JP2895286B2 - Method of forming light receiving member for electrophotography - Google Patents

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 light-receiving member for electrophotography, in which a light-receiving portion layer containing silicon atoms as a base material 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.
High S / N ratio [photocurrent (Ip) / dark current (Id)], having an absorption spectrum suitable for the spectral characteristics of the radiated electromagnetic wave, fast photoresponse, having desired dark resistance, Harmless to the human body in
And other characteristics are required. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-polluting property at the time of use is important.

Based on this viewpoint, amorphous silicon (hereinafter referred to as “A
-Si "), for example, German Published Patent No.
JP-A-2746967 and JP-A-2855718 describe applications as light-receiving members for electrophotography.

FIG. 3 is a cross-sectional view schematically showing a layer structure of a conventional electrophotographic light receiving member 20, in which 21 is a conductive support, and 22 is a light receiving layer made of A-Si. Generally, such an electrophotographic light-receiving member heats the conductive support 21 to 50 to 400 ° C., and performs a vacuum deposition method on the support,
Sputtering method, ion plating method, thermal CVD
A by a film forming method such as a plasma CVD method, a photo CVD method, and a plasma CVD method.
A photosensitive layer 22 made of -Si is produced. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an A-Si deposited film on a support has been put to practical use.

JP-A-56-83746 discloses a conductive support, an A-Si film containing a halogen atom as a constituent element.
Electrophotographic light receiving members comprising a photoconductive layer have been proposed. In the publication, a halogen atom is added to A-Si by 1-4.
By containing 0 atomic%, dangling bonds are compensated to reduce the localized level density in the energy gap, and electric and optical characteristics suitable as a light receiving layer of a light receiving member for electrophotography are obtained. It can be done.

On the other hand, amorphous silicon carbide (hereinafter, referred to as amorphous silicon carbide)
(Referred to as “A-SiC”), has high heat resistance and surface hardness, has high dark resistivity as compared with A-Si, and has an optical band gap of 1.
It is known that it can be changed over a range of 6 to 2.8 eV. Japanese Patent Application Laid-Open No. Sho 54-145540 proposes an electrophotographic light-receiving member having a photoconductive layer made of A-SiC. In this publication, an excellent electron with high dark resistance and good photosensitivity is obtained by using A-Si containing 0.1 to 30 atomic% of carbon as a chemical modifier as a photoconductive layer of an electrophotographic light receiving member. It is disclosed to exhibit photographic properties.

Further, Japanese Patent Publication No. 63-35026 discloses an A-Si (hereinafter referred to as AS) containing carbon, hydrogen and / or fluorine atoms as constituents 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 an A-SiC containing at least a hydrogen atom and / or a fluorine atom has been proposed.
It is alleged that the (H, F) intermediate layer can reduce cracks and peeling of the A-Si photoconductive layer without deteriorating the photoconductive properties.

JP-A-58-219560 proposes an electrophotographic photoreceptor having a surface layer in which amorphous hydrogenated and / or fluorinated silicon carbide contains a Group 3B element of the periodic table.

Further, Japanese Patent Application Laid-Open Nos. 60-67950 and 60-679
No. 51 proposes a photoreceptor having a light-transmitting insulating overcoat layer in which A-Si contains carbon, fluorine and oxygen.

[0010]

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

In recent years, in particular, electrophotographic apparatuses are required to have higher image quality, higher speed, and higher durability. As a result, there is a demand for electrophotographic light-receiving members to further improve their electrical and photoconductive properties, and to significantly increase their durability under any environment 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 an attempt is made to increase the sensitivity and the dark resistance at the same time, a potential may remain in the conventional use. This type of photoreceptor is often observed, and if it is used for a long period of time, the so-called "ghost" occurs due to the accumulation of fatigue due to repeated use and afterimages.
There were many inconveniences such as causing a phenomenon. Conventionally, it has been difficult to achieve both high charging ability and prevention of image deletion at a high level.

Further, when the A-Si material is applied to a light receiving member for electrophotography, the temperature of the light receiving member is changed so as to change the room temperature or stabilize the electrostatic latent image. Due to the variation in temperature control, the dark resistance changes due to the change in the temperature of the light receiving member, and as a result,
There has been an inconvenience that uneven image density occurs between images when continuously obtaining copy images. Further, in the past, when the device was continuously used for a long period of time, it was often observed that the unevenness of the image density between the images became more remarkable due to fatigue due to repeated use.

When the photoreceptive layer is made of an A-Si material, a hydrogen atom (H), a fluorine atom (F), a chlorine atom or the like is used in order to improve the electric and photoconductive properties. A halogen atom (X) such as (Cl), a boron atom (B) or a phosphorus atom (P) for controlling the electric conduction type, or another atom for improving other characteristics. Although atoms are contained in the photoconductive layer, depending on how these constituent atoms are contained, problems may occur in the electrical or photoconductive properties of the formed layer and its uniformity. That is, if there is a non-uniform portion in the charge transporting ability of the photoconductive layer, unevenness in image density occurs, particularly in a halftone image, so that a high degree of tissue structural, electrical, and optical film quality is required. High uniformity is required.

In addition, since higher image quality and higher function are demanded of recent electrophotographic copying machines, it is also essential to be able to faithfully reproduce originals including halftones such as photographs. Therefore, there is a strong demand for electrophotographic photoreceptors to reduce halftone unevenness. In particular, in a full-color copying machine that has become widespread in recent years, this unevenness becomes a subtle unevenness in color and becomes visually apparent, which poses a serious problem.

Further, as a result of the improvement of the optical exposure system, the developing device, the transfer device and the like in the electrophotographic apparatus in order to improve the image characteristics of the electrophotographic apparatus, the light receiving member for electrophotography has a higher image quality than before. Improvements in characteristics have been required. There has been a demand for a reduction in black spot or white spot image defects, commonly referred to as “pots”, and in particular, a reduction in minute size “pots” which has not been regarded as a problem in the past.

In particular, with regard to the “pochi”, most of the cause is abnormal growth of a film called a spherical projection, and it is important to reduce the number of occurrences. In addition, when a large number of images are continuously formed, a phenomenon in which “pots” increase from the initial image may be observed, and it is possible to reduce the increase in “pots” due to such long-term use. It has been demanded. One of the causes is that part of the paper dust of the transfer paper accumulates on the charging wire of the separation charger due to continuous image formation and induces abnormal discharge, and part of the light receiving member undergoes dielectric breakdown. It is caused by being done. A so-called "leak potch" is included. Furthermore, the presence of abnormal growth on the surface of the light receiving member damages the cleaning blade during continuous image formation, causing poor cleaning and deteriorating image quality. The scattering of the residual toner causes the toner to accumulate on the charging wire of the separation charging device and easily causes abnormal discharge, which also causes the occurrence of “leak spots”. Furthermore, a relatively large abnormal growth portion may be lost due to the light receiving member rubbing against the transfer paper or the cleaning blade, which also causes an increase in “pocks”. As described above, in order to reduce "pocks" generated from several causes, it is required to improve the material properties of the light receiving member for electrophotography and to take measures against the "pocks" including the manufacturing process. .

In recent years, the use of recycled paper in electrophotographic apparatuses has been increasing as part of the promotion of protection of the global environment.
The surface of the electrophotographic light-receiving member is damaged by additives such as clay, which is used as a bleaching agent when recycling old newspapers, etc. Rosin used as an agent) adheres to the surface of the photoreceptor agent, causing problems such as fusion of the toner and image deletion. Therefore, it has been required to further improve the surface of the electrophotographic light receiving member at the same time as improving the quality of the recycled paper.

Also, due to the inherently high durability characteristics of the amorphous silicon photoreceptor, the photoreceptor may be considered as a part of a copying machine instead of being viewed as a consumable, and may be released from maintenance such as replacement of the photoreceptor. Is starting to appear. Therefore, new products are required to have the same or higher durability as the copying machine itself, and the electrophotographic photoreceptor has high electrical and photoconductive properties. It is desired that the durability be further extended while maintaining the above.

In recent years, in order to reduce the manufacturing cost of the electrophotographic light-receiving member, for example, the electrophotographic light-receiving member is deposited at a high deposition rate 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 non-uniformity occurs in the film quality, or a minute crack or peeling occurs in the A-Si film due to stress inside the film, thereby reducing the yield in productivity. .

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

The present invention has been made in view of the above points, and has various problems in a light receiving member for electrophotography having a conventional light receiving layer composed of a material containing silicon atoms as a base material as described above. It is intended to solve the problem. That is, the main object of the present invention is electrical, optical,
The photoconductive properties are virtually always stable without depending on the usage environment, are excellent in light fatigue resistance, do not cause deterioration phenomenon even after repeated use, and have no image defects or changes in image flow over a long period of use. , High concentration, particularly excellent in durability and moisture resistance, and a residual potential is hardly observed, and a light receiving member for electrophotography having a light receiving layer composed of a material containing silicon atoms as a base material has a good yield. To provide.

[0023] Another object of the present invention is to provide a silicon substrate having excellent adhesion between layers provided on a support and between the layers to be laminated, and having uniform and high quality. An object of the present invention is to provide an electrophotographic light-receiving member having a light-receiving layer made of the following material.

Still another object of the present invention is to provide a photoreceptor for electrophotography, which has a sufficient charge retention ability during the charging process for forming an electrostatic image and clearly produces halftones. And a photoreceptor composed of a silicon atom-based material exhibiting excellent electrophotographic properties to which a normal electrophotographic method can be applied very effectively so that a high-quality image with high resolution can be easily obtained. An object of the present invention is to provide an electrophotographic light-receiving member having a layer.

[0025]

According to the present invention, there is provided a method for forming a light receiving member for electrophotography, comprising forming a photoconductive layer and a surface layer on a conductive support in order. In the method, the photoconductive layer is based on silicon atoms, contains at least carbon atoms and hydrogen atoms throughout the entire layer, distributes the carbon atoms non-uniformly in the layer thickness direction, and has a content of the conductive layer. A non-single-crystal material in which the carbon atoms are distributed so as to be more on the side of the support and less on the side of the surface layer, and the surface layer has silicon atoms as a base material, carbon atoms, hydrogen atoms, A non-single-crystal material containing a halogen atom and an element belonging to Group 3B of the Periodic Table at the same time, containing an oxygen atom and / or a nitrogen atom, and increasing the formation rate of the deposited film of the photoconductive layer in the layer thickness direction. Change the said Faster in conductive support side, and forming the photoconductive layer so as to slow down at the surface layer side.

Further, 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 throughout the entire layer, the carbon atoms are unevenly distributed in the layer thickness direction, and the content is large on the conductive support side,
A non-single crystal material in which the carbon atoms are distributed so as to be reduced on the side of the first region of the photoconductive layer, wherein the first region of the photoconductive layer contains 1 to 40 atomic% of hydrogen atoms; It is also characterized by being composed of a material.

Embodiments of the present invention include the following.

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

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

3. The photoconductive layer may contain fluorine atoms.

4. The fluorine atoms in the photoconductive layer may be unevenly distributed in a 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 unevenly distributed in a layer thickness direction.

7. The carbon atom, the hydrogen atom, the halogen atom and the element belonging to Group 3B of the Periodic Table in the surface layer;
And at least one of oxygen atoms and / or nitrogen atoms may be distributed in the layer thickness direction.

8. The content of the carbon atoms in the surface layer at or near the outermost surface in the surface layer is 70 to 90 with respect to the sum of the content of the silicon atoms and the content of the carbon atoms.
Atomic% may be used.

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

[0037]

In the present invention, the photoconductive layer is formed such that the distribution of carbon atoms changes continuously from the side of the conductive support in the layer thickness direction.
And the transport of the generated charges, which are important functions for the electrophotographic photoreceptor member, can be smoothly connected, and a so-called function-separated type photoreceptor in which the conventional charge generation layer and the charge transport layer are separated. This prevents a charge running failure due to a difference in an optical energy gap between the charge generation layer and the charge transport layer, which has been a problem in the member, and contributes to improvement in photosensitivity and reduction in residual potential. In particular, in the case where the photoconductive layer is composed of the two regions described above, by providing the photoconductive layer first region containing no carbon atoms on the surface layer side, the absorptance of long-wavelength light is improved, and further light An improvement in sensitivity can be achieved.

Further, since the photoconductive layer contains carbon atoms, the dielectric constant of the light receiving layer can be reduced, so that the capacitance per layer thickness can be reduced, and a high charging ability can be realized. However, a remarkable improvement in light sensitivity is observed, and the withstand voltage against a high voltage is further improved.

Further, by providing 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 performance is improved and the adhesion between the support and the photoconductive layer is improved. In addition, peeling of the film and generation of minute defects can be suppressed.

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

The effect of this effect is that the speed of forming a deposited film on or near the surface on the surface layer side is 30 to 90 times the speed of forming a deposited film on or near the surface on the conductive support side.
%, It becomes more noticeable.

In the present invention, it is also effective to include a fluorine atom in the photoconductive layer. Fluorine atoms have the effect of suppressing the aggregation of carbon and hydrogen atoms contained in the photoconductive layer and reducing the localized level density within the band gap,
Ghosts and halftone unevenness are further improved.

Further, in the present invention, it is also effective to non-uniformly distribute at least the fluorine atoms contained in the photoconductive layer in the layer thickness direction. By distributing the fluorine atoms non-uniformly in the layer thickness direction, the change of the internal stress on the substrate side and the surface layer side caused by the change of the carbon atom content in the layer thickness direction is further reduced. Defects in the deposited film are reduced and 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 use environment of the light receiving member, 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 is more effectively reduced by a synergistic effect with fluorine atoms. Suppresses structural defects in the film. For this reason, the potential shift which is a problem in the A-SiC-based photoconductive layer is improved.

In addition, in the present invention, by distributing at least the oxygen atoms contained in the photoconductive layer non-uniformly in the layer thickness direction, the stress of the deposited film can be alleviated more effectively. Can be greatly improved. For this reason, especially in order to suppress the deterioration of the photoconductive layer due to continued use for a long period of time, it is possible to greatly improve the electrophotographic characteristics such as sensitivity, residual potential and potential shift after long-term use.

According to the present invention, high chargeability, high sensitivity, low residual potential, no ghost or halftone unevenness, and uneven image density between copied images, and durability is improved while maintaining excellent electric characteristics. Thus, it is possible to obtain a light receiving member for electrophotography which is significantly improved, and it is possible to greatly improve the yield in productivity.

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

In the present invention, a carbon atom, a hydrogen atom, a halogen atom and an element belonging to Group 3B of the periodic table are simultaneously contained in the surface layer, and an oxygen atom and / or a nitrogen atom are contained. Due to the synergistic effect, the surface strength and the electric pressure resistance are dramatically improved. Therefore, by improving the surface strength, it is possible to prevent the generation of surface scratches due to additives of the recycled paper even when the recycled paper is used at the time of durability. Further, it is possible to effectively prevent the sizing agent such as rosin, which is often contained in the recycled paper, from adhering to the surface of the electrophotographic light receiving member, and to eliminate the fusion of the toner and the flow of images during long-term use. Further, by improving the electric withstand voltage, even if spherical projections, which are abnormal growth of the film, are present to some extent, they can be very rarely generated as image defects such as “spots”. In addition, at the time of endurance, even if the separation charger causes abnormal discharge in the electrophotographic process, a part of the electrophotographic light receiving member is not destroyed, and the occurrence of "leak spots" can be extremely reduced. .

The same effect can be obtained irrespective of whether oxygen atoms or nitrogen atoms are contained in the surface layer, and the effect remains the same even if both are contained simultaneously.

Hereinafter, the light receiving member for electrophotography of the present invention will be described in detail with reference to the drawings.

FIGS. 1 and 2 are schematic diagrams schematically illustrating a preferred layer structure of the light receiving member for electrophotography according to the present invention. The electrophotographic light-receiving member 10 shown in FIG. 1 has a layer structure including 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. FIG. 2 shows an example in which the photoconductive layer 12 in FIG. 1 is composed of the second photoconductive layer region 15 and the first photoconductive layer region 16.

The conductive support 1 used in the present invention
For example, Al, Cr, Mo, Au, In,
Examples include metals such as Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Further, at least the side on which at least a photoconductive layer is formed of a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, or an electrically insulating support such as glass or ceramics. A support whose surface has been subjected to a conductive treatment can also be used. In the case of using an electrically insulating support, it is more preferable that the surface opposite to the side on which the photoconductive layer is formed is subjected to a conductive treatment.

The shape of the conductive support 11 can be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness thereof can be used to form the electrophotographic light-receiving member 10 as desired. In the case where flexibility as the electrophotographic light receiving member 10 is required, the thickness should be as thin as possible within a range where the function as the conductive support 11 can be sufficiently exhibited. Can be. However, it is usually required to be 10 μm or more from the viewpoint of production and handling of the conductive support 11 or mechanical strength.

In particular, when image recording is performed using coherent light such as laser light, the surface of the conductive support 11 is removed for the purpose of eliminating image defects due to so-called interference fringe patterns appearing in a visible image. May be provided with irregularities. Such irregularities are disclosed in JP-A-60-168156 and JP-A-60-178457.
And JP-A-60-225854. In addition, as another method for eliminating the image defect due to the interference fringe pattern, a concave-convex shape formed by a plurality of spherical trace depressions may be provided on the surface of the conductive support 11.
That is, the surface of the conductive support 11 is provided with irregularities due to the spherical trace depressions smaller than the resolution required for the electrophotographic light receiving member. Such irregularities can be formed by the method described in JP-A-61-231561.

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

The carbon atoms contained in the photoconductive layer 12 form a distribution, and the distribution is non-uniform in the thickness direction of the layer. The distribution is such that the ratio is high and decreases as the distance from the conductive support increases. When the carbon atom content is less than 0.5 atomic% at or near the surface on the side where the conductive support 11 is provided, if the content is less than 0.5 atomic%, the adhesion to the conductive support 11 and the prevention of charge injection are prevented. The function deteriorates, and the effect of improving the charging ability due to the decrease in the capacitance is lost. Also
If it exceeds 50 atomic%, a residual potential is generated. For this reason, practically 0 ... It is 5 to 50 atomic%, preferably 1 to 40 atomic%, and most preferably 1 to 30 atomic%. Further, in the present invention, it is necessary that the photoconductive layer 12 contains hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the quality of the layer, in particular, the photoconductivity and the charge retention characteristics. This is because it is essential for improvement. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality. Therefore, it is desirable that the amount of hydrogen atoms contained be adjusted according to the carbon content. Therefore, the content of hydrogen atoms on or near the surface of the conductive support 11 is preferably 1 to 40 atomic%, more preferably 5 to 35 atomic%, and most preferably 10 to 30 atomic%.

In the present invention, the stress of the deposited film is reduced by changing the speed of forming the deposited film of the photoconductive layer 12 in the thickness direction, and increasing the speed on the conductive support 11 side and decreasing the speed on the surface layer 13 side. It is possible to more effectively mitigate and improve the denseness of the deposited film, to further improve image characteristics such as halftone unevenness, and to significantly suppress the peeling of the deposited film and the occurrence of minute defects. it can. Further, electrical characteristics such as charging ability can be further improved.

The effect of this is that the speed of forming a deposited film on the surface on the side of the surface layer 13 or near the surface is reduced by the conductive support 1.
30 to the formation rate of the deposited film on or near the surface on one side
Appearing more remarkably by setting it to 90%. If it is lower than 30%, the stress of the deposited film is not sufficiently relieved, and the effect of suppressing the peeling of the deposited film and the defects becomes insufficient.
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 improvement of the image characteristics such as halftone unevenness and the electric characteristics such as charging ability are not sufficient.

It is also effective that the photoconductive layer 12 of the present invention contains fluorine atoms. Fluorine atoms are contained in the photoconductive layer 12.
Suppress aggregation of carbon and hydrogen atoms contained in,
This has the effect of reducing the density of localized states in the band gap, and further improves ghosts and halftone unevenness. If the content of fluorine atoms in the photoconductive layer 12 is less than 1 atomic ppm, the effect of improving ghost and halftone unevenness due to the fluorine atoms cannot be sufficiently exhibited, and if it exceeds 95 atomic ppm, the film quality deteriorates conversely. The ghost phenomenon is caused. 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 in the above-mentioned range, by setting the content of fluorine atoms in the above range, the photoconductive characteristics, image characteristics and durability are remarkably improved. It was confirmed that.

Further, in the present invention, it is also effective to distribute at least the fluorine atoms contained in the photoconductive layer 12 non-uniformly in the layer thickness direction. By distributing the fluorine atoms non-uniformly in the layer thickness direction, it is possible to reduce the change in the internal stress on the conductive support 11 side and the surface layer 13 side caused by the change in the carbon atom content in the layer thickness direction. Therefore, 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
It is also possible to include oxygen atoms in 2, in which case the stress of the deposited film is more effectively alleviated by the synergistic effect with the fluorine atoms and the structural defects of the film are suppressed. For this reason, 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
If it is less than m, it is not possible to sufficiently improve the adhesion of the film and to suppress the occurrence of abnormal growth, and the potential shift becomes large. If it exceeds 5000 atomic ppm, the electric characteristics for responding to the high speed of electrophotography will not be sufficient.
Therefore, the content of oxygen atoms is 10 to 5000 atomic ppm
It is preferred that

In addition, in the present invention, by distributing at least oxygen atoms contained in the photoconductive layer 12 non-uniformly in the layer thickness direction, the stress of the deposited film can be more effectively relieved. It is possible to significantly suppress structural defects of the film. For this reason, deterioration of the photoconductive layer due to continuous use for a long period of time is particularly suppressed, and electrophotographic characteristics 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 a method of forming a vacuum deposited film by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. Specifically, for example, an AC discharge CVD method such as a glow discharge method (low-frequency CVD method, high-frequency CVD method, microwave CVD method, or the like)
Method, DC discharge CVD method, etc.), sputtering method, vacuum deposition method, ion plating method, optical CVD
And a thin film deposition method such as a thermal CVD method. These thin film deposition methods are appropriately selected depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics required for the electrophotographic light-receiving member to be manufactured, but have desired characteristics. The glow discharge method, the sputtering method, and the ion plating method are preferable because the conditions for producing the electrophotographic light-receiving member are relatively easily controlled. These methods may be used together in the same apparatus system to form a thin film deposition. For example, to form an A-SiC (H) photoconductive layer by a glow discharge method, a source gas for supplying Si capable of supplying silicon atoms (Si) and a carbon gas (C) are basically supplied. The raw material gas for supplying C and the raw material gas for supplying H that can supply hydrogen atoms (H) are introduced into a reaction vessel capable of reducing the pressure in a desired gas state, and are introduced into the reaction vessel. Glow discharge may be caused to form a layer made of A-SiC (H) on the surface of a predetermined conductive support which is previously set at a predetermined position.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H
₈ , silicon hydrides (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified can be used effectively. Among them, ease of handling at the time of forming a layer, good Si supply efficiency, etc. In view of the above, SiH ₄ and Si ₂ H ₆ are preferred. These source gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

In the present invention, it is preferable that a material that can be a raw material for introducing carbon atoms be a gaseous material at normal temperature and normal pressure or a material that can be easily gasified at least under layer forming conditions.

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

Examples of the raw material gas containing Si and C as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

[0070] In addition, from the viewpoint in addition to the introduction of the carbon atoms (C), allows the introduction of fluorine atoms, CF _4, C ₂
Fluorocarbon compounds such as F ₆ , C ₃ F ₈ and C ₄ F ₁₀ , CHF ₃
And the like.

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

The fluorine-supplying gas used in the present invention is preferably a gaseous or gasifiable fluorine compound such as fluorine gas, fluorinated compound, interhalogen compound containing fluorine, or silane derivative substituted by fluorine. Are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a fluorine atom, which contains a silicon atom and a fluorine atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the fluorine compound that can be suitably 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, that is, a silane derivative substituted with a fluorine atom, specifically,
Silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be mentioned as a preferable example. When a characteristic electrophotographic light-receiving member of the present invention is formed by glow discharge or the like by employing such a silicon compound containing a fluorine atom, a silicon hydride gas as a Si supply gas is not used. However, nc-SiC containing a fluorine atom is formed on a predetermined conductive support 11.
The photoconductive layer 12 made of (H, F) can be formed. However, in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the formed photoconductive layer 12, 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 a single species but also with a plurality of species at a predetermined mixture ratio.

In the present invention, the above-mentioned fluoride or silicon compound containing fluorine is effectively used as the fluorine atom supply gas.
Fluorine-substituted silicon hydrides, such as HF, SiH ₃ F, SiH ₂ F ₂ , and SiHF ₃ , and substances in a gaseous state or capable of being gasified can also be cited as effective starting materials for forming a photoconductive layer. Of these substances, fluorides containing hydrogen atoms are introduced into the photoconductive layer simultaneously with the introduction of fluorine atoms into the layer, and at the same time, hydrogen atoms that are extremely effective in controlling electrical or photoelectric characteristics are introduced. In the present invention, it is used as a suitable gas for supplying fluorine atoms.

In the present invention, starting materials that can be effectively used as a gas for introducing oxygen atoms (O) include:
For example, oxygen, ozone, nitrogen monoxide, nitrogen dioxide, nitrogen monoxide, nitrogen trioxide, nitrogen tetroxide, nitrogen pentoxide and the like can be mentioned.

In addition, since oxygen atoms (O) can be introduced in addition to carbon atoms (C), C
O, CO _{2 and the} like can be mentioned.

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, a raw material used for containing hydrogen atoms or fluorine atoms, It is only necessary to control the amount of gas introduced into the reaction vessel, the discharge power, and the like. Further, in the present invention, it is preferable that the photoconductive layer 12 contains an atom (M) for controlling conductivity as necessary. The atoms (M) for controlling the conductivity may be contained in the photoconductive layer 12 in a state of being distributed uniformly and evenly, or there may be portions which are contained in a non-uniform distribution state in the layer thickness direction. You may.

The atom (M) for controlling the conductivity can be a so-called impurity in the field of semiconductors, and is an element belonging to Group 3B of the Periodic Table that provides p-type conductivity (hereinafter referred to as “Group 3B”). An element) or an element belonging to Group 5B of the Periodic Table that gives n-type conduction characteristics (hereinafter abbreviated as “Group 5B element”).
As the Group 3B element, specifically, B, Al, Ga,
In, Tl, etc., and B, Al, Ga are particularly preferable. As the Group 5B element, specifically, P, As, S
b, Bi, etc., and P and As are particularly preferable.

The content of atoms (M) for controlling the conductivity contained in the photoconductive layer 12 is preferably 1 × 10 ^−3.
-5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ^{-2 -1}
× 10 ⁴ atomic ppm, optimally 1 × 10 ^{-1 to} 5 × 10 ³ atomic p
pm 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) in the photoconductive layer 12 is as follows:
Preferably, the concentration is 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm. When the carbon atom content exceeds 1 × 10 ³ atomic ppm, the atomic (M) content is preferably 1 × 10 ³ atomic ppm. 1
It is desirable that the concentration be 0 ^{-1 to} 5 × 10 ⁴ atomic ppm.

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 is formed in a gas state as a raw material for introducing a Group 3B element or a raw material for introducing a Group 5B element when forming a layer. It may be introduced together with another gas for forming the photoconductive layer 12 therein. As a source material for introducing a Group 3B element or a source material for introducing a Group 5B element, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified under at least layer forming conditions is employed. Is desirable.

As a raw material for introducing a Group 3B element,
Specifically, for example, for boron atom introduction, 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 borohydride such as B ₆ H ₁₄ and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . Other raw materials for introducing a Group 3B element include AlCl ₃ , GaC
l ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like.

[0082] As raw material for the Group 5B element introduction, those effectively used in the present invention, for example, as the use of phosphorus atom introduction, PH _3, P ₂ H _4, etc. phosphorus hydride, PH _{4
I, PF 3, PF 5,} PCl 3, PCl 5, PBr 3, PB
and phosphorus halides such as r ₅ and PI ₃ . As a raw material 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
Cl ₃ , BiBr _{3 and the} like can be mentioned.

The atoms controlling these conductivity (M)
Raw materials for introduction may be H ₂ , He, A
It may be used after being diluted with a gas such as r or Ne.

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 about 0.1 to 10,000 ppm. Is also good. The elements may be uniformly distributed in the photoconductive layer 12 or may be uniformly distributed in the photoconductive layer 12, but are non-uniformly distributed in the layer thickness direction. There is no problem if there is a part contained in the state.

As the Group 1A elements, specifically, Li,
Na and K can be mentioned, and as the Group 2A element,
Be, Mg, Ca, Sr and Ba can be mentioned.
The group 6A element includes Cr, Mo, and W, and the group 8 element includes Fe, Co, Ni, and the like.

In the present invention, the thickness of the photoconductive layer 12 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 5 to 50 μm.
More preferably, the thickness is 10 to 40 μm, and most preferably, 15 to 30 μm.

A having properties capable of achieving the object 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 usually, preferably 20 to 500 ° C., more preferably 50 to 480 ° C.
° C, optimally between 100 and 450 ° C.

The optimum pressure of the gas pressure in the reaction vessel is also appropriately selected according to the layer design, but in the normal case, preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to} 3 To
rr, optimally 1 × 10 ^-4 to 1 Torr.

In the present invention, the layer forming factors include the above-mentioned numerical ranges of the surface temperature and the gas pressure of the conductive support 11, but these factors are not usually determined independently and separately. It is desirable to determine the optimal values of these factors based on their mutual and organic relationships to form photoconductive layer 12 having the desired properties.

In the present invention, at least an aluminum atom is provided on the conductive 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 second photoconductive layer region 15 and a first photoconductive layer 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 above-described method. The photoconductive layer first region 16 is made of A-Si (H) containing silicon atoms and hydrogen atoms as constituent elements, and has desired photoconductive properties, particularly, charge generation properties and charge transport properties.

The first region 16 of the photoconductive layer is composed of silicon atoms,
Non-single crystalline consisting of hydrogen atoms, hydrogen atoms are 1 to 40
Atomic% is formed. This photoconductive layer first region 16
Is provided to efficiently generate photocarriers, enhance absorption of long-wavelength light, and improve sensitivity. 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 photoconductive layer second region 15, an unexpected effect that ghost is reduced can be obtained.

The above-described photoconductive layer 12 (photoconductive layer second region 1)
5) Similarly, the first region 16 of the photoconductive layer is also produced by a vacuum deposition film forming method by appropriately setting numerical conditions of film formation parameters so as to obtain desired characteristics. Specifically, for example, in order to form the photoconductive layer first region 16 of A-Si (H) by a glow discharge method, a source gas for supplying Si that can supply silicon atoms (Si) is basically used. And a source gas for supplying hydrogen capable of supplying hydrogen atoms (H) is introduced in a desired gas state into a reaction vessel capable of reducing the pressure therein, and a glow discharge is generated in the reaction vessel. The second photoconductive layer on the surface of the predetermined support provided at the position
A layer made of A-Si (H) may be formed over the region 15.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H
₈ , silicon hydrides (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified can be used effectively. Among them, ease of handling at the time of forming a layer, good Si supply efficiency, etc. In view of the above, SiH ₄ and Si ₂ H ₆ are preferred. These source gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the first region 16 of the photoconductive layer to be formed, hydrogen gas or a silicon compound gas containing hydrogen atoms is added to these gases. Also, it is preferable to form a layer by mixing desired amounts. Each gas is not limited to a single species, and may be a mixture of a plurality of species at a predetermined mixture ratio.

In order to introduce hydrogen atoms (H) into the photoconductive layer first region 16 structurally, in addition to the above, H ₂ , or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ a silicon hydride of H _10, etc., can also be carried out be to generate discharge by the silicon or silicon compound coexist in the reaction vessel for supplying Si.

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 to contain the hydrogen atoms What is necessary is just to control the amount of introduction into the fuel cell and the discharge power.

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

The content of the atom (M) for 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
0 ⁴ atomic ppm, being optimally with 1 × 10 ^-1 ~5 × 10 ³ atomic ppm is desirable. To structurally introduce atoms for controlling conductivity into the photoconductive layer first region 16, the above-described photoconductive layer 12 is used.
The method described in the method of forming is adopted.

Further, the first region 16 of the photoconductive layer also contains at least one element selected from the above-mentioned groups 1A, 2A, 6A and 8 of the periodic table in an amount of about 0.1 to 10,000 ppm. You may. The element is the first region 16 of the photoconductive layer.
It may be distributed evenly and uniformly, or may be contained evenly, but may contain a portion that is distributed unevenly 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 from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
5-15 μm, more preferably 1-10 μm, optimally 1-5 μm
It is desirable that

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 usually, preferably 20 to 500 ° C., more preferably 50 to 480 ° C.
° C, optimally between 100 and 450 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected in an optimum range according to the layer design. In a normal case, the gas pressure 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.

In the present invention, the above-mentioned numerical values of the surface temperature and the gas pressure of the conductive support 11 can be cited as layer forming factors, but these factors are not usually determined independently and separately. It is desirable to determine the optimal values of these factors based on their mutual and organic relationships to form photoconductive layer first region 16 having the desired properties.

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

The surface layer 13 of the present invention is made of a non-single-crystal material having silicon and hydrogen atoms as constituents, and simultaneously contains at least carbon atoms, halogen atoms and elements belonging to Group 3B of the periodic table. And further contains an oxygen atom and / or a nitrogen atom.

A silicon atom contained in the surface layer 13;
A hydrogen atom, a halogen atom, a Group 3B element of the periodic table, a carbon atom, an oxygen atom and / or a nitrogen atom may be contained in the layer in a uniformly distributed state, or in a layer thickness direction. However, there may be a portion that is contained in a state of being unevenly distributed.

Since the surface layer 13 simultaneously contains a silicon atom, a hydrogen atom, a carbon atom, a halogen atom, a Group 3B element of the Periodic Table, and an oxygen atom and / or a nitrogen atom, a synergistic effect of these atoms is obtained. The electric withstand voltage is improved, and the effect of suppressing the occurrence of “pocks” and “leak spots” can be obtained even during long-term use.

In the present invention, the surface layer contains a carbon atom, a hydrogen atom, a halogen atom and an element belonging to Group 3B of the Periodic Table at the same time, and contains an oxygen atom and / or a nitrogen atom to provide a surface strength. Is improved, even when using recycled paper during durability,
It effectively prevents surface scratches caused by additives of recycled paper, and adhesion of a sizing agent such as rosin, which is often contained in recycled paper, to the surface of a light receiving member for electrophotography. Image deletion can be eliminated.

The same effect can be obtained regardless of whether oxygen atoms or nitrogen atoms are contained in the surface layer 13, and the effect is not changed even if both are contained simultaneously.

In the surface layer 13, if the content of carbon atoms on the outermost surface or in the vicinity of the outermost surface is 70 atom% or more with respect to the sum of the content of silicon atoms and the content of carbon atoms, the surface strength is increased. Can be effectively prevented from being injected from the surface when the charging treatment is further performed, so that the charging ability and durability can be improved. On the other hand, when the carbon atom content exceeds 90 atom% with respect to the above sum, the sensitivity is lowered. Therefore, the content of carbon atoms at or near the outermost surface of the surface layer 13 is as follows:
Preferably from 70 to 90 at.%, More preferably from 70 to 90 at.
It is desirable that the content be ~ 86 at%, optimally 70-83 at%.

The oxygen atom content is preferably 1 × 10 ^{-4 to} 3
Desirably, it is 0 atomic%, and optimally 3 × 10 ^{-4 to} 20 atomic%. The content of nitrogen atoms is preferably 1 × 10 ⁻⁴ to 30 atomic%, and most preferably 3 × 10 ^{−4 to} 20 atomic%.
In addition, when simultaneously containing an oxygen atom and a nitrogen atom,
It is desirable that the sum of these contents is preferably 1 × 10 ⁻⁴ to 30 atomic%, and most preferably 3 × 10 ^{−4 to} 20 atomic%.

The hydrogen atoms and halogen atoms contained in the surface layer 13 in the present invention are A-SiC (H,
X) compensates for dangling bonds existing in X), is effective in improving the film quality, and reduces carriers trapped at the interface between the photoconductive layer 12 and the surface layer 13, thereby improving image deletion. Further, since the halogen atoms improve 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 atomic% or less, and the sum of the content of hydrogen atoms and halogen atoms is preferably 15 to 80 atomic%, more preferably 20 to 75 atomic%. %, Optimally between 25 and 70 atomic%.

Specific examples of Group 3B elements of the periodic table include B, Al, Ga, In, and Tl.
l and Ga are preferred. The content of Group 3B element of the periodic table is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁵ atomic ppm, more preferably 5 × 1
0 ^{-5 to} 5 × 10 ⁴ atomic ppm, optimally 1 × 10 ^{-4 to} 3 × 10 ⁴ atomic ppm
It is desirable that

Further, in the present invention, the above-described periodic table of Groups 1A, 2A, 6A, and 8
0.1-10000pp at least one element selected from the group
m may be contained. These elements are contained in the surface layer 1
3 may be distributed uniformly and evenly, or may be contained evenly, but may contain a part that is distributed unevenly in the layer thickness direction. .

Examples of the substance that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
₈ , silicon hydrides (silanes) in a gaseous state such as Si ₄ H ₁₀ or the like, which can be gasified, can be used effectively. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. These source gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

In the present invention, as a raw material for introducing carbon atoms, it is preferable to employ a gaseous substance at normal temperature and pressure or a substance which can be easily gasified at least under layer forming conditions.

Examples of the raw material for carbon atom (C) introduction include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 carbon atoms having C and H as constituent atoms. To 3 acetylene-based hydrocarbons. Specifically, examples of the saturated hydrocarbon include methane, ethane, propane, n-butane, and pentane. Examples of the ethylene-based hydrocarbon include ethylene, propylene, 1-butene,
-Butene, isobutylene, pentene and acetylene-based hydrocarbons include acetylene, methylacetylene, butyne and the like.

Examples of the source gas containing Si and C as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

In addition to these, CF ₄ and C ₂ can be introduced because fluorine atoms can be introduced in addition to carbon atoms (C).
Fluorocarbon compounds such as F ₆ , C ₃ F ₈ and C ₄ F ₁₀ , CHF ₃
And the like.

In the present invention, starting materials that can be effectively used as a gas for introducing oxygen atoms (O) and / or nitrogen atoms (N) include, for example, oxygen, ozone,
Examples include nitrogen, nitrogen monoxide, nitrogen dioxide, nitrogen monoxide, nitrogen trioxide, nitrogen trioxide, nitrogen pentoxide, and the like.

In addition, compounds such as CO and CO ₂ can be cited in that oxygen atoms can be introduced in addition to carbon atoms.

As the gas for supplying a halogen atom used in the present invention, a gaseous or gasizable halogen compound such as a halogen gas, a halide, an interhalogen compound, or a silane derivative substituted with halogen is preferable. No. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , and Br.
Inter-halogen compounds such as F 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 so-called halogen atom, specifically, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be preferably mentioned. When the characteristic electrophotographic light receiving member 10 of the present invention is formed by glow discharge or the like by employing such a silicon compound containing a halogen atom, a silicon hydride gas is used as a gas for supplying Si. Although the surface layer 13 containing a halogen atom can be formed without the above, the gas is further added to these gases in order to further facilitate the control of the introduction ratio of hydrogen atoms introduced into the formed surface layer 13. 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 a single species but also with a plurality of species at a predetermined mixture ratio.

In the present invention, the above-mentioned halides or halogen-containing silicon compounds are effectively used as the halogen atom supply gas. In addition, HF, SiH ₃ F, SiH ₂ F ₂ , SiH
Substances in a gaseous state or capable of being gasified, such as fluorine-substituted silicon hydrides such as F _3, can also be mentioned as effective surface layer forming raw materials. Of these substances, halides containing hydrogen atoms are introduced into the layer at the time of forming the surface layer, and at the same time, hydrogen atoms which are extremely effective in controlling electric or photoelectric characteristics are also introduced. In the present invention, it is used as a suitable halogen atom supply gas.

In order to introduce hydrogen atoms into the surface layer 13 structurally, in addition to the above, H ₂ , SiH ₄ , Si
_The discharge can also be performed by causing silicon hydride such as ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in a reaction vessel to generate a discharge.

The hydrogen atoms contained in the surface layer 13 and / or
Alternatively, in order to control the amount of the halogen atoms, for example, the temperature of the conductive support 11, the amount of the raw material used to contain the hydrogen atoms or the halogen atoms, the discharge power, and the like are controlled. I just need.

In the present invention, the thickness of the surface layer 13 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 0.01 to 30 μm.
m, more preferably 0.05 to 20 μm, and most preferably 0.1 to 10 μm.

In order to form the surface layer 13 having 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 influencing the characteristics of the surface layer. It is.

The surface temperature of the conductive support 11 is appropriately selected in an optimum range, but is preferably 20 to 500 ° C., more preferably 50 to 480 ° C., and most preferably 100 to 450 ° C.

The gas pressure in the reaction vessel is also appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 10 Torr, more preferably 5 × 10 ^{−5 to} 3 Torr, and most preferably 1 × 10 ⁻⁴ to Preferably, it is 1 Torr.

In the present invention, the important factors for forming the surface layer 13 include the above-mentioned numerical ranges of the surface temperature and the gas pressure of the conductive support 11, and these factors are usually independently and separately. Rather than being determined, it is desirable to determine the optimal values of these factors based on their mutual and organic relevance to form a surface layer 13 having the desired properties.

Hereinafter, an apparatus and a method for forming a deposited film by the high-frequency plasma CVD method and the microwave plasma CVD method will be described in detail.

FIG. 4 shows a high-frequency plasma CVD (hereinafter referred to as “RF
FIG. 1 is a schematic configuration diagram illustrating an example of an apparatus for manufacturing a light-receiving member for electrophotography by a method described as “-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 a reaction vessel 4111 in the deposition apparatus 4100.
3. A source gas introduction pipe 4114 is installed, and a high frequency matching box 4115 is connected.

The raw material gas supply device 4200 includes SiH ₄ ,
H _2, CH _4, NO, cylinder material gas such as NH _3, SiF ₄ 4221~4226 and the valve 4231～4236,4
241 to 4246, 4251 to 4256 and mass flow controllers 4211 to 4216, and a cylinder of each raw material gas is supplied to the reaction vessel 41 via a valve 4260.
11 is connected to a gas introduction pipe 4114.

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

First, the cylindrical support 4112 is set in the reaction vessel 4111, and the inside of the reaction vessel 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.
2 is controlled to a predetermined temperature of 20 to 500 ° C.

A source gas for forming a deposited film is supplied to a reaction vessel 411.
In order to allow the gas to flow into
4236, it was confirmed that the leak valve 4117 of the reaction vessel was closed.
46, outflow valves 4251 to 4256, auxiliary valve 42
First, the main valve 4118 is opened and the reaction vessel 4111 and the gas pipe 41 are opened.
Exhaust 16.

Next, the reading of the vacuum gauge 4119 was about 5 × 10 ^−5.
Auxiliary valve 4260 and outflow valve 4 at Torr
251 to 4256 are closed. After that, gas cylinder 422
Each gas is introduced from 1 to 4226 by opening valves 4231 to 4236, and each gas pressure is adjusted to ² kg / cm ² by pressure regulators 4261 to 4266. Next, inflow valve 4
By gradually opening 241 to 4246, each gas is introduced 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 temperature of 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.
Introduce into 111. Next, mass flow controller 4
According to 211 to 4216, adjustment is performed so that each source gas has a predetermined flow rate. At this time, the vacuum gauge 4119 is set so that the pressure in the reaction vessel 4111 becomes a predetermined pressure of 1 Torr or less.
And adjust the opening of the main valve 4118. When the internal pressure is stabilized, an RF power source (not shown) is set to a predetermined power, and RF power is introduced into the reaction vessel 4111 through the high-frequency matching box 4115 to generate RF glow discharge. The source gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposition film containing silicon as a main component is formed on the cylindrical support 4112. After the formation of the desired film thickness, the supply of the 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 multilayer structure is formed.

In forming each layer, it goes without saying that all outflow valves other than necessary gas are closed. In addition, each gas is supplied to the reaction vessel 4111.
, Outflow valves 4251 to 4256 to reaction vessel 411
In order to avoid remaining in the piping leading to 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 once evacuated to a high vacuum as necessary. 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 types and valve operations are changed according to the production conditions of each layer.

The heating method of the cylindrical support may be carried out by using a heating element having a vacuum specification. Specific examples of the heating element having such a vacuum specification include a winding heater of a sheath-like heater, a plate-like heater, and a like. Examples of the heating element 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 formed by a heat exchange unit 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 resins, and the like can be used. In addition to the above, a method is also used in which a container dedicated to heating is provided other than the reaction container 4111, and after the cylindrical support 4112 is heated, the cylindrical support is conveyed into the reaction container 4111 in a vacuum. .

Next, a method of manufacturing an electrophotographic light-receiving member formed by a 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 deposited film for a light receiving member for electrophotography by the μW-PCVD method. ) Shows a side cross section, and (b) shows a XX ′ cross section. FIG. 6 is an explanatory view of an entire apparatus for manufacturing a light receiving member for electrophotography by the μW-PCVD method.

By replacing the deposition apparatus 5100 by the μW-PCVD method shown in FIG. 5 with the deposition apparatus 4100 shown in FIG.
An electrophotographic light-receiving member manufacturing apparatus having the following configuration by the μW-PCVD method shown in FIG. 6 can be obtained.

The apparatus 5100 comprises a reaction vessel 5111 having a vacuum-tight structure and capable of reducing pressure, a supply apparatus 5200 for raw material gas, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. . The microwave power is efficiently transmitted through the reaction vessel 5111 into the reaction vessel, and
A microwave power supply (not shown) through a microwave introduction window 5112, a stub tuner (not shown), and an isolator (not shown) formed of a material (for example, quartz glass, alumina ceramics or the like) capable of maintaining vacuum tightness. ), A cylindrical support 5115 on which a deposited film is to be formed, a heater 5116 for heating the support, a source gas introduction pipe 5117, and an external electric bias for controlling the plasma potential. An electrode 5118 for supplying the gas is provided, and the inside of the reaction vessel 5111 can be evacuated through an exhaust pipe 5121 by an exhaust device (not shown) (for example, a diffusion pump). The raw material gas supply device 4200 includes SiH ₄ , H ₂ , CH ₄ , N
O, cylinder material gas such as NH _3, SiF ₄ 4221~4
226 and valves 4231 to 4236, 4241 to 424
6, 4251 to 4256, mass flow controllers 4211 to 4216, and the like, and a cylinder for each source gas 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 a deposited film in the apparatus by the μW-PCVD method can be performed as follows.

First, the cylindrical support 5115 is set in the reaction vessel 5111, the support 5115 is rotated by the support rotating motor 5120, and the inside of the reaction vessel 5111 is exhausted by the exhaust device (not shown) through the exhaust pipe 5121. Evacuation is performed to adjust the pressure in the reaction vessel 5111 to 1 × 10 ⁻⁵ Torr or less. Subsequently, 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.

The raw material gas for forming the deposited film is supplied to the reaction vessel 511.
In order to make the gas flow into the valve 1, the gas cylinder valves 4231-4
236, confirming that the leak valve (not shown) of the reaction vessel is closed,
46, outflow valves 4251 to 4256, auxiliary valve 42
First, the main valve (not shown) is opened, and the reaction vessel 5111 and the gas pipe 51 are opened.
The inside of 22 is exhausted.

Next, a vacuum gauge (not shown) reads about 5 × 10 ⁻⁵ T
Auxiliary valve 4260 and outflow valve 4 at orr
251 to 4256 are closed. After that, gas cylinder 422
Each gas is introduced from 1 to 4226 by opening valves 4231 to 4236, and each gas pressure is adjusted to ² kg / cm ² by pressure regulators 4261 to 4266. Next, the inflow valve 4241
4246 are gradually opened, and each gas is introduced into the mass flow controllers 4211-4216.

After 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 temperature of 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 a discharge space 5130 in 111. Next, each source gas is adjusted by the mass flow controllers 4211 to 4216 so as to have a predetermined flow rate. At this time, the opening of the main valve (not shown) is adjusted while watching the vacuum gauge (not shown) so that the pressure in the reaction vessel 5111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stabilized, a microwave of frequency 500 MHz or more, preferably 2.45 GHz is generated by a microwave power supply (not shown), and microwave energy is introduced into the discharge space 5130 through the microwave introduction window 5112, Generates a microwave glow discharge. At the same time, the power supply 5119
For example, an electric bias such as a direct current is applied to 8. Thus, the raw material gas introduced into the discharge space 5130 is excited by the microwave energy and dissociated, and a deposited film mainly containing silicon 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 achieve uniform layer formation.

After the formation of the desired film thickness, the supply of the microwave 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 desired light-receiving layer having a multilayer structure is formed.

In forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed. In addition, each gas is supplied to the reaction vessel 5111.
, Outflow valves 4251 to 4256 to reaction vessel 511
In order to avoid remaining in the pipe reaching 1, the operation of closing the outflow valves 4251 to 4256, opening the auxiliary valve 4260, and further fully opening the main valve to once evacuate the system to a high vacuum is performed as necessary. .

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

The heating method of the cylindrical support 5115 may be performed by a heating element having a vacuum specification. Examples of such a heating element having a vacuum specification include a winding heater of a sheath-like heater and a plate-like heater. , 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 formed 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 resins, and the like can be used. In addition, a method other than providing a container dedicated for heating other than 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. .

[0165] 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, especially at 5 × 10 ⁻² Torr or less, when the pressure in the discharge space is three times or more the pressure outside the discharge space, the effect of improving the deposited film characteristics is particularly large.

As a method for introducing microwaves to the reaction vessel, a method using a waveguide 5113 can be mentioned, and a method for introducing microwaves into one or more microwave introduction windows 5112 can be used. 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), and polystyrene. Fewer materials are usually 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, any case may be used as long as the direction of the voltage does not change with time. For example, a constant voltage whose magnitude does not change with time, a pulsed voltage,
It is also effective with a pulsating voltage whose magnitude changes depending on the time rectified by the rectifier.

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

The size and shape of the electrode 5118 may be any as long as it does not disturb the discharge.
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 any particular limitation as long as the electric field is uniformly applied to the support.

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

[0172]

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

Example 1 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 as shown in Table 1.
A light receiving member for electrophotography was produced under the following production conditions. In this example, the flow rate of CH ₄ introduced during the formation of the photoconductive layer was changed linearly in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIG. At the same time, the flow rate of SiH ₄ introduced during the formation of the photoconductive layer was changed linearly in order to change the change pattern of the deposition rate of the photoconductive layer as shown in FIG. At this time, the carbon content on the surface of the photoconductive layer on the conductive support side should be about 30 atomic%, and the carbon content on the surface layer side relative to the deposition film formation rate (R1) on the conductive support side of the photoconductive layer. Film deposition rate (R2)
Was set to about 50%.

For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount of the standard sample and the prepared sample was determined from the ratio of signal intensities by Auger spectroscopy. . In measuring the deposition film formation rate, a deposition film sample was prepared in advance with the flow rate of SiH _{4 in the} photoconductive layer constant, and the thickness of the deposition film was measured by a stylus method to determine the deposition film formation rate.

[0175]

[Table 1] The manufactured photoreceptor for electrophotography was copied by Canon copier NP
-6650 was installed in an electrophotographic apparatus modified for experiments, and the electrophotographic properties such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness were evaluated. Each item is
Evaluation was made by the following method.

Charging Ability, Sensitivity, Residual Potential: Charging Ability: A photoreceptor for electrophotography was installed in an experimental device, a high voltage of +6 kV was applied to a charger, corona charging was performed, and a surface electrometer was used for electrophotography. The surface potential of the dark part of the light receiving member is measured.

Sensitivity: The photoreceptor for electrophotography is charged to a constant dark area surface potential. Then, the light image is immediately emitted.
The light image is filtered using a xenon lamp light source and a filter.
Light excluding light in a wavelength range of 550 nm or less was applied. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured by a surface electrometer. The exposure is adjusted so that the bright portion surface potential becomes a predetermined potential, and the exposure is used as the sensitivity.

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

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

Halftone Unevenness: A halftone chart made by Canon (part number FY9-9042) is placed on a platen.
Using a 0.05 mm circular area as one unit on the copy image obtained at the time of copying, 100 image densities were measured, and variations in the image densities were evaluated.

◎ indicates particularly good, 特 に indicates good, △ indicates no practical problem, and × indicates practical problem.

Next, the produced electrophotographic light-receiving member was installed in an electrophotographic apparatus in which a Canon copier NP-6650 was modified for an experiment, and an accelerated durability test corresponding to 3 million sheets was performed. An evaluation was performed. Table 4 shows the results.

Example 2 In the same manner 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 sequentially deposited on a conductive support. The formation was performed to produce a light receiving member for electrophotography. The light receiving member for electrophotography thus obtained was evaluated in the same manner as in Example 1. Table 4 shows the results.

[0184]

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

[0185]

[Table 3]

[0186]

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

Example 3 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
A light receiving member for electrophotography was produced on a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method under the production conditions shown in Table 5 according to the procedure described in detail above. When the same evaluation as in Example 1 was performed on the produced light receiving member for electrophotography, the same result as in Example 1 was obtained.

[0188]

[Table 5] Example 4 A deposited film was formed on a conductive support in the order of the photoconductive layer second region, the photoconductive layer first region, and the surface layer under the manufacturing conditions shown in Table 6 in the same manner as in Example 3. 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 result as in Example 1 was obtained.

[0189]

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

[0190]

[Table 7] Example 5 Using the apparatus for manufacturing a photoreceptor member for electrophotography shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, the RF glow discharge method was used to carry out a test according to the procedure described in detail above.
The electrophotographic light-receiving member 10 was produced under the following production conditions. In this embodiment, the flow rate of SiH ₄ introduced at the time of forming the photoconductive layer 12 is changed in order to change the change pattern of the formation speed of the deposited film of the photoconductive layer 12 as shown in FIGS. Photographic light receiving member 10 was produced. In any of the patterns, the ratio R2 /
R1 was set to about 50%. At this time, the photoconductive layer 1
The change pattern of the carbon content in Sample No. 2 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 atomic%.

For the measurement of the carbon content, a calibration curve of a standard sample was prepared by elementary analysis by Rutherford backscattering method, and the absolute value of the standard sample and the prepared sample was determined from the ratio of signal intensities by Auger spectroscopy. . In measuring the deposition film formation rate, a deposition film sample was prepared in advance with the flow rate of SiH _{4 in the} photoconductive layer constant, and the thickness of the deposition film was measured by a stylus method to determine the deposition film formation rate.

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

[0193]

[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 formation rate of the deposited film of the photoconductive layer was changed as shown in FIGS. At this time, the ratio R2 / R1 of the deposition film formation speed is 100% in FIG.
20%.

The thus-obtained electrophotographic light-receiving member 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 in the variation pattern of the deposition rate of the photoconductive layer of the present invention, better results were obtained in both electrical and image characteristics than in Comparative Example 3.

[0196]

[Table 9] Example 6 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 as shown in Table 1.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In the present embodiment, SiH ₄ to be introduced during formation of the photoconductive layer and the second region 15 in order to change the change pattern of the deposited film forming speed of the photoconductive layer and the second region 15 as shown in FIGS. 7-10
Of the electrophotographic light receiving member 10
Was prepared. In any of the patterns, the ratio R1 / R1 of the deposition film formation speed was set to about 50%. At this time, the change pattern of the carbon content in the second region 15 of the photoconductive layer is changed as shown in FIG. 13 so that the carbon content on the conductive support side surface of the second region 15 of the photoconductive layer is about 10 atomic%. It was made to become.

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

[0198]

[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 deposition film forming speed in the second region of the photoconductive layer was changed as shown in FIGS. . At this time, the ratio R2 / R1 of the deposition film formation speed is 100% in FIG.
FIG. 12 shows 120%.

The light receiving member for electrophotography 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 in the change pattern of the deposition film formation speed in the second region of the photoconductive layer of the present invention, better results were obtained in both electrical and image characteristics as compared with Comparative Example 4.

[0201]

[Table 11] Example 7 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
A light receiving member for electrophotography was produced on a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by a microwave glow discharge method under the production conditions shown in Table 12 according to the procedure described in detail above. In Table 12, four types of photoreceptor members 10 for electrophotography were produced by changing the change pattern of the deposition rate of the photoconductive layer 12 as shown in FIGS.

Example 5 was applied to the produced light receiving member for electrophotography.
The same evaluation as in Example 5 was performed, and the same result as in Example 5 was obtained.

[0203]

[Table 12] Comparative Example 5 Two kinds of electrophotographic light-receiving members were produced in the same manner as in Example 7, except that the pattern of changing the deposition film forming speed of the photoconductive layer was changed as shown in FIGS. At this time, the ratio R2 / R1 of the deposition film formation speed is 100% in FIG.
20%.

The light receiving member for electrophotography 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, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 as shown in Table 1.
The light receiving member for electrophotography 10 was manufactured under the manufacturing conditions shown in FIG. In the present embodiment, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer 12 is changed in order to change the change pattern of the carbon content in the photoconductive layer 12 as shown in FIGS.
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 about 10 atomic%.
Further, the change pattern of the deposition film formation speed of the photoconductive layer 12 at this time was changed as shown in FIG. 7 so that the ratio R1 / R1 of the deposition film formation speed was about 50%. The measurement of the carbon content and the deposition film forming rate was performed in the same manner as described above.

The light receiving member 10 for electrophotography was installed in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon Inc. was modified for an experiment, and charging ability, sensitivity, residual potential, white spots,
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.

[0208]

[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 change pattern of the carbon content of the photoconductive layer 12 was changed as shown in FIGS.

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

The evaluation results of Example 8 and Comparative Example 6 are shown in Table 14.
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, better results were obtained in both electrical and image characteristics as compared with Comparative Example 6.

[0211]

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

[0212]

[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 changing pattern of the carbon content in the second region 15 of the photoconductive layer 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 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 was obtained.
It was found that in the change pattern of the carbon content of No. 5, good results were obtained in both electrical and image characteristics as compared with Comparative Example 7.

[0215]

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

Example 8 was applied to the produced light receiving member for electrophotography.
The same evaluation as in Example 8 was performed, and the same result as in Example 8 was obtained.

[0219]

[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 change pattern of the carbon content 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 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, a mirror-finished aluminum made of 108 mm in diameter and 3 mm in length was used.
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 as shown in Table 1.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In this embodiment, the change pattern of the deposition film formation speed of the photoconductive layer 12 is changed linearly as shown in FIG. 7, and the deposition film formation speed (R1) of the photoconductive layer 12 on the surface of the conductive support 11 is changed. The flow rate of SiH ₄ introduced during the formation of the photoconductive layer 12 was changed in order to change the ratio R2 / R1 of the formation rate (R2) of the deposited film on the surface layer 13 side surface with respect to. 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 30 atomic%.

[0220]

[Table 18] The light receiving member 10 for electrophotography prepared was installed in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon was modified for experiments, and electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness were 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.

The evaluation results are shown in Table 19. from this result,
The ratio R2 / R1 of the deposition film forming speed of the photoconductive layer 12 is set to 30 to 90.
%, It was found that extremely good results were obtained.

[0222]

[Table 19] Example 12 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm.
A light receiving member for electrophotography was produced in the same manner as in Example 11, except that the production was carried out under the conditions shown in FIG.

Example 1 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 1 was performed, the same result as that of Example 11 was obtained.

[0224]

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

Example 1 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 1 was performed, the same result as that of Example 11 was obtained.

[0226]

[Table 21] Example 14 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In the present embodiment, in order to change the change pattern of the carbon content in the photoconductive layer 12 linearly as shown in FIG. 13 and to change the carbon content of the surface of the photoconductive layer 12 on the side of the conductive support 11. CH ₄ introduced during the formation of the photoconductive layer 12
Was changed. At this time, the change pattern of the deposition film formation speed of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposition film formation speed was set to about 85%.

[0227]

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

The entire surface of the light receiving member for electrophotography was observed with an optical microscope, and the diameter was 20 μm within an area of 100 cm ^2.
The number of the above spherical protrusions was examined. The results were obtained for each light receiving member for electrophotography, and the layer pair having the largest number of spherical projections was set to 100%, and the layer pairs were compared. The results were classified as follows.

◎ indicates less than 60%, は indicates less than 80% to 60% or more, and Δ indicates 100 to 80% or more.

Table 23 shows the evaluation results. from this result,
As for the carbon content of the photoconductive layer 12 on the side of the conductive support 11, the characteristics are improved when the content is 0.5 to 50 at%, and very good results are obtained when the carbon content is 1 to 30 at%.

[0231]

[Table 23] Example 15 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm.
An electrophotographic light-receiving member was produced in the same manner as in Example 14 except that the production conditions shown in FIG.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 4 was performed, the same result as that of Example 14 was obtained.

[0233]

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

Example 1 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 4 was performed, the same result as that of Example 14 was obtained.

[0235]

[Table 25] Example 17 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In this embodiment, the fluorine content in the photoconductive layer 12 is shown in FIG.
As shown in FIG. 8, the light receiving members for electrophotography having different fluorine contents were produced by changing the flow rate of SiF ₄ introduced at the time of forming the photoconductive layer 12 while keeping the thickness constant in the layer thickness direction.

At this time, the change pattern of the deposition film formation speed of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposition film formation speed was set to about 85%. Further, the change pattern of the carbon content of 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 11 was about 30 atomic%.
The fluorine content in the photoconductive layer 12 is determined by SIMS (CAM
ECA, IMS-3F).

[0237]

[Table 26] The produced electrophotographic light-receiving member 10 was set in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon was remodeled for experiments, and electrophotographic properties such as white spots and halftone unevenness were evaluated in the same manner as in Example 1. Was performed, and the ghost was further evaluated. The evaluation of the ghost was performed according to the following method.

A ghost test chart made by Canon (part number: FY9-9040) with a black circle having a reflection density of 1.1 and a diameter of 5 mm adhered thereto is placed at the leading end of the image on the document table, and a halftone chart made by Canon is superimposed 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 copied image when placed was measured. The relative difference was set as 100% with the largest difference. The results were classified as follows.

◎ indicates less than 60%, は indicates less than 80% to 60% or more, and Δ indicates 100 to 80% or more.

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

The evaluation results are shown in Table 27. From these results, by setting the fluorine content of the photoconductive layer 12 to a range of 95 atomic ppm or less, it is possible to produce a light receiving member for electrophotography which is very excellent in image characteristics and durability. It was shown that there is.

[0242]

[Table 27] Example 18 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm.
A light receiving member for electrophotography was produced in the same manner as in Example 17, except that the production conditions shown in FIG.

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 7 was performed, the same result as that of Example 17 was obtained.

[0244]

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

Example 1 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 7 was performed, the same result as that of Example 17 was obtained.

[0246]

[Table 29] Example 20 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 in accordance with the RF glow discharge method.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In this embodiment, the fluorine content in the photoconductive layer 12 is shown in FIG.
As shown in FIGS. 8 to 22, the flow rate of SiF ₄ introduced at the time of forming the photoconductive layer 12 is changed in order to change the thickness in the layer thickness direction.
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. A sample in which the photoconductive layer 12 did not contain fluorine atoms was also manufactured.

At this time, the change pattern of the deposition film formation speed of the photoconductive layer 12 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposition film formation speed was set to about 85%. Further, the change pattern of the carbon content of 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 11 was about 30 atomic%.
The fluorine content in the photoconductive layer 12 is determined by SIMS (CAM
ECA, IMS-3F).

[0248]

[Table 30] The six types of electrophotographic light-receiving members 10 thus prepared were installed in an electrophotographic apparatus obtained by modifying a Canon copier NP-6650 for an experiment, and charging ability, sensitivity, residual potential, white spots, halftone unevenness, and ghosts 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 temperature characteristics and image density unevenness.

Temperature characteristics: The surface temperature of the produced electrophotographic light-receiving member 10 was changed from 30 to 45 ° C.
A high voltage of V is applied, corona charging is performed, and the surface potential of the dark part is measured with a surface voltmeter. The change in the surface temperature of the dark part with respect to the surface temperature of the electrophotographic light-receiving member 10 is approximated by a straight line, and the slope is expressed as “temperature characteristics” in units of [V / deg].

The evaluation was as follows: ◎ indicates “particularly good”, and ○
Indicates “good”, Δ indicates “no practical problem”, and “x” indicates “practical problem”.

Image density unevenness: A half-tone chart made by Canon (part number FY9-9042) was placed on a platen and a circular area of 0.05 mm in diameter was obtained on each copy image obtained when 200 sheets were continuously copied. 100 as one unit
The image density of the point is measured, and the average of the image density is obtained.
The evaluation was made on the average variation of the image density between the obtained 200 images.

The evaluation was as follows: ◎ means “particularly good”;
Indicates “good”, Δ indicates “no practical problem”, and “x” indicates “practical problem”.

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 results of the evaluation. From these results, it was confirmed that including fluorine atoms in the photoconductive layer 12 and changing the fluorine content in the layer thickness direction were extremely effective in terms of image characteristics and durability.

[0255]

[Table 31] Example 21 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 in accordance with the RF glow discharge method.
An electrophotographic light-receiving member was produced in the same manner as in Example 20, except that the production conditions shown in FIG.

Example 2 was applied to the produced electrophotographic light-receiving member.
The same evaluation as in Example 20 was obtained when the same evaluation as 0 was performed.

[0257]

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

Example 2 was applied to the produced light receiving member for electrophotography.
The same evaluation as in Example 20 was obtained when the same evaluation as 0 was performed.

[0259]

[Table 33] Example 23 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter,
Cylindrical conductive support 11 having a length of 358 mm and a thickness of 5 mm
Then, the electrophotographic light-receiving member 10 was produced by the RF glow discharge method under the production conditions shown in Table 34 in accordance with the procedure described in detail above. In this embodiment, the oxygen content in the photoconductive layer 12 is made constant as shown in FIG. 23, and the oxygen content is changed as shown in Table 35 by changing the flow rate of CO ₂ introduced when the photoconductive layer 12 is formed. To produce light receiving members 10 for electrophotography. At this time, the photoconductive layer 12
7 was changed as shown in FIG. 7, and the ratio R2 / R1 of the deposited film formation speed was set to about 85%. 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 is about 30 atomic%. I made it.

Incidentally, the oxygen content in the photoconductive layer 12 is
The analysis was performed by elementary analysis using MS (CAMECA, IMS-3F).

[0261]

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

The prepared electrophotographic light receiving member 10 was set 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 with a surface electrometer. Measure the potential. At this time, the dark portion surface temperature potential when the voltage was started to be applied to the charger was Vd0,
The dark area surface potential after 2 minutes is defined as Vd. And Vd0 and V
The difference from d is used as the potential shift amount.

The evaluation was as follows: ◎ means “particularly good”;
Indicates “good”, Δ indicates “no practical problem”, and “x” indicates “practical problem”.

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

[0265]

[Table 35] Example 24 Using an electrophotographic light-receiving member manufacturing apparatus shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter,
Cylindrical conductive support 11 having a length of 358 mm and a thickness of 5 mm
Example 2 was performed in accordance with the procedure described in detail above by the RF glow discharge method under the manufacturing conditions shown in Table 36.
In the same manner as in Example 3, an electrophotographic light-receiving member was produced.

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

[0267]

[Table 36] Example 25 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a diameter of 108 mm made of mirror-finished aluminum,
Cylindrical conductive support 11 having a length of 358 mm and a thickness of 5 mm
Then, an electrophotographic light-receiving member was produced in the same manner as in Example 23 except that the production conditions shown in Table 37 were used by a microwave glow discharge method.

Example 2 was applied to the produced light receiving member for electrophotography.
When the same evaluation as in Example 3 was performed, the same result as that in Example 23 was obtained.

[0269]

[Table 37] Example 26 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
According to the procedure described in detail above, an RF glow discharge method was applied to a 58 mm, 5 mm thick cylindrical conductive support 11 in accordance with the RF glow discharge method.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In this embodiment, 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,
Various kinds of electrophotographic light receiving members 10 were produced. At this time, the oxygen content in the photoconductive layer 12 was changed within the range of 10 to 800 atomic ppm. A sample in which oxygen atoms were not contained in the photoconductive layer 12 was also prepared.

Incidentally, the oxygen content in the photoconductive layer 12 is
The analysis was performed by elementary analysis using MS (CAMECA, IMS-3F).

[0271]

[Table 38] The six types of electrophotographic light receiving members 10 thus prepared were installed in an electrophotographic apparatus in which a Canon copier NP-6650 was modified for an experiment, and 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 the potential shift was evaluated. The potential shift was evaluated according to the following method.

The prepared electrophotographic light receiving member 10 was set 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 portion surface temperature potential at the time when the voltage was started to be applied to the charger was set to Vd0.
The dark portion surface potential after one minute is Vd. The difference between Vd0 and Vd is used as the potential shift amount.

The evaluation was as follows: ◎ means “particularly good”;
Indicates “good”, Δ indicates “no practical problem”, and “x” indicates “practical problem”.

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

The evaluation results are shown in Table 39. From these results, it was confirmed that when the photoconductive layer 12 contains fluorine atoms and further contains oxygen atoms, it is very effective in improving electrophotographic characteristics such as potential shift.

[0276]

[Table 39] Example 27 Using the apparatus for manufacturing a photoreceptor member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, the RF glow discharge method was used.
A light receiving member for electrophotography was produced in the same manner as in Example 26 except that the production was carried out under the conditions shown in FIG.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 6 was performed, the same result as that of Example 26 was obtained.

[0278]

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

Example 2 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 6 was performed, the same result as that of Example 26 was obtained.

[0280]

[Table 41] Example 29 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, the RF glow discharge method was used.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In the present embodiment, the amount of carbon atoms contained in the vicinity of the outermost surface of the surface layer 13 is determined based on the power introduced when the surface layer 13 is formed,
By changing the flow rate of CH _4, the flow rate was changed within the range of 20 to 95 atomic% based on the sum of silicon atoms and carbon atoms. However, at this time, the carbon atom content on the surface of the surface layer 13 on the side of the photoconductive layer 12 was set to 10 atomic%.

[0281]

[Table 42] The produced electrophotographic light receiving member 10 was set in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon was remodeled for an experiment, and the electrophotographic properties such as charging ability, sensitivity, residual potential, and white spots were measured in Example 1. Evaluation was performed in the same manner as described above, and further, image characteristics such as image deletion, black spots and flaws due to toner fusion were evaluated. Image deletion, black spots due to toner fusion,
The evaluation for scratches was made according to the following method.

Image deletion: A Canon test chart (part number FY9-9058) consisting of whole characters on a white background was placed on a platen and exposed at twice the normal exposure.
Make a copy. The image thus obtained was observed, and it was evaluated whether the fine lines on the image were connected without interruption by the following four steps. However, when there was unevenness in the image at this time, the evaluation was made at the worst part in the entire image area.

The evaluation was as follows: ◎ indicates “good”, ○ indicates “partially interrupted”, Δ indicates “there are many interrupts but can be interpreted as characters, and there is no practical problem”. Difficult to read, and there is a problem in practical use. "

Black spots due to fusion of toner: All-white test chart made by Canon was placed on a document table, and a copy image obtained when copying was 0.1 mm wide and 0.1 mm long within the same area.
The black spots of 5 mm or more were evaluated on a 4-point scale as shown below.

◎ indicates “especially good”, ○ indicates “good”, Δ indicates “no practical problem”, and x indicates “practical problem”.

Scratches: A halftone test chart made by Canon was placed on a platen and a copy image obtained when copying was made 340 mm in width (for one rotation of the light receiving member for electrophotography) × 297 in height.
The number of flaws having a width of 0.05 mm and a length of 0.2 mm or more in the area of mm was counted, and evaluated in four steps as shown below.

◎ indicates “especially good”, ○ indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

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

The results of the evaluation are shown in Table 43. From these results, by setting the carbon atom content in the vicinity of the outermost surface of the surface layer 15 in the range of 70 to 90 atomic% with respect to the sum of silicon atoms and carbon atoms, good electrophotographic characteristics can be obtained, It was confirmed that very good image characteristics were obtained even after the test.

[0290]

[Table 43] Example 30 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, the RF glow discharge method was used.
A light receiving member for electrophotography was produced in the same manner as in Example 29 except that the production was carried out under the conditions shown in FIG.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 9 was performed, the same result as that of Example 29 was obtained.

[0292]

[Table 44] Example 31 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a mirror-finished aluminum made of a diameter of 108 mm and a length of 3
A light receiving member for electrophotography was produced on a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method under the production conditions shown in Table 45 in the same manner as in Example 29. did.

Example 2 was applied to the produced electrophotographic light-receiving member.
When the same evaluation as that of Example 9 was performed, the same result as that of Example 29 was obtained.

[0294]

[Table 45] Example 32 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum of 108 mm in diameter and 3 mm in length was used.
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, the RF glow discharge method was used.
The electrophotographic light-receiving member 10 was manufactured under the manufacturing conditions shown in FIG. In this embodiment, the light receiving member 10 for electrophotography was manufactured by using NO gas at the time of forming the surface layer 13 and allowing the surface layer 13 to simultaneously contain oxygen atoms and nitrogen atoms.

[0295]

[Table 46] The produced electrophotographic light-receiving member 10 was set in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon was remodeled for an experiment, and after a continuous paper image formation durability test of 2.5 million sheets using recycled paper, an image was formed. Image characteristics such as flow, white spots, black spots due to toner fusion, and flaws were evaluated in the same manner as in Example 29. As a result, each of the characteristics showed very good results even after the durability test as in the initial image characteristics.

Example 33 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a mirror-finished aluminum made of 108 mm in diameter and 3 mm in length was used.
On a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm, according to the procedure described in detail above, the RF glow discharge method was used.
A light receiving member for electrophotography was produced in the same manner as in Example 32 except that the production was carried out under the conditions shown in FIG.

Example 3 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 2 was performed, the same result as that of Example 32 was obtained.

[0298]

[Table 47] Example 34 Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a mirror-finished aluminum made of 108 mm in diameter and 3 mm in length was used.
A light receiving member for electrophotography was produced on a cylindrical conductive support 11 having a thickness of 58 mm and a thickness of 5 mm by the microwave glow discharge method under the production conditions shown in Table 48 in the same manner as in Example 32. did.

Example 3 was applied to the produced light receiving member for electrophotography.
When the same evaluation as that of Example 2 was performed, the same result as that of Example 32 was obtained.

[0300]

[Table 48] Example 35 (a) Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 4, a diameter of 108 m made of mirror-finished aluminum was used.
m, a length of 358 mm, and a thickness of 5 mm on the cylindrical conductive support 11 by the RF glow discharge method under the production conditions shown in Table 49 according to the procedure described in detail above.
Was prepared.

[0301]

[Table 49] On the other hand, in Table 49, (b) performed without using SiF ₄ when forming the surface layer 13 (c) performed without using N ₂ when forming the surface layer 13 (d) B ₂ H was used when forming the surface layer 13 (b) was prepared ~ three types electrophotographic light-receiving member 10 of the (d) in each condition performed without the use of _6.

The four types of electrophotographic light-receiving members thus produced were installed in an electrophotographic apparatus in which a copying machine NP-6650 manufactured by Canon was remodeled for experiments, and 2.5 million continuous paper images were formed using recycled paper. After the endurance test, the image characteristics such as image deletion, white spots, black spots due to toner fusion, flaws and the like were obtained in Example 29.
The evaluation was performed in the same manner as described above. As a result, the light receiving member for electrophotography of (a) showed very good results after the endurance test as well as the initial image characteristics in all of the characteristics. On the other hand, (b) to (d)
The three types of electrophotographic light-receiving members produced under the above conditions were slightly inferior to the characteristics of the electrophotographic light-receiving member (a) in any of the results.

From the above results, it was found that carbon atoms
It has been found that by simultaneously containing a hydrogen atom, a halogen atom, an element belonging to Group 3B of the periodic table, and a nitrogen atom, a light-receiving member for electrophotography having excellent image durability can be produced.

Example 36 (a) Using the apparatus for manufacturing a light-receiving member for electrophotography shown in FIG. 6, a diameter of 108 m made of mirror-finished aluminum was used.
m, a length of 358 mm, and a thickness of 5 mm on a cylindrical conductive support 11 by a μW glow discharge method under the production conditions shown in Table 50 by the μW glow discharge method according to the procedure described in detail above.
Was prepared.

[0305]

[Table 50] On the other hand, in Table 50, (b) performed without using SiF ₄ when forming the surface layer 13 (c) performed without using CO ₂ when forming the surface layer 13 (d) B ₂ H was performed when forming the surface layer 13 (b) was prepared ~ three types electrophotographic light-receiving member 10 of the (d) in each condition performed without the use of _6.

The four types of electrophotographic light-receiving members thus prepared were set in an electrophotographic apparatus in which a Canon copier NP-6650 was modified for experiments, and 2.5 million continuous paper images were formed using recycled paper. After the endurance test, the image characteristics such as image deletion, white spots, black spots due to toner fusion, flaws and the like were obtained in Example 29.
The evaluation was performed in the same manner as described above. As a result, the light receiving member for electrophotography of (a) showed very good results after the endurance test as well as the initial image characteristics in all of the characteristics. On the other hand, (b) to (d)
The three types of electrophotographic light-receiving members produced under the above conditions were slightly inferior to the characteristics of the electrophotographic light-receiving member (a) in any of the results.

From the above results, it was found that carbon atoms,
It has been found that by simultaneously containing a hydrogen atom, a halogen atom, an element belonging to Group 3B of the periodic table, and an oxygen atom, a light-receiving member for electrophotography having excellent image durability can be produced.

[0308]

According to the method of the present invention, it is possible to solve various problems in the conventional electrophotographic light-receiving member composed of A-Si, and in particular, extremely excellent electric and optical characteristics. Thus, an electrophotographic light-receiving member exhibiting photoconductive properties, image properties, durability and use environment properties can be formed. In particular, in the present invention, the generation of electric charges (photo carriers) and the transport of the generated electric charges are achieved by continuously decreasing the carbon atoms contained in the photoconductive layer from the conductive support side toward the surface layer side. Thus, an important function for the electrophotographic light receiving member can be smoothly maintained, and an electrophotographic light receiving member excellent in light sensitivity can be manufactured. In addition, since the photoconductive layer contains carbon atoms, the dielectric constant of the photoconductive layer composed of the photoconductive layer and the surface layer can be reduced, so that the capacitance per layer thickness can be reduced. This realizes a high charging ability, a remarkable improvement in photosensitivity, a further improvement in pressure resistance against a high voltage, and an improvement in durability. Furthermore, by increasing the rate of formation of the photoconductive layer on the support side and decreasing the rate on the surface layer, the content of carbon atoms in the photoconductive layer changes in the thickness direction. And the synergistic effect of the change in the deposition film formation rate and the change in the carbon content improves the denseness of the deposited film, thereby improving the uniformity of the deposited film and reducing defects in the deposited film. Decrease. As a result, image characteristics such as halftone unevenness can be particularly improved, and injection of electric charge from the surface layer side can be more effectively prevented, so that higher charging ability can be obtained.
Further, peeling of the deposited film and generation of minute defects can be significantly suppressed.

The photoconductive layer is composed of two regions, 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 set to 0.5 to 50 μm, so that the length is longer. The ghost is improved because the sensitivity of the wavelength light is improved and the traveling property of the carrier opposite to the charging polarity is improved. In addition, by providing the surface layer according to the present invention, the surface strength and the electric pressure resistance are improved, and it is effective in reducing image defects such as "potches", and in particular, in suppressing the increase in "potches" during long-term use. In addition, electrophotographic light that exhibits extremely excellent image characteristics, durability and use environment characteristics by preventing the occurrence of "scratch" when using recycled paper and eliminating "toner fusing" and "image deletion" during long-term use A receiving member can be provided.

[Brief description of the drawings]

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

FIG. 2 is a schematic configuration diagram for explaining a layer configuration of another preferred embodiment of the light receiving member for electrophotography 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, wherein RF is used.
FIG. 3 is a schematic explanatory view of an apparatus for manufacturing an electrophotographic light-receiving member 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 typical explanatory drawing of the deposition apparatus part of the manufacturing apparatus of the photoreceptor member for electrophotography by a glow discharge method, (a) is a side sectional view of an apparatus, (b) is a cross-sectional view in XX '. is there.

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

FIG. 7 is a photoconductive layer (second photoconductive layer region) in the present invention.
4 is a graph showing a change pattern of a deposition film formation speed of FIG.

FIG. 8 is a photoconductive layer (second photoconductive layer region) in the present invention.
4 is a graph showing a change pattern of a deposition film formation speed of FIG.

FIG. 9 is a photoconductive layer (second region of the photoconductive layer) in the present invention.
4 is a graph showing a change pattern of a deposition film formation speed 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 rate of a photoconductive layer (photoconductive layer second region) outside the present invention.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 photoreceptor member for electrophotography 11 conductive support 12 photoconductive layer 13 surface layer 14 free surface 15 photoconductive layer second region 16 photoconductive layer first region 4100 deposited film forming apparatus by RF glow discharge method 4111 reaction vessel 4112 Cylindrical support 4113 Heater for supporting support 4114 Source gas introduction pipe 4115 Matching box 4116 Source gas pipe 4117 Reaction vessel leak valve 4118 Main exhaust valve 4119 Vacuum gauge 4200 Source gas supply device 4211-4216 Mass flow controller 4221-4226 Source gas cylinder 4231 4236 Raw material gas cylinder valve 4241-4246 Gas inflow valve 4251-4256 Gas outflow valve 4261-4266 Pressure regulator 5100 μW Deposition film forming apparatus 511 by glow discharge method Reference Signs List 1 reaction vessel 5112 microwave introduction window 5113 waveguide 5114 support holder 5115 cylindrical support 5116 support heating heater 5117 raw material gas introduction pipe 5118 bias electrode 5119 bias power supply 5120 support rotation motor 5121 exhaust pipe 5130 discharge space

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03G 5/08 305 G03G 5/08 305 306 306 312 312 313 313 314 314

Claims (17)

(57) [Claims] 1. An electrophotographic light-receiving member comprising: a conductive support; and a photoreceptive layer composed of a silicon-based photoconductive layer and a surface layer sequentially laminated on the conductive support. In the forming method, the photoconductive layer contains at least carbon atoms and hydrogen atoms throughout the entire layer, the content of the carbon atoms is unevenly distributed in the layer thickness direction, and is large on the conductive support side, The surface layer is composed of a non-single-crystal material that is less distributed on the surface layer side, and the surface layer simultaneously contains carbon atoms, hydrogen atoms, halogen atoms, and elements belonging to Group 3B of the periodic table, and contains oxygen atoms and / Or a non-single-crystal material containing a nitrogen atom, changing the deposition film formation rate of the photoconductive layer in the layer thickness direction,
The method of forming a light-receiving member for electrophotography, wherein the photoconductive layer is formed such that the photoconductive layer is formed faster on the conductive support side and slower on the surface layer side. 2. The method according to claim 1, wherein the rate of forming a deposited film on or near the surface of the photoconductive layer is 30 to 9 with respect to the rate of forming a deposited film on or near the surface of the conductive support.
The method for forming a light receiving member for electrophotography according to claim 1, wherein the amount is set to 0%. 3. The method according to claim 1, wherein the content of the carbon atoms in the photoconductive layer is set to a value of 0.1 at or near the surface of the conductive support.
5. The atomic percentage of the hydrogen atom in the photoconductive layer is 1 to 40 atomic%, 5 to 50 atomic%, substantially 0% at or near the surface on the surface layer side. 1
Or the method for forming an electrophotographic light-receiving member according to item 2. 4. The method for forming an electrophotographic light-receiving member according to claim 1, wherein a fluorine atom is contained in the photoconductive layer. 5. The method according to claim 4, wherein the fluorine atoms in the photoconductive layer are non-uniformly distributed in a layer thickness direction. 6. The method for forming an electrophotographic light-receiving member according to claim 4, wherein oxygen atoms are further contained in the photoconductive layer. 7. The method according to claim 6, wherein the oxygen atoms in the photoconductive layer are non-uniformly distributed in a thickness direction. 8. A light-receiving member for electrophotography, comprising: a conductive support; and a light-receiving layer composed of a photoconductive layer having silicon atoms as a base material and a surface layer sequentially laminated on the conductive support. In the formation method, the photoconductive layer includes 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 over the entire layer. The photoconductive layer is composed of a non-single-crystal material in which the carbon atom content is unevenly distributed in the layer thickness direction, and is more distributed on the conductive support side and less distributed on the photoconductive layer first region side; The first layer region is made of a non-single-crystal material containing 1 to 40 atomic% of hydrogen atoms, and the deposition film forming speed of the second region of the photoconductive layer is changed in a layer thickness direction. Fast, the photoconductive layer first
The method 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 forming speed on the surface or near the surface of the second region of the photoconductive layer on the side of the first region of the photoconductive layer is compared with the forming speed of the deposited film on the surface or near the surface of the conductive support. The method for forming a light receiving member for electrophotography according to claim 8, wherein the 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 atomic% at or near the surface on the side of the conductive support, and the content of the carbon atom is in the first region of the photoconductive layer. 10. The electron according to claim 8, wherein the content of the hydrogen atoms in the second region of the photoconductive layer is 1 to 40 at. A method for forming a photographic light receiving member. 11. The method according to claim 8, wherein a fluorine atom is contained in the second region of the photoconductive layer. 12. The method according to claim 11, wherein the fluorine atoms in the second region of the photoconductive layer are non-uniformly distributed in a layer thickness direction. 13. The method for forming a light receiving member for electrophotography according to claim 11, wherein an oxygen atom is further contained in the second region of the photoconductive layer. 14. The method according to claim 13, wherein oxygen atoms in the second region of the photoconductive layer are unevenly distributed in a layer thickness direction. 15. The film thickness of the first region of the photoconductive layer is 0.5
The method for forming an electrophotographic light-receiving member according to any one of claims 8 to 14, wherein the thickness is set to 15 m. 16. The method according to claim 16, wherein at least one of the carbon atom, the halogen atom, the element belonging to Group 3B of the periodic table, and the oxygen atom and / or the nitrogen atom in the surface layer is formed. The method for forming an electrophotographic light-receiving member according to claim 1, wherein the member is formed so as to be distributed in a thickness direction. 17. The content of the carbon atoms in the outermost surface or in the vicinity of the outermost surface in the surface layer is set to 70 atom% to 90 atom with respect to the sum of the silicon atom content and the carbon atom content. %.
7. The method for forming an electrophotographic light-receiving member according to any one of 6.