing a change pattern of carbon content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 15 is a graph showing a change pattern of carbon content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 16 is a graph showing a change pattern of carbon content in the photoconductive layer (photoconductive layer second region) outside the present invention.

FIG. 17 is a graph showing a change pattern of carbon content in the photoconductive layer (photoconductive layer second region) outside the present invention.

FIG. 18 is a graph showing a change pattern of fluorine content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 19 is a graph showing a change pattern of the fluorine content of the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 20 is a graph showing a change pattern of fluorine content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 21 is a graph showing a change pattern of fluorine content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 22 is a graph showing a change pattern of fluorine content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 23 is a graph showing a change pattern of oxygen content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 24 is a graph showing a change pattern of oxygen content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 25 is a graph showing a change pattern of oxygen content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 26 is a graph showing a change pattern of oxygen content in the photoconductive layer (photoconductive layer second region) in the present invention.

FIG. 27 is a graph showing a change pattern of oxygen content in the photoconductive layer (photoconductive layer second region) in the present invention.

[Explanation of symbols]

 10 Electrophotographic Photoreceptive Member 11 Conductive Support 12 Photoconductive Layer 13 Surface Layer 14 Free Surface 15 Photoconductive Layer Second Region 16 Photoconductive Layer First Region 4100 RF Glow Discharge Deposition Device 4111 Reaction Vessel 4112 Cylindrical support 4113 Support heating heater 4114 Raw material gas introduction pipe 4115 Matching box 4116 Raw material gas pipe 4117 Reaction vessel leak valve 4118 Main exhaust valve 4119 Vacuum gauge 4200 Raw material gas supply device 4211-4216 Mass flow controller 4221-4226 Raw material gas cylinder 4231 ˜4236 Raw material gas cylinder valve 4241 to 4246 Gas inflow valve 4251 to 4256 Gas outflow valve 4261 to 4266 Pressure regulator 5100 μW Deposition film forming apparatus by glow discharge method 511 1 Reaction vessel 5112 Microwave introduction window 5113 Waveguide 5114 Support holder 5115 Cylindrical support 5116 Support heating heater 5117 Raw material gas introduction tube 5118 Bias electrode 5119 Bias power supply 5120 Support rotation motor 5121 Exhaust pipe 5130 Discharge space

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location G03G 5/08 305 7144-2H 312 7144-2H 313 7144-2H (72) Inventor Toshiyasu Shirasuna Tokyo 3-30-2 Shimomaruko, Ota-ku Canon Inc.

Claims (17)

[Claims] 1. A method for forming a photoreceptive member for electrophotography, comprising: a conductive support; and a photoreceptive layer comprising a photoconductive layer having a silicon atom as a base and a photoreceptive layer including a surface layer, which are sequentially laminated on the conductive support. In the method, the photoconductive layer contains at least carbon atoms and hydrogen atoms over the entire layer, the content of the carbon atoms is unevenly distributed in the layer thickness direction, and many on the side of the conductive support, It is composed of a non-single-crystal material that is less distributed on the surface layer side, and the surface layer is a non-single crystal containing silicon atoms as a matrix and simultaneously containing carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms and nitrogen atoms. Forming a photoconductive layer made of a crystalline material, changing the deposition film formation rate of the photoconductive layer in the layer thickness direction so that the photoconductive layer is faster on the conductive support side and slower on the surface layer side. Featured electronic photography Method of forming the light receiving member. 2. The deposition film forming rate of the surface of the photoconductive layer on the surface layer side or near the surface is 30 to 9 with respect to the deposition film forming rate of the surface on the conductive support side or near the surface.
The method for forming a light-receiving member for electrophotography according to claim 1, wherein the content is 0%. 3. The content of the carbon atom in the photoconductive layer is set to 0 or less on the surface on the conductive support side or in the vicinity of the surface.
The content of the hydrogen atoms in the photoconductive layer is 5 to 50 atomic%, substantially 0% at or near the surface on the surface layer side, and the content of the hydrogen atoms in the photoconductive layer is 1 to 40 atomic%. 1
Alternatively, the method for forming a light receiving member for electrophotography according to the item 2. 4. The method for forming a photoreceptive member for electrophotography according to claim 1, wherein the photoconductive layer contains a fluorine atom. 5. The method for forming a photoreceptive member for electrophotography according to claim 4, wherein the fluorine atoms in the photoconductive layer are non-uniformly distributed in the layer thickness direction. 6. The method for forming a photoreceptive member for electrophotography according to claim 1, wherein oxygen atoms are contained in the photoconductive layer. 7. The method for forming a photoreceptive member for electrophotography according to claim 6, wherein the oxygen atoms in the photoconductive layer are non-uniformly distributed in the layer thickness direction. 8. The photoconductive layer comprises a photoconductive layer first region and a photoconductive layer second region, and the photoconductive layer second region contains at least carbon atoms and hydrogen atoms all over the layer, The carbon atom content is non-uniformly distributed in the layer thickness direction, and is composed of a non-single-crystal material having a large distribution on the conductive support side and a small distribution on the photoconductive layer first region side, The conductive layer first region is made of a non-single-crystal material containing 1 to 40 atomic% of hydrogen atoms, and the deposition film formation rate of the photoconductive layer second region is changed in the layer thickness direction, and the conductive support side is provided. And fast, the photoconductive layer first
The method for forming a light-receiving member for electrophotography according to claim 1, wherein the second region of the photoconductive layer is formed so as to be delayed on the region side. 9. The deposition film formation rate of the surface of the photoconductive layer second region on the side of the photoconductive layer first region or near the surface of the second region of the photoconductive layer with respect to the deposition film formation rate on the surface of the conductive support side or near the surface thereof. 9. The method for forming a photoreceptive member for electrophotography according to claim 8, wherein the total content is 30 to 90%. 10. The content of the carbon atom in the second region of the photoconductive layer is 0.5 to 50 atom% at or near the surface on the side of the conductive support, and the first region side of the photoconductive layer. The content of the hydrogen atoms in the second region of the photoconductive layer is substantially 1% on the surface of or near the surface, and the content of the hydrogen atoms is 1 to 40 atom%. A method for forming a photographic light-receiving member. 11. The method for forming a light receiving member for electrophotography according to claim 8, wherein a fluorine atom is contained in the second region of the photoconductive layer. 12. The method for forming a photoreceptive member for electrophotography according to claim 11, wherein the fluorine atoms in the second region of the photoconductive layer are non-uniformly distributed in the layer thickness direction. 13. The method for forming a photoreceptive member for electrophotography according to claim 8, wherein oxygen atoms are contained in the second region of the photoconductive layer. 14. The method for forming a photoreceptive member for electrophotography according to claim 13, wherein oxygen atoms in the second region of the photoconductive layer are non-uniformly distributed in the layer thickness direction. 15. The film thickness of the first region of the photoconductive layer is 0.5.
15. The method for forming a photoreceptive member for electrophotography according to any one of claims 8 to 14, wherein the thickness is from 15 to 15 [mu] m. 16. The surface layer, wherein the sum of the content of carbon atoms, oxygen atoms and nitrogen atoms in the surface layer is relative to the sum of the content of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. 40 to 90 atomic%, the content of halogen atoms is 20 atomic% or less, and the sum of the content of hydrogen atoms and halogen atoms is 30 to 70 atomic%. 16. The method for forming a light-receiving member for electrophotography according to any one of items 1 to 15. 17. The surface layer is formed so that the sum of the contents of the oxygen atom and the nitrogen atom in the surface layer is 10 atom% or less. 2. The method for forming a light receiving member for electrophotography according to item 1.