JPH04352158A - Production of electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To inexpensively and stably produce a non-single crystalline silicon sensitive body free from surface cloudiness and having slight unevenness in electrification ability such as electrostatic charge-ability, sensitivity and halftone without causing environmental pollution. CONSTITUTION:An electric conductive substrate 101 is machined, washed with water 121 and brought into contact with pure water 131 and a first photoconductive layer of non-single crystalline SiC:H in which carbon is largely distributed in the lower part, a second photoconductive layer of non-single crystalline Si:H and a surface layer consisting of Si, C, H and F are laminated on the substrate 101 by plasma CVD.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrophotographic photoreceptor in which a light-receiving layer made of silicon is formed on a conductive substrate.

The present invention relates to a method for producing an electrophotographic photoreceptor that can be widely used in electrophotographic application fields such as electrophotographic copying machines, laser beam printers, LED printers, liquid crystal printers, and laser plate making machines.

0003

Conventionally, non-single crystal deposited films, such as amorphous deposited films such as amorphous silicon compensated with hydrogen and/or halogen (for example, fluorine, chlorine, etc.), have been proposed for use in electrophotographic photoreceptors. , some of which have been put into practical use. Conventional methods for forming such deposited films include sputtering, a method of decomposing source gas with heat (thermal CVD method), a method of decomposing source gas with light (photoCVD method), and a method of decomposing source gas with plasma ( Many methods are known, such as plasma CVD (plasma CVD). Among them, the plasma CVD method, in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge, and a thin film is formed on a substrate, is the most suitable method for forming amorphous silicon deposited films for electrophotography. , and its practical application is currently very advanced. Such an example is described in, for example, Japanese Unexamined Patent Publication No. 54-86341.

[0004] This amorphous silicon photoreceptor has the characteristics of being non-polluting, high image quality, and highly durable, and the amorphous silicon photoreceptor currently in practical use fully exhibits these characteristics. . however,
In order for amorphous silicon photoreceptors to become more widespread in the future, further cost reduction, further improvement in electrical properties, and even higher durability are desired.

[0005] Furthermore, in recent years, environmental pollution has become a problem on a global scale, and there is an urgent need to improve not only the products that lead to environmental pollution, but also the use of products at the manufacturing stage. Although the amorphous silicon photoreceptor itself is non-polluting, it has become necessary to reconsider everything from cleaning the cylinder, which is the base portion of the photoreceptor, to packaging after manufacturing.

From this point of view, the conventional method of cleaning an amorphous silicon photoreceptor will be reviewed. It has been known that when manufacturing an amorphous silicon photoreceptor, care must be taken in cleaning the substrate before forming a film. When using metal as a substrate for depositing an amorphous silicon photoreceptor, it can withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and also maintains high positional accuracy to avoid deterioration of image quality. There are many. For this reason, aluminum alloys, which have particularly excellent workability and dimensional stability, are widely used. Generally, when processing these substrates, lathe processing is performed using an oil-based substance such as cutting oil. Therefore, there is always a residue of oil-based substances on the substrate after processing, and there is also cutting powder during processing.
Dust, etc. in the air is attached. If these residues remain due to insufficient cleaning, it may not be possible to form a uniform deposited film with no defects, it may not be possible to obtain sufficient electrical characteristics, and it may cause image defects, especially when used for a long time. Problems are known. Therefore, when manufacturing an electrophotographic photoreceptor, it is necessary to pay close attention and thoroughly clean the substrate.

Under these circumstances, for example, Japanese Patent Laid-Open No. 171-1989
No. 798 describes a technique related to a method of processing a substrate of an electrophotographic photoreceptor. This publication discloses a technique for obtaining an electrophotographic photoreceptor of good quality such as amorphous silicon by cutting a substrate using a cutting oil with specific components. The publication also states that after cutting, the substrate is treated with triethane (trichloroethane: C2 H3 Cl3
). Photoreceptors manufactured using substrates cleaned by this method have certain characteristics and are now widely used without any major problems, but organic solvents such as trichloroethane Its use must be avoided because it has a negative impact not only on the human body but also on the local environment.

In order to solve this problem, several aqueous cleaning methods have been proposed in recent years to replace the above-mentioned cleaning method.

For example, Japanese Unexamined Patent Publication No. 63-264764 discloses a technique for roughening the surface of a substrate using a water jet.

Furthermore, Japanese Patent Laid-Open No. 1-130159 discloses a technique for cleaning an electrophotographic substrate using a water jet. This publication mentions amorphous silicon as well as selenium and an organic photoconductor as examples of photoconductors, and suggests that the present technology can be applied to amorphous silicon photoconductors as well. However, the actual situation is that this publication does not mention at all the problems encountered in actual implementation, particularly the problems unique to the plasma CVD method.

On the other hand, studies on improving the quality of amorphous silicon photoreceptors are steadily progressing by studying the layer structure.

For example, Japanese Patent Laid-Open No. 54-145540 discloses that when amorphous silicon containing 0.1 to 30 atom % of carbon as a chemical modifier is used as a photoconductive layer of an electrophotographic photoreceptor, the dark resistance is high; It has been shown to exhibit excellent electrophotographic properties with good photosensitivity.

Furthermore, Japanese Patent Laid-Open No. 57-119357 discloses that an electrophotographic photoreceptor with excellent characteristics can be obtained by distributing more carbon atoms toward the substrate side in amorphous silicon.

Although the performance of electrophotographic photoreceptors has been improved by these techniques, there is still room for improvement.

Under these circumstances, conventional problems in terms of high image quality, high durability, and non-pollution are listed below.

First of all, reduction of image defects in the form of black dots or white dots called spots is one of the problems that is highly desired. Nowadays, due to the demand for high image quality, there is a desire to reduce the small size of spots, which has not been a problem in the past. Analysis of the cause of this spot is progressing day by day, and some new knowledge is being obtained. Most of the spots are caused by abnormal growth called spherical protrusions caused by dust generated during the deposition of the amorphous silicon film. Furthermore, there are also durability spots that increase as the durability continues, and this is caused by toner scattering and paper dust entering the separation charger. In order to reduce image defects caused by these various causes, those who manufacture photoreceptors must not only improve the cleanliness of the deposited film forming equipment, but also improve the method of forming deposited films and reduce the number of amorphous films from the production process. Measures must be taken to increase the voltage resistance of the silicon photoreceptor. Furthermore, in recent years, electrophotographic copying machines are desired to have higher image quality and higher functionality, so it is also essential that they be able to faithfully reproduce documents containing halftones, such as photographs. Therefore, in electrophotographic photoreceptors, it is particularly desired to reduce unevenness in halftones. Particularly in full-color copying machines that have become popular in recent years, this unevenness becomes a subtle unevenness in color that is clearly recognized visually, and is therefore a big problem.

Furthermore, it is desired that electrophotographic photoreceptors maintain high image quality and high sensitivity and have significantly increased durability under all environments. This durable property, which is the best feature of amorphous silicon photoreceptors, means that there is no need to replace them until the end of the lifespan of the copying machine itself, so the photoreceptor is not considered a consumable item, but rather a part of the copying machine. We are beginning to see the possibility of being free from maintenance such as replacing photoreceptors. Therefore, new products are required to have durability equal to or higher than that of the copying machine itself, and it is desired that the durability be further increased significantly. In response to these demands, it has been difficult to achieve both high charging performance and prevention of image blurring at a high level, and to significantly extend durability in all environments, and this has not been sufficient.

[0018] In order to solve these problems, it is currently necessary to review and comprehensively consider everything from the process of cleaning the conductive substrate to the process of manufacturing the electrophotographic photoreceptor.

[0019]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and provides an electrophotographic photoreceptor having a conventional photoreceptive layer made of a material containing silicon atoms as described above. The purpose of this invention is to provide a photoreceptor with excellent electrical characteristics and extremely reduced image defects at low cost and with a high yield.

That is, an object of the present invention is to avoid the use of organic solvents in the manufacturing process, which is therefore environmentally friendly, and to significantly increase the yield of manufactured electrophotographic photoreceptors with poor appearance, thereby eliminating image defects, halftone unevenness, etc. An object of the present invention is to provide a method for manufacturing an electrophotographic photoreceptor at a low cost that has particularly excellent properties and can be used in any environment.

Another object of the present invention is to provide excellent adhesion between a layer provided on a conductive substrate and the conductive substrate as well as between each of the laminated layers, and to use uniform and high quality silicon atoms as a base material. An object of the present invention is to provide an electrophotographic photoreceptor having a photoreceptive layer made of a material.

Still another object of the present invention is that when applied as an electrophotographic photoreceptor, it has sufficient charge retention ability during charging processing for electrostatic image formation, and can easily produce high-quality images with high resolution. A method for producing an electrophotographic photoreceptor having a photoreceptor layer composed of a common silicon-based material, which exhibits excellent electrophotographic properties that can be obtained in the electrophotography process and can be applied very effectively to electrophotography. Our goal is to provide the following.

[0023]

[Means for Solving the Problems] In order to overcome the above-mentioned problems in conventional deposited film forming methods, the present inventors have conducted intensive studies from the viewpoint of productivity and cost reduction, as well as from the standpoint of environmental protection. As a result, the above objectives were achieved.

The present invention has been completed based on this knowledge, and its main points are (a) cutting the surface of a conductive substrate with a predetermined precision; and (b) cutting the surface of the substrate after cutting. (c) contacting the cleaned substrate surface with pure water to clean the substrate surface; (d) the cleaned substrate surface contains carbon atoms and hydrogen atoms throughout the entire layer; and a first photoconductive layer made of a non-single crystal material containing silicon atoms and carbon, in which the carbon atom content is non-uniform in the layer thickness direction and highly distributed on the conductive substrate side. (e) forming a second photoconductive layer containing silicon atoms as a matrix on the first photoconductive layer formed by plasma CVD;
(f) forming a surface layer containing silicon atoms as a matrix and containing carbon atoms and hydrogen atoms on the second photoconductive layer formed by the plasma CDV method; wherein the content of carbon atoms in the first photoconductive layer is 0.5 to 50 atomic % at the interface with the conductive substrate, and at or near the interface with the second photoconductive layer. is essentially 0% in
The content of hydrogen atoms in the photoconductive layer is 1 to 40 at%, and the content of carbon atoms in the surface layer is 40 to 9.
0 atom % and contains a halogen, the content of the halogen atom is 20 atom % or less, and the sum of the content of hydrogen atoms and halogen atoms is 30 to 70 atom %, the first photoconductive This includes containing halogen in the layer, and distributing the halogen in the first photoconductive layer so that it has a maximum value at or near the interface with the second photoconductive layer.

An example of the procedure for actually forming an electrophotographic photoreceptor according to the method of manufacturing an electrophotographic photoreceptor of the present invention using an aluminum alloy cylinder as a conductive substrate will be described below. Pretreatment device, and Figure 2 (a
), (b) will be explained using the deposited film forming apparatus using the microwave CVD method.

In FIG. 1, a diamond cutting tool (product name: Miracle Bit,
(manufactured by Tokyo Diamond) to the center angle of the cylinder.
Set to obtain a rake angle of °. Next, the base body was vacuum chucked on the rotating flange of this lathe, and white kerosene was sprayed from an attached nozzle, while cutting chips were sucked from the same attached vacuum nozzle at a circumferential speed of 1000 m/mi.
n, the outer diameter is 108 at a feed rate of 0.01 mm/R.
Perform mirror cutting to obtain a diameter of mm. After cutting, the surface of the substrate is processed by a substrate pretreatment device. Figure 1
The substrate preprocessing apparatus shown in FIG. 1 includes a processing section 102 and a substrate transport mechanism 103. The processing unit 102 includes a substrate loading table 1
11, Substrate cleaning tank 121, pure water contact tank 131, drying tank 1
41, and a substrate unloading table 151. Cleaning tank 121
Both the pure water contact tank 131 are equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. Transport mechanism 103
consists of a transport rail 165 and a transport arm 161, and the transport arm 161 includes a moving mechanism 162 that moves on the rail 165, a chucking mechanism 163 that holds the conductive substrate 101, and an air cylinder that moves the chucking mechanism 163 up and down. It consists of 164. After cutting, the conductive substrate 101 placed on the input table 111 is transferred to the transport mechanism 1
03 to the cleaning tank 121. Cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in a cleaning liquid 122 made of an aqueous surfactant solution in a cleaning tank 121. Next, the conductive substrate 101 is transported to a pure water contact tank 131 by a transport mechanism 103, and is heated to a temperature of 25°C.
Pure water with a resistivity of 17.5 MΩ-cm maintained at a temperature of 17.5 MΩ-cm is sprayed from the nozzle 132 at a pressure of 50 Kg·f/cm 2 . The conductive substrate 101 that has undergone the pure water contact step is moved to the drying tank 141 by the conveyance mechanism 103, and is placed in the nozzle 1.
It is dried by blowing high-temperature, high-pressure air from 42. The conductive substrate 101 after the drying process is transferred to the transport mechanism 103
It is carried to the unloading table 151 by.

Next, amorphous silicon is deposited on the surface of the conductive substrate after these cutting processes and pretreatments using the apparatus for forming a photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2(a) and 2(b). Forms a mainly deposited film. In FIGS. 2(a) and 2(b), 201 is a reaction vessel, which has a vacuum-tight structure. Further, 202 is a microwave introduction dielectric window made of a material (for example, quartz glass, alumina ceramics, etc.) that can efficiently transmit microwave power into the reaction vessel 201 and maintain vacuum tightness. . A waveguide 203 transmits microwave power, and consists of a rectangular portion extending from the microwave power source to the vicinity of the reaction vessel, and a cylindrical portion inserted into the reaction vessel. The waveguide 203 is a stub tuner (
(not shown), an isolator (not shown) and a microwave power source (not shown). Dielectric window 2
02 is a waveguide 20 to maintain the atmosphere inside the reaction vessel.
The cylindrical opening of No. 3 is hermetically sealed to the inner wall of the reaction vessel. 204 is an exhaust pipe whose one end opens into the reaction vessel 201 and whose other end communicates with an exhaust device (not shown). 206 indicates a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias application electrode 212,
It is electrically connected to electrode 212.

Manufacturing of an electrophotographic photoreceptor using such a deposited film forming apparatus is carried out as follows. First, the inside of the reaction container 201 is evacuated by a vacuum pump (not shown) through the exhaust pipe 204, and the pressure inside the reaction container 201 is reduced to 1×10
Adjust to -7 Torr or less. Next, the temperature of the base 205 is heated and maintained at a predetermined temperature by the heater 207. Thereafter, raw material gases such as silane gas as a raw material gas for amorphous silicon, diborane gas as a doping gas, and helium gas as a diluent gas are introduced into the reaction vessel 201 through a gas introducing means (not shown). At the same time, microwaves with a frequency of 2.45 GHz are generated by a microwave power source (not shown) and introduced into the reaction vessel 201 through the waveguide 203 and the dielectric window 202. Furthermore, a DC voltage is applied to the bias electrode 212 with respect to the base body 205 by a DC power supply 211 electrically connected to the bias electrode 212 in the discharge space 206 . Thus, the discharge space 20 surrounded by the conductive substrate 205
In step 6, the raw material gas is excited and dissociated by microwave energy, and is further connected to the bias electrode 212 and the substrate 205.
A deposited film is formed on the surface of the conductive substrate 205 while receiving constant ion bombardment on the conductive substrate 205 due to the electric field between the two electrodes. At this time, the rotating shaft 209 on which the conductive base 205 is installed
is rotated by a motor 210, and the conductive substrate 205 is rotated around the central axis in the direction of the substrate generatrix, thereby forming a deposited film layer uniformly over the entire circumference of the conductive substrate 205.

By using such a manufacturing apparatus and under the conditions shown in Table 2, for example, the first photoconductive layer 502 and the second photoconductive layer 50, which are essential requirements of the present invention, are formed as shown in FIG.
3 and a surface layer 504 can be produced. Note that 501 is a base body.

[0030] By following these procedures, electrophotographic photoreceptors can be produced continuously and efficiently.

In the present invention, the cleaning liquid used in the cleaning step is preferably water or water with a surfactant added thereto. Surfactants used in the cleaning process include anionic surfactants, cationic surfactants, nonionic surfactants,
Any amphoteric surfactant or a mixture thereof may be used. The present invention is also effective even if additives such as sodium tripolyphosphate are added.

If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be formed on the surface of the conductive substrate, causing the deposited film to peel off. On the other hand, if it is too low, the cleaning effect will be small and the effects of the present invention will not be sufficiently obtained. For this reason, the water temperature should be 10℃ or higher and 90℃ or lower.
Preferably, a temperature of 20°C or higher and 75°C or lower, optimally 30°C or higher and 55°C or lower, is suitable for the present invention.

[0033] In the present invention, it is important to use ultrasonic waves in the cleaning step in order to obtain the full effect of the present invention. The frequency of the ultrasonic wave is preferably 100Hz or more, 10MHz
Below, more preferably 1 KHz or more and 5 MHz or less, most preferably 10 KHz or more and 100 kHz or less is effective. The output of the ultrasonic wave is preferably 10 W or more and 100 kW or less, more preferably 100 W or more, 1
0kW or less is effective.

The quality of the water used in the pure water contacting step of the present invention is very important.
SI grade ultrapure water is preferred. Specifically, water temperature 2
A resistivity at 5° C. of 1 MΩ-cm or more, preferably 4 MΩ-cm or more, and optimally 10 MΩ-cm or more is suitable for the present invention. The amount of fine particles is 0.2 μm
It is suitable for the present invention that the number of the above particles per milliliter is 100,000 or less, preferably 10,000 or less, and optimally 1,000 or less. As for the amount of microorganisms, the total number of viable bacteria is 1
Less than 1000, preferably less than 100, optimally less than 10 are suitable for the present invention in a milliliter. The amount of organic matter (TOC) is 100 mg or less per liter,
Preferably 10 mg or less, optimally 2 mg or less are suitable for the present invention.

Methods for obtaining water with the above-mentioned quality include activated carbon method, distillation method, ion exchange method, filter filtration method, reverse osmosis method, and ultraviolet sterilization method. It is desirable to improve the water quality to the level that is expected.

When bringing pure water into contact with the surface of the conductive substrate, it is desirable to spray it under water pressure. If the water pressure during spraying is too weak, the effect of the present invention will be small, and if it is too strong, the resulting image on the electrophotographic photoreceptor will be affected.
Particularly, pear-like patterns appear on halftone images. Therefore, the water pressure is 2Kg・f/cm2
above, 300Kg・f/cm2 or less, preferably 1
0Kg・f/cm2 or more, 200Kg・f/cm2 or less, optimally 20Kg・f/cm2 or more, 150Kg・f
/cm2 or less is suitable for the present invention. However, the pressure unit Kg・f/cm2 in the present invention means gravitational kilogram per square centimeter, and 1Kg・f/cm2 is 9
It is equal to 8066.5Pa. The method of spraying pure water of the present invention includes a method of spraying high-pressure water using a pump from a nozzle, or a method of mixing pumped water with high-pressure air in front of the nozzle and spraying using the air pressure. There is.

[0037] The flow rate of pure water in the present invention is 1 liter/mi per conductive substrate in view of the effects of the invention and economic efficiency.
n or more and 200 liters/min or less, preferably 2 liters/min or more and 100 liters/min
Below, the optimum speed is 5 liters/min or more and 50 liters/min or less suitable for the present invention.

If the temperature of the pure water of the present invention is too high, an oxide film will be formed on the conductive substrate, causing peeling of the deposited film, and furthermore, the effects of the present invention will not be sufficiently obtained. Moreover, if it is too low, the effects of the present invention cannot be obtained sufficiently. Therefore, the temperature of pure water should be 5°C or higher and 90°C or lower, preferably 10°C or higher and 55°C or lower, and optimally 15°C.
As mentioned above, a temperature of 40° C. or lower is suitable for the present invention.

The treatment time of the water contact treatment is 10 seconds or more and 30 minutes or less, preferably 20 seconds, because if it is too long, an oxide film will be generated on the conductive substrate, and if it is too short, the effect of the present invention will be small. or more, less than 20 minutes, optimally more than 30 seconds, 1
A time of 0 minutes or less is suitable for the present invention.

In the present invention, it is important to cut the surface of the substrate immediately before forming the deposited film in order to eliminate the influence of an oxide film on the surface of the substrate during the formation of the deposited film. The time from cutting to water contact treatment is 1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours, because if it is too long, an oxide film will form on the substrate surface again, and if it is too short, the process will not be stable. Hereinafter, a time of 3 minutes or more and 4 hours or less is most suitable for the present invention. If the time from water contact treatment to input into the deposited film forming apparatus is too long, the effect of the present invention will be reduced, and if it is too short, the process will not be stable, so it is 1 minute or more and 8 hours or less, preferably 2 minutes or more. , 4 hours or less, optimally 3 minutes or more and 2 hours or less are suitable for the present invention.

[0041] The conductive substrate used in the present invention includes:
For example, Al, Cr, Mo, Au, In, Nb, Te,
Examples include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. In addition, at least the side forming the photoreceptive layer of an electrically insulating and conductive substrate such as a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, or polyamide, glass, or ceramic, etc. Although a substrate whose surface has been subjected to conductive treatment can also be used, metal is preferable from the viewpoint of mechanical strength and the like.

In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined precision. For example, when recording an image using coherent light such as a laser beam, irregularities may be provided on the surface of the conductive substrate in order to eliminate image defects due to interference fringe patterns that appear in visible images. The unevenness provided on the surface of the conductive substrate is described in Japanese Patent Application Laid-open Nos. 60-168156 and 60-178.
It is produced by a known method described in JP-A No. 457, JP-A No. 60-225854, and the like. Further, as another method for eliminating image defects caused by interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions may be provided on the surface of the conductive substrate. That is, the surface of the conductive substrate has irregularities that are finer than the resolving power required for an electrophotographic photoreceptor, and the irregularities are caused by a plurality of spherical trace depressions. The unevenness caused by a plurality of spherical trace depressions provided on the surface of a conductive substrate is described in Japanese Patent Application Laid-Open No. 61-2315.
It is produced by a known method described in Japanese Patent No. 61.

The first photoconductive layer in the present invention includes silicon atoms, carbon atoms, and silicon atoms as constituent elements from the conductive substrate side.
Amorphous silicon carbide nc-Si containing hydrogen atoms
It is composed of a photoconductive layer made of C(H) and has desired photoconductive properties, particularly charge retention properties, charge generation properties, and charge transport properties. The carbon atoms contained in the photoconductive layer have a distribution, and the distribution is substantially uniform in each plane parallel to the surface of the conductive substrate, and is non-uniform in the thickness direction of the layer. , at each point in the film thickness direction, the content on the conductive substrate side is high and the content on the surface layer side is low. If the content of carbon atoms is 0.5% or less on the surface or near the surface on which the conductive substrate is provided, the adhesion with the conductive substrate and the function of preventing charge injection will deteriorate. Furthermore, the effect of improving charging ability due to a decrease in capacitance is lost. Moreover, if it exceeds 50%, a residual potential will occur. Therefore, it is practically 0.5 to 50 atom%, preferably 1 to 40 atom%, and optimally 1 to 30 atom%.
It is preferable that Note that atomic % here represents a percentage based on the number of atoms. In addition, in the present invention, it is necessary for the photoconductive layer to contain hydrogen atoms, which compensate for the dangling bonds of silicon atoms and improve the layer quality, especially photoconductivity and charge retention properties. This is because it is essential for achieving this goal. In particular, when carbon atoms are contained, more hydrogen atoms are required to maintain the film quality, so it is desirable to adjust the amount of hydrogen contained according to the carbon content. Therefore, the content of hydrogen atoms on the surface on which the conductive substrate is provided is preferably 1 to 40 at%, more preferably 5 to 35 at%.
, most preferably 10 to 30 atom %.

In the present invention, the first photoconductive layer is produced by a vacuum deposition film forming method, with numerical conditions of film forming parameters set appropriately so as to obtain desired characteristics. Specifically, glow discharge method (AC discharge CVD method such as low frequency CVD method, high frequency CVD method or microwave CVD method)
method, direct current discharge CVD method, etc.). nc-SiC by glow discharge method:
To form the H photoconductive layer, basically silicon atoms (
A raw material gas for Si supply that can supply Si), a raw material gas for C supply that can supply carbon atoms (C), and a raw material gas for C supply that can supply carbon atoms (C), and hydrogen atoms (
A raw material gas for H supply that can supply H) is introduced in a desired ratio gas state into a reaction vessel whose interior can be reduced in pressure, a glow discharge is generated in the reaction vessel, and a glow discharge is caused in advance at a predetermined position. n on the surface of a predetermined conductive substrate placed on
A layer made of c-SiC:H may be formed.

In the present invention, the layer thickness of the first photoconductive layer is determined as desired from the viewpoint of obtaining desired electrophotographic properties and economical effects, and is generally 5 to 5.
It is desirable that the thickness be 0 μm, more preferably 10 to 40 μm, and optimally 20 to 30 μm.

In the present invention, the second photoconductive layer is made of amorphous silicon nc-Si:H containing silicon atoms and hydrogen atoms as constituent elements, and has desired photoconductive properties, particularly charge generation properties and charge transport properties. have The second photoconductive layer of the present invention is used in order to increase the absorption of long wavelength light and improve sensitivity, and because the mobility of carriers with opposite polarity to the charged polarity is better than that of the first photoconductive layer. This is provided for the purpose of reducing ghosting.

In the present invention, the second photoconductive layer is produced by a vacuum deposition film forming method, with numerical conditions of film forming parameters set appropriately so as to obtain desired characteristics. Specifically, glow discharge method (low frequency CVD method, high frequency C
It can be formed by a VD method, an AC discharge CVD method such as a microwave CVD method, a DC discharge CVD method, etc.). In order to form an nc-Si:H photoconductive layer by the glow discharge method, basically a raw material gas for supplying Si that can supply silicon atoms (Si) and an H supply that can supply hydrogen atoms (H) are required. A raw material gas for use is introduced in a desired gas state into a reaction vessel whose interior can be reduced in pressure to generate a glow discharge in the reaction vessel, and a predetermined conductive substrate previously installed at a predetermined position is nc-Si:H on the surface
What is necessary is to form a layer consisting of. In the present invention, the layer thickness of the second photoconductive layer is determined as desired from the viewpoints of obtaining desired electrophotographic properties and economical effects, and the thickness of the second photoconductive layer is preferably 0.5 to 0.5. 15μm
, more preferably 1 to 10 μm, optimally 1 to 5 μm
It is desirable that this is done.

[0048] n having the characteristics capable of achieving the object of the present invention
In order to form a photoconductive layer made of c-SiC:H, it is necessary to appropriately set the temperature of the conductive substrate and the gas pressure in the reaction vessel as desired.

[0049] Substances that can be used as the Si supply gas used in the present invention to fabricate the first and second photoconductive layers include SiH4, Si2H6, and Si3.
Examples include silicon hydride (silanes) in a gaseous state or that can be gasified, such as H8, Si4 H10, etc., and Si
Preferred examples include H4 and Si2H6. Further, these raw material gases for supplying Si may be diluted with gases such as H2, He, Ar, Ne, etc. as necessary.

[0050] In the present invention, as the raw material for introducing carbon atoms, it is preferable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

[0051] Starting materials that can be effectively used as raw material gases for introducing carbon atoms (C) include saturated hydrocarbons having 1 to 5 carbon atoms, for example, containing C and H as constituent atoms;
Examples include ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH4), ethane (C2H
6), propane (C3H8), n-butane (n-
C4 H10), pentane (C5H12), ethylene hydrocarbons include ethylene (C2 H4), propylene (C3 H6), butene-1 (C4 H8),
Butene-2 (C4 H8), Isobutylene (C4 H8)
8), pentene (C5 H10), acetylene hydrocarbons include acetylene (C2 H2), methylacetylene (C3 H4), butyne (C4 H6), and the like.

[0052] Also, as the raw material gas containing Si and C as constituent atoms, Si(CH3)4, Si(C2H5
) 4 and the like can be mentioned.

In order to introduce hydrogen atoms into the first and second photoconductive layers in a state bonded to silicon, in addition to the above, H2
, or SiH4, Si2 H6, Si3 H
8. It can also be carried out by making silicon hydride such as Si4H10 and silicon or a silicon compound for supplying Si coexist in a reaction vessel to cause discharge.

In order to control the amount of hydrogen atoms contained in the first and second photoconductive layers, for example, the temperature of the conductive substrate, the temperature of the raw material used to contain the hydrogen atoms in the reaction vessel, etc. can be controlled. What is necessary is to control the amount introduced into the battery, the discharge power, etc.

Further, in the present invention, it is preferable that the first and second photoconductive layers contain atoms (M) for controlling conductivity, if necessary. The atoms that control conductivity are
It may be contained in the photoconductive layer in a uniformly distributed state, or it may be contained in a non-uniformly distributed state in the layer thickness direction.

[0056] Examples of atoms that control conductivity include so-called impurities in the semiconductor field, and atoms belonging to Group III of the periodic table (hereinafter abbreviated as "Group III atoms") that provide p-type conductivity. ) or atoms belonging to group V of the periodic table (hereinafter abbreviated as "group V atoms") that provide n-type conductivity.

Specifically, the group III atoms include:
Boron (B), aluminum (Al), gallium (Ga)
, indium (In), thallium (Tl), etc., and B, Al, and Ga are particularly suitable. As group V atoms,
Specifically, phosphorus (P), arsenic (As), antimony (Sb
), bismuth (Bi), etc., with P and As being particularly preferred.

The content of atoms (M) controlling conductivity contained in the photoconductive layer is preferably from 1×10 −3 to
5x104 atomic ppm, more preferably 1x10-2
~1x104 atomic ppm, optimally 1x10-1~5
It is desirable that the amount is x103 atoms ppm. especially,
The content of carbon atoms (C) in the photoconductive layer is 1x103
In the case of atomic ppm or less, the content of atoms (M) contained in the photoconductive layer is preferably 1x10-3 to 1
It is desirable that the content of carbon atoms (C) exceeds 1x103 atoms ppm, and the content of atoms (M) is preferably 1x103 atoms ppm.
It is desirable that the content be 10-1 to 5x104 atomic ppm.

[0059] Here, atomic ppm refers to parts per million based on the number of atoms.

In order to structurally introduce atoms that control conductivity, for example, group III atoms or group V atoms, into the photoconductive layer, a raw material for introducing group III atoms is used during layer formation. The substance or raw material for introducing Group V atoms may be introduced in a gaseous state into the reaction vessel together with other gases for forming the photoconductive layer. As the raw material for introducing Group III atoms or the raw material for introducing Group V atoms, those that are gaseous at normal temperature and pressure, or that can be easily gasified at least under layer-forming conditions, are adopted. It is desirable to Specifically, raw materials for introducing group III atoms include B2 H6, B4 H10, B5 H9, B5 for boron atom introduction.
H11, B5 H10, B6 H12, B6 H14
and boron halides such as BF3, BCl3, and BBr3. In addition, AlCl3
, GaCl3, Ga(CH3)3, InCl3
, TlCl3, etc. can also be mentioned.

[0061] In the present invention, the raw materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms include hydrogenated phosphorus such as PH3, P2 H4, PH4 I
, PF3, PF5, PCl3, PCl5, PB
Examples include phosphorus halides such as r3, PBr5, and PI3. In addition, AsH3, AsF3, AsCl3
, AsBr3, AsF5, SbH3, SbF3
, SbF5, SbCl3, SbCl5, BiH3
, BiCl3, BiBr3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

[0062] The raw materials for introducing atoms to control these conductivities may be H2, He, Ar, Ne, etc. as necessary.
It may be used after being diluted with gas such as.

Furthermore, the photoconductive layer of the photoreceptive member of the present invention includes compounds of groups Ia, IIa, VIb, and VIII of the periodic table.
It may contain at least one element selected from the group consisting of: The element may be uniformly distributed throughout the photoconductive layer, or it may be uniformly contained in the photoconductive layer but distributed non-uniformly in the layer thickness direction. There may be a portion containing it. However, in any case, it is necessary that the content be uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the conductive substrate in order to ensure uniform properties in the in-plane direction. be. Specifically, the Group Ia atoms include lithium (Li)
, sodium (Na), potassium (K), and group IIa atoms include beryllium (Be),
Examples include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).

Further, specific examples of Group VIb atoms include chromium (Cr), molybdenum (Mo), and tungsten (W), and examples of Group VIII atoms include iron (Fe) and cobalt. (Co), nickel (Ni)
etc. can be mentioned.

[0065] The temperature (Ts) of the conductive substrate is appropriately selected in an optimum range according to the layer design, but in general, it is preferably 20 to 500°C, more preferably 50 to 480°C.
℃, most preferably 100 to 450℃.

In the light-receiving member of the present invention, a layer region whose composition is continuously varied may be provided between the second photoconductive layer and the surface layer. By providing this layer region, the adhesion between each layer can be further improved.

Furthermore, in the light-receiving member of the present invention, a layer containing at least aluminum atoms, silicon atoms, carbon atoms, and hydrogen atoms in a non-uniform distribution state in the layer thickness direction is provided on the conductive substrate side of the photoconductive layer. It is desirable to have a region.

The surface layer in the present invention is composed of a non-single crystal material containing silicon atoms, carbon atoms, hydrogen atoms and, if necessary, halogen atoms as constituent elements. The surface layer does not substantially contain a substance that controls conductivity, such as that contained in the photoconductive layer.

[0069] The carbon atoms contained in the surface layer may be distributed uniformly throughout the layer, or they may be uniformly contained in the layer thickness direction but distributed non-uniformly. There may be a portion contained in the state. however,
In either case, it is necessary to uniformly distribute the content evenly in the in-plane direction parallel to the surface of the conductive substrate in order to make the properties uniform in the in-plane direction.

[0070] Carbon atoms contained in the entire surface layer region of the present invention have effects such as high dark resistance and high hardness. The content of carbon atoms contained in the surface layer is preferably 40 to 90 at%, more preferably 45 to 85 at%,
The optimum content is preferably 50 to 80 atomic %.

Note that the carbon atom content (atomic %) in the surface layer is defined as 100x carbon atoms/(carbon atoms+silicon atoms).

Further, the hydrogen atoms and halogen atoms contained in the surface layer in the present invention are nc-SiC(H,X)
It is effective in improving film quality by compensating for dangling bonds present in the photoconductive layer and reducing carriers trapped at the interface between the photoconductive layer and the surface layer, thereby improving image blurring. Furthermore, since the halogen atoms improve the water repellency of the surface layer, they also reduce high-humidity flow due to adsorption of water vapor. The content of halogen atoms in the surface layer is 20 at % or less, and the sum of the hydrogen atoms and halogen atoms is preferably 30 to 70 at %, more preferably 35 to 65 at %, most preferably is 40-6
It is desirable to set it to 0 atomic %.

Furthermore, in the present invention, the surface layer may contain at least one element selected from Group Ia, Group IIa, Group VIb, and Group VIII of the Periodic Table. The element may be uniformly distributed throughout the photoconductive layer,
Or, although it is evenly contained in the photoconductive layer,
There may be a portion where the content is non-uniformly distributed in the layer thickness direction. However, in any case, it is necessary that the content be uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the conductive substrate in order to ensure uniform properties in the in-plane direction. be.

Specific examples of Group Ia atoms include lithium (Li), sodium (Na), and potassium (K), and examples of Group IIa atoms include beryllium (Be) and magnesium (Mg). ), calcium (Ca
), strontium (Sr), barium (Ba), etc.

Further, specific examples of Group VIb atoms include chromium (Cr), molybdenum (Mo), and tungsten (W), and examples of Group VIII atoms include iron (Fe) and cobalt. (Co), nickel (Ni)
etc. can be mentioned.

In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.01 to 30 μm, from the viewpoint of obtaining desired electrophotographic properties and economical effects.
It is desirable that the thickness be 0.05 to 20 μm, most preferably 0.1 to 10 μm.

In the present invention, to form the surface layer composed of nc-SiC(H,X), a vacuum deposition method similar to the method for forming the photoconductive layer described above is employed.

When forming a surface layer having characteristics that can achieve the objects of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The optimum range for the conductive substrate temperature is selected as appropriate, but preferably 2
It is desirable that the temperature be 0 to 500°C, more preferably 50 to 480°C, and optimally 100 to 450°C.

[0079] The gas pressure inside the reaction vessel is also appropriately selected within the optimum range, preferably 1 x 10-5 to 10 Torr, more preferably 5 x 10-5 to 3 Torr, most preferably 1 x
It is desirable to set it to 10-4 to 1 Torr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges for the conductive substrate temperature and gas pressure for forming the surface layer, but these layer formation factors are usually determined independently and separately. Instead, it is desirable to determine the optimum value of each layer fabrication factor based on mutual and organic relationships in order to form a surface layer with desired properties.

[0081] In the present invention, the energy for generating plasma can be DC, high frequency, microwave, etc., but in particular, when microwaves are used for the energy for plasma generation, the microwaves can be applied to the adsorbed water. The effect of the present invention becomes more remarkable because the change in the interface becomes more remarkable.

In the present invention, when microwaves are used to generate plasma, the microwave power may be any power as long as it can generate discharge, but is 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW.
The following are suitable for practicing the invention.

The present invention can be applied to any method of manufacturing an electrophotographic photoreceptor, but in particular, a base body is provided to surround a discharge space, and microwaves are introduced through a waveguide from at least one end of the base body. There is a great effect when forming a deposited film depending on the structure.

[0084] Hereinafter, the effects of the present invention will be specifically explained using examples, but the present invention is not limited by these in any way.

[0085]

【Example】

<Example 1 and Comparative Example 1> Example 1 Diameter 108 mm made of 99.5% pure aluminum
The surface of a cylindrical substrate with a length of 358 mm and a wall thickness of 5 mm was cut in the same manner as the above-described example of the procedure of the method for manufacturing an electrophotographic photoreceptor according to the present invention, and 15 minutes after the cutting process was completed, the surface was cut as shown in FIG. The surface of the substrate was pretreated under the conditions shown in Table 1 using the surface treatment apparatus shown below. However, in this example, polyethylene glycol nonylphenyl ether was used as a 1 wt % aqueous solution as the surfactant. Electrophotography was performed on the aluminum cylinder pretreated in this way using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. A photoreceptor was produced. In this example, in order to change the pattern of change in carbon content in the photoconductive layer as shown in FIG. 7, the flow rate of CH4 introduced during formation of the photoconductive layer was varied linearly. At this time, the carbon content at the interface between the photoconductive layer and the substrate was set to about 30 atomic %. The carbon content was determined by creating a calibration curve for a standard sample through elemental analysis using the Rutherford backscattering method, and by comparing the signal intensities of the standard sample and the prepared sample using Auger spectroscopy to determine the absolute amount.

The surface quality of the produced electrophotographic photoreceptor was first visually evaluated, and then the surface quality was evaluated using a Canon copier NP-755.
0 was installed in an electrophotographic device modified for experiments, and the charging ability,
The following evaluations were made regarding electrophotographic properties such as sensitivity and residual potential. (4) Surface cloudiness The produced electrophotographic photoreceptor was visually inspected for the degree of surface cloudiness.

◎ means no clouding; ○ means partly cloudy; △ means partly cloudy; and x means cloudy all over. ■Charging ability, sensitivity, residual potential Charging ability...The electrophotographic photoreceptor was installed in the experimental equipment, a high voltage of +6 kV was applied to the charger to perform corona charging, and the dark area surface potential of the electrophotographic photoreceptor was measured using a surface potentiometer. Measure.

Charging ability unevenness: The above measurement is performed at 9 locations, 3 locations each on the top, middle, and bottom of one electrophotographic photoreceptor, and the value is calculated by subtracting the smallest potential from the highest potential. shows.

Sensitivity: The electrophotographic photoreceptor is charged to a constant dark area surface potential. Then, a light image is immediately irradiated. The light image was created using a xenon lamp light source and a filter.
Irradiate with light excluding light in the wavelength range of 0 nm or less. At this time, the bright area surface potential of the electrophotographic photoreceptor is measured using a surface electrometer. The exposure amount is adjusted so that the bright area surface potential becomes a predetermined potential, and the exposure amount at this time is defined as the sensitivity.

Sensitivity unevenness...Measure the above measurements at 9 locations, 3 locations each on the top, middle, and bottom of one electrophotographic photoreceptor, and calculate the value obtained by subtracting the smallest potential from the largest potential. show.

Residual potential: The electrophotographic photoreceptor is charged to a constant dark area surface potential. Then, a constant amount of relatively strong light is immediately applied. The optical image uses a xenon lamp light source,
Light excluding light in a wavelength range of 550 nm or less was irradiated using a filter. At this time, the bright area surface potential of the electrophotographic photoreceptor is measured using a surface electrometer. ■ White spots and uneven halftones...The electrophotographic photoreceptor was used with a Canon Co., Ltd. copier NP7550.
was placed in a copying machine modified for experimental purposes, and an image was formed on paper by transferring it using a normal electrophotographic process, and the image was evaluated according to the following procedure.

[0092] White dots...Diameter 0.2 within the same area of the copy image obtained when copying a full black chart made by Canon (part number: FY9-9073) on the document table
The number of white spots smaller than mm was counted.

[0093] Halftone unevenness...Canon halftone chart (part number: FY9-90
The image density was measured at 100 points on the copy image obtained when copying 42) was placed on a document table, with each unit being a circular area with a diameter of 0.05 mm, and the variation in the image density was evaluated.

For each, ◎ is "particularly good", ○ is "good", △ is "no problem in practical use", and x is "problem in practical use". These results are shown in Table 3. Comparative Example 1 A conductive substrate similar to that of Example 1 was cut in the same manner as in Example 1, and the surface of the conductive substrate after cutting was cleaned under the conditions shown in Table 4 using the conventional conductive substrate cleaning apparatus shown in FIG. was processed. The conductive substrate cleaning apparatus shown in FIG. 3 includes a processing tank 302 and a substrate transport mechanism 303. Processing tank 3
02 consists of a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transport mechanism 303 includes a transport rail 365 and a transport arm 361, and the transport arm 361 includes a moving mechanism 362 that moves on the rail 365, a chucking mechanism 363 that holds the base 301, and this chucking mechanism 363.
It consists of an air cylinder 364 for raising and lowering.

After cutting, the base 3 placed on the input table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichloroethane (trade name: Eterna VG, manufactured by Asahi Kasei Industries, Ltd.) 322 in a cleaning tank 321 performs cleaning to remove cutting oil and chips adhering to the surface.

After cleaning, the substrate 301 is transported to a carry-out table 351 by a transport mechanism 303. In the same way as in Example 1, Table 5
A so-called functionally separated electrophotographic photoreceptor having a three-layer structure consisting of a base 601, a charge transport layer 602, a charge generation layer 603, and a surface layer 604 as shown in FIG. 6 was prepared under the conditions shown in FIG. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1,
The results are shown in Table 3 together with the results of Example 1.

As is clear from Table 3, according to the method of the present invention, the sensitivity is improved and the residual potential is kept low. In particular, it can be seen that the photoreceptor exhibits excellent characteristics with respect to cloudiness on the surface, uneven chargeability, uneven sensitivity, and uneven halftone. <Example 2 and Comparative Example 2> Example 2 The electrons shown in FIGS. 2(a) and 2(b) were applied onto a substrate that had been pretreated in the same manner as in Example 1 using the substrate surface treatment apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under the conditions shown in Table 6 by a microwave glow discharge method using a photographic photoreceptor manufacturing apparatus. The produced electrophotographic photoreceptor was evaluated in the same manner as in Example 1. As a result, exactly the same results as in Example 1 were obtained. Comparative Example 2 Using the electrophotographic photoreceptor manufacturing apparatus shown in FIGS. 2(a) and 2(b), A so-called functionally separated electrophotographic photoreceptor having a three-layer structure consisting of a substrate, a first photoconductive layer, a second photoconductive layer, and a surface layer was prepared under the conditions shown in Table 7 by a microwave glow discharge method. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 2. As a result, exactly the same results as Comparative Example 2 were obtained. <Example 3 and Comparative Example 3> Example 3 Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4, on a substrate that had been pretreated in the same manner as in Example 1 using the substrate surface treatment apparatus shown in FIG. In accordance with the procedure detailed above, an electrophotographic photoreceptor was produced using a high frequency glow discharge method under the production conditions shown in Table 8. In this example, in order to change the pattern of change in carbon content in the photoconductive layer as shown in FIGS. 8 and 9, the flow rate of CH4 introduced during formation of the photoconductive layer was changed, and two types of photosensitive The body was created. In either pattern, the carbon content on the substrate-side surface of the photoconductive layer was about 30 atomic %. For the carbon content, a calibration curve of a standard sample was prepared by elemental analysis using Rutherford backscattering method, and the absolute amount was determined by comparing the signal intensity of the standard sample and the prepared sample using Auger spectroscopy.

[0098] The surface cloudiness of the produced electrophotographic photoreceptor, and the Canon NP-7550 copying machine were installed in an electrophotographic apparatus modified for experimental purposes, and the charging ability, sensitivity, residual potential, etc. were the same as in Example 1. The method was evaluated. Table 9 shows the results.
Shown below. Comparative Example 3 Example 3 was applied onto a substrate pretreated in the same manner as Comparative Example 1.
In the same manner as above, an electrophotographic photoreceptor was produced with the carbon content pattern shown in FIGS. 10 and 11, and the same evaluation as in Example 3 was performed. The results are shown in Table 9 together with the evaluation results of Example 3.

[0099] Compared with the results of Comparative Example 3, the carbon content variation pattern of the photoconductive layer according to the present invention yields particularly good results in terms of surface haze, chargeability unevenness, sensitivity unevenness, and halftone unevenness. I understand that. <Example 4 and Comparative Example 4> Example 4 Using the substrate surface treatment apparatus shown in FIG. 1, the electrophotographic photosensitive material shown in FIGS. An electrophotographic photoreceptor was manufactured using the body manufacturing apparatus under the manufacturing conditions shown in Table 10 in the same manner as in Example 3 except that the microwave glow discharge method was used. In this example, in order to change the pattern of change in the carbon content in the photoconductive layer as shown in FIGS. 8 and 9, C was introduced at the time of forming the photoconductive layer.
The flow rate of H4 was varied. In either pattern, the carbon content on the surface of the photoconductive layer on the substrate side is approximately 30 at.%.
I made it so that For the carbon content, a calibration curve of a standard sample was prepared by elemental analysis using Rutherford backscattering method, and the absolute amount was determined by comparing the signal intensity of the standard sample and the prepared sample using Auger spectroscopy. The produced electrophotographic photoreceptor gave exactly the same results as in Example 3. Comparative Example 4 Using the substrate surface treatment apparatus shown in FIG. 3, electrophotography was performed on a substrate pretreated in the same manner as in Comparative Example 1 with the carbon content patterns shown in FIGS. 10 and 11 in the same manner as in Example 4. A photoreceptor was produced. When the obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 4, results exactly the same as in Comparative Example 3 were obtained. <Example 5> Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4, the procedure detailed above was carried out on a substrate that had been pretreated in the same manner as in Example 1 using the substrate surface treatment apparatus shown in FIG. According to the above, an electrophotographic photoreceptor was manufactured using the high frequency glow discharge method under the manufacturing conditions shown in Table 2. In this example, the change pattern of the carbon content in the photoconductive layer is as shown in FIG.
4 by changing the flow rate. The carbon content on the substrate-side surface of the photoconductive layer was determined by Auger spectroscopy in the same manner as described above.

[0100] The number of occurrences of cloudiness and spherical protrusions on the surface of the produced electrophotographic photoreceptor, and also the number of occurrences of the Canon copier NP-75.
No. 50 was installed in an electrophotographic apparatus modified for experimental use, and electrophotographic characteristics such as charging ability, sensitivity, residual potential, white spots, and halftone unevenness, and image quality were evaluated. Each item was evaluated using the following method. (2) Surface cloudiness Evaluation was made in the same manner as in Example 1. (2) Number of spherical protrusions The entire surface of the produced electrophotographic photoreceptor was observed with an optical microscope, and the number of spherical protrusions with a diameter of 20 μm or more within an area of 100 cm 2 was determined. Results are obtained for each electrophotographic photoreceptor, and the one with the largest number of spherical protrusions is given 100%.
A relative comparison was made as follows. The results were classified as follows.

◎: Less than 60% ○: 80 to 60% △: 100 to 80% (2) Charging ability, sensitivity, sensitivity unevenness, and residual potential Evaluations were made in the same manner as in Example 1. ■ White spots/halftone unevenness White spots/halftone unevenness: Evaluation was made in the same manner as in Example 1.

The results thus obtained are summarized in Table 11. The results show that the properties are improved when the amount of carbon on the surface of the photoconductive layer on the substrate side is 0.5 to 50 atomic %, and very good results are obtained when the carbon content is 1 to 30 atomic %. <Example 6> The substrate shown in FIGS.
) Using the electrophotographic photoreceptor manufacturing apparatus shown in Table 6, an electrophotographic photoreceptor was manufactured under the manufacturing conditions shown in Table 6 by a microwave glow discharge method according to the procedure detailed above. In this example, the change pattern of the carbon content in the photoconductive layer was determined by using the pattern shown in FIG. Changed.

[0103] As a result of evaluation in the same manner as in Example 5, exactly the same results as in Table 11 were obtained. <Example 7> Table 12 was formed on a substrate pretreated in the same manner as in Example 1 by high-frequency glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under the manufacturing conditions shown below. In this example, in order to change the fluorine content in the photoconductive layer as shown in FIG. 12, the flow rate of SiF4 introduced during formation of the photoconductive layer was changed. (I) Transfer the produced electrophotographic photoreceptor to a Canon copier NP.
-7550 was installed in an electrophotographic device modified for experiments,
White spots and uneven halftones before the accelerated durability test.
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Example 1 and Example 5. Further, ghost evaluation was performed as follows.

Ghost...Reflection density 1.1 on Canon ghost test chart (part number: FY9-9040)
, a 5mm black circle pasted is placed at the leading edge of the image on the document table, and a Canon halftone chart is placed on top of it.The 5mm ghost chart that is observed on the halftone copy of the copied image. The difference between the reflection density of the image and the reflection density of the halftone area was measured. For each, ◎
indicates "particularly good"; ○ indicates "good"; △ indicates "no practical problem"; × indicates "practical problem".

[0105] The results are summarized in Table 13. (II) Next, the produced electrophotographic photoreceptor was installed in an electrophotographic apparatus which was a modified Canon NP-7550 copying machine for experimental purposes, and an accelerated durability test was conducted for the equivalent of 3 million copies. Then, electrophotographic characteristics such as white spots, halftone unevenness, and ghosts were evaluated in the same manner as in (I). Table 1 shows the results.
They are summarized in 4.

From the results in Tables 13 and 14, it is clear that by setting the fluorine content in the photoconductive layer to a range of 95 atomic ppm or less, an electrophotographic photoreceptor with excellent image characteristics and durability can be produced. It was shown that this is possible. <Example 8> Using the substrate surface treatment apparatus shown in FIG. 1, the substrate shown in FIG. 2(a),
Using the electrophotographic photoreceptor manufacturing apparatus shown in (b), an electrophotographic photoreceptor was manufactured using the microwave glow discharge method under the manufacturing conditions shown in Table 15 in the same manner as in Example 7. The produced electrophotographic photoreceptor was evaluated in the same manner as in Example 7. The results were exactly the same as Tables 13 and 14. <Example 9> Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4, a substrate was subjected to the same pretreatment as in Example 1 using the substrate surface treatment apparatus shown in FIG. Electrophotographic photoreceptors were manufactured under 16 manufacturing conditions. In this experiment, the flow rate of CH4 introduced during the formation of the surface layer was varied so as to vary the amount of carbon contained in the surface layer.

[0107] The produced electrophotographic photoreceptor was installed in an electrophotographic device that was modified from a Canon copier NP-8580 for experimental purposes, and the charging ability, charging ability unevenness, residual potential, image evaluation before durability, and 3 million copies were evaluated. Image evaluation after a correspondingly accelerated durability test was performed by the method shown below.

Charging ability: Conducted in the same manner as in Example 1.

Residual potential: The same procedure as in Example 1 was carried out.

[0110] Image evaluation after durability...5-level limit samples were prepared for each of white spots and scratches, and the total evaluation results were classified into the following 4 levels.

◎: "Particularly good" ○: "Good" △: "No practical problem" ×: "Practical problem" The following results are shown in Table 17. As is clear from the table, when the carbon content is 40 to 90 atom %, the charging ability and durability are significantly improved. <Example 10> Using the substrate surface treatment apparatus shown in FIG. 1, the substrate shown in FIG.
Using the electrophotographic photoreceptor manufacturing apparatus shown in . In this experiment, the flow rate of CH4 introduced during the formation of the surface layer was varied so as to vary the amount of carbon contained in the surface layer.

The produced electrophotographic photoreceptor was evaluated in the same manner as in Example 9. As a result, results completely similar to those in Table 17 were obtained. <Example 11> Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4, a substrate was subjected to the same pretreatment as in Example 1 using the substrate surface treatment apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under 19 manufacturing conditions. In this experiment, H2 was introduced during the formation of the surface layer to change the amount of hydrogen atoms and fluorine atoms contained in the surface layer.
and/or the flow rate of SiF4 was varied.

The produced electrophotographic photoreceptor was installed in an electrophotographic apparatus that was a modified copying machine NP-8580 manufactured by Canon for experimental purposes, and evaluated in terms of three items: residual potential, sensitivity, and image deletion.

Residual potential: The same procedure as in Example 1 was carried out.

Sensitivity: The same procedure as in Example 1 was carried out.

Sensitivity unevenness: The same procedure as in Example 1 was carried out.

Image deletion: A test chart made by Canon (part number: FY9-9058) consisting of characters on a white background is placed on a document table, and a copy is made by irradiating it with twice the normal exposure amount. The obtained copy image was observed and it was evaluated whether the thin lines on the image were connected without interruption. However, if there was unevenness on the image at this time, the entire image area was evaluated and the results for the worst part were shown.

0118]◎…Good ○…There are some interruptions.

0119] △…There are many breaks, but it can be recognized as characters,
There is no practical problem.

The results obtained are shown in Table 20. As is clear from Table 20, the sum of hydrogen content and fluorine content in the surface layer is 30 to 70 at%, and the fluorine content is 20
It has been found that by setting the amount within the range of atomic % or less, good results can be obtained in both residual potential and sensitivity, and furthermore, image blurring at strong exposure can be significantly suppressed. <Example 12> Using the substrate surface treatment apparatus shown in FIG. 1, the substrate shown in FIG.
, Table 21 was prepared in the same manner as in Example 10 by the microwave glow discharge method using the electrophotographic photoreceptor manufacturing apparatus shown in (b).
An electrophotographic photoreceptor was manufactured under the manufacturing conditions shown below. In addition, H
The e flow rate is 2000 sccm including the H2 flow rate.
The internal pressure was kept constant. The produced electrophotographic photoreceptor was evaluated in the same manner as in Example 10. As a result, results completely similar to those in Table 20 were obtained. <Example 13> The electrophotographs shown in FIGS. 2(a) and 2(b) were formed on a substrate that had been pretreated in the same manner as in Example 1 using the substrate surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 22. An electrophotographic photoreceptor was manufactured using a photoreceptor manufacturing apparatus under the conditions shown in Table 23 by a microwave glow discharge method. In this example, the value of SiF4/SiH4 was set to 10 to 10 so that the fluorine content in the photoconductive layer had the distribution shape shown in FIGS. 12 to 15.
Change the flow rate smoothly within the range of 50 ppm,
Various types of electrophotographic photoreceptors were manufactured. An electrophotographic photoreceptor was also produced under the same conditions except that it did not contain fluorine. The following evaluations were performed on the above five types of electrophotographic photoreceptors.

[0121] Surface haze, charging ability, sensitivity, residual potential, white spots, halftone unevenness, ghost...Evaluation temperature characteristics similar to those in Example 1...The prepared electrophotographic photoreceptor was used for experimental purposes using a Canon Co., Ltd. copying machine NP7550. The electrophotographic photoreceptor was placed in a modified copying machine, the surface temperature of the electrophotographic photoreceptor was varied to 30-45°C, and a high voltage of +6 kV was applied to the charger to perform corona charging.
Measure the surface potential of the dark area using a surface electrometer. The change in the surface temperature of the dark area with respect to the surface temperature of the photoreceptor is approximated by a straight line, and the slope thereof is defined as a "temperature characteristic" and is expressed in units of [V/deg].

◎...Excellent.

○...Excellent.

△...No practical problem.

×...Not practical.

The above results are shown in Table 24. The table shows that all electrophotographic properties including ghost and temperature properties are improved when fluorine is contained in the photoconductive layer and distributed in the film thickness direction.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

[Table 8]

[0135]

[Table 9]

[0136]

[Table 10]

[0137]

[Table 11]

[0138]

[Table 12]

[0139]

[Table 13]

[0140]

[Table 14]

[0141]

[Table 15]

[0142]

[Table 16]

[0143]

[Table 17]

[0144]

[Table 18]

[0145]

[Table 19]

[0146]

[Table 20]

[0147]

[Table 21]

[0148]

[Table 22]

[0149]

[Table 23]

[0150]

[Table 24]

[0151]

Effects of the Invention As explained above, according to the present invention, in an electrophotographic photoreceptor manufacturing method including a step of forming a functional film on a metal substrate, the layer of the present invention can be applied particularly on a metal substrate. In a method for manufacturing an electrophotographic photoreceptor, which includes a step of forming an electrophotographic photoreceptor film using amorphous silicon as a matrix by a plasma CVD method, the surface of the conductive substrate is The method includes a step of cutting the layer with a predetermined precision, a step of cleaning the cut surface of the conductive substrate after the cutting step, and a step of bringing the cleaned surface of the conductive substrate into contact with pure water. ,
An inexpensive electrophotographic photoreceptor that provides uniform, high-quality images.
Moreover, it can be produced stably without worrying about environmental pollution due to organic solvents and the like.

Furthermore, according to the present invention, the photoconductive layer is formed by continuously changing carbon atoms from the conductive substrate.
It is now possible to smoothly connect the important functions for electrophotographic photoreceptors, which are the generation of charge (photocarriers) and the transport of the generated charge, and the conventional charge generation layer and charge transport layer are separated, so-called functional separation. This prevents poor charge travel due to the difference in optical energy gap between the charge generation layer and the charge transport layer, which is a problem in type photoreceptive members, and contributes to improving photosensitivity and reducing residual potential.

[0153] Furthermore, since the first photoconductive layer contains carbon, the dielectric constant of the photoreceptive layer can be lowered, so that the capacitance per layer thickness can be reduced and the capacitance can be increased. Significant improvements were seen in chargeability and photosensitivity,
Furthermore, the voltage resistance against high voltage is also improved.

[0154] By disposing a layer containing a large amount of carbon on the conductive substrate side, charging ability is improved by blocking charge injection from the conductive substrate, and furthermore, the adhesion between the conductive substrate and the photoconductive layer is improved. The film properties are improved, and peeling of the film and generation of minute defects can be suppressed. By improving the adhesion of the film, there is less damage to the cleaning blade and separation claw even when a large number of images are continuously formed, and the cleaning performance and separation performance of the transfer paper are also improved. Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the dielectric constant is lowered, durability against high voltage is improved, so that "leak spots" caused by dielectric breakdown in a part of the light-receiving member are less likely to occur.

By using the second photoconductive layer of the present invention, particularly high sensitivity and low residual potential can be achieved, and further, ghost reduction is also excellent.

Further, according to the present invention, the yield rate for defects in appearance such as clouding of the surface of the photoreceptor after manufacture can be greatly increased, and in particular, unevenness in electrical properties such as uneven charging performance, uneven sensitivity, and uneven halftone can be significantly suppressed.

[0157] The above effects can be achieved by, for example, microwave C
This is especially noticeable when layer formation is performed at a high deposition rate, such as in the VD method.

[Brief explanation of the drawing]

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

FIG. 2(a) is a schematic vertical cross-sectional view showing an example of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by microwave plasma CVD, and FIG. 2(b) is a cross-sectional view thereof.

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

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

FIG. 5 is an explanatory diagram showing a layer structure constructed in the method for manufacturing an electrophotographic photoreceptor of the present invention.

FIG. 6 is an explanatory diagram showing the layer structure of a conventional electrophotographic photoreceptor.

FIG. 7 is a graph showing a pattern of changes in carbon content of a photoconductive layer of an example of the present invention.

FIG. 8 is a graph showing a pattern of changes in carbon content of a photoconductive layer of an example of the present invention.

FIG. 9 is a graph showing a pattern of changes in carbon content of a photoconductive layer of an example of the present invention.

FIG. 10 is a graph showing the carbon content distribution pattern of a photoconductive layer of a comparative product.

FIG. 11 is a graph showing the carbon content distribution pattern of a photoconductive layer of a comparative product.

FIG. 12 is a graph showing a pattern of changes in the fluorine content of the photoconductive layer of an example of the present invention.

FIG. 13 is a graph showing a pattern of changes in the fluorine content of the photoconductive layer of an example of the present invention.

FIG. 14 is a graph showing a pattern of changes in the fluorine content of the photoconductive layer of an example of the present invention.

FIG. 15 is a graph showing a pattern of changes in the fluorine content of the photoconductive layer of a product according to the present invention.

[Explanation of symbols]

101 Substrate 102 Processing tank 103 Substrate transport mechanism 111 Substrate loading table 121 Substrate cleaning tank 122 Cleaning liquid 131 Pure water contact tank 132, 142 Nozzle 141 Drying tank 151 Substrate unloading table 161 Transport arm 162 Moving mechanism 163 Chucking mechanism 164 Air cylinder 165 Rail 201 Reaction container 202 Microwave introduction window 203 Waveguide 204 Exhaust pipe 205 Cylindrical substrate 206 Discharge space 207 Heater 209 Rotating shaft 210 Motor 211 DC bias power supply 212 Bias application electrode 301 Substrate 302 Processing tank 303 Substrate transport mechanism 311 Substrate loading Table 321 Substrate cleaning tank 322 Cleaning liquid 351 Substrate unloading table 361 Transport arm 362 Movement mechanism 363 Chucking machine 364 Air cylinder 365 Rail 400 Deposited film forming device 401 Reaction vessel 402 Cylindrical substrate 403 Cylindrical substrate heating heater 404
Raw material gas introduction pipe 405 High frequency matching box 406
Raw material gas introduction piping 407 Reaction vessel leak valve 408 Main exhaust valve 409 Vacuum gauge 410 Raw material gas supply devices 411 to 416 Mass flow controller 41
7-422 Raw material gas cylinder 423-428
Raw material gas cylinder valves 429 to 424 Raw material gas inflow valves 435 to 440 Raw material gas outlet valves 441 to 446 Pressure regulator 447 Valve 501, 601 Substrate 502 First photoconductive layer 503 Second photoconductive layer 504, 604 Surface layer 505, 605 Photoreceptor layer 602 Charge transport layer 603 Charge generation layer

Claims (5)

[Claims] Claims 1: (a) cutting the surface of a conductive substrate with a predetermined precision; (b) cleaning the substrate surface after cutting with water; (c) bringing the cleaned substrate surface into contact with pure water. (d) the cleaned substrate surface contains carbon atoms and hydrogen atoms throughout the layer, and the content of the carbon atoms is non-uniform in the layer thickness direction, and the conductive substrate a step of forming a first photoconductive layer made of a non-single-crystal material having silicon atoms and carbon as a matrix, which are highly distributed on the sides, by a plasma CVD method; (e) the first photoconductive layer formed as described above; (f) forming a second photoconductive layer based on silicon atoms by plasma CVD; (f) forming a second photoconductive layer based on silicon atoms and containing carbon atoms and hydrogen atoms on the second photoconductive layer formed above; A method for manufacturing an electrophotographic photoreceptor, comprising the steps of forming a surface layer by plasma CVD, and each of the above steps. 2. The content of carbon atoms in the first photoconductive layer is 0.5 to 50 at % at the interface with the conductive substrate and at or near the interface with the second photoconductive layer. 2. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the content of hydrogen atoms in the photoconductive layer is substantially 0% and the content of hydrogen atoms in the photoconductive layer is 1 to 40 at%. 3. The content of carbon atoms in the surface layer is 1
The value expressed as 00 x carbon atom/(carbon atom + silicon atom) is 40 to 90 atom%, and contains a halogen, and the content of the halogen atom is 20 atom% or less, and contains hydrogen atoms and halogen atoms. 3. The method for producing an electrophotographic photoreceptor according to claim 2, wherein the sum of the amounts is 30 to 70 atom %. 4. The method for manufacturing an electrophotographic photoreceptor according to claim 1, wherein the first photoconductive layer contains halogen. 5. The halogen in the first photoconductive layer is
5. The method for manufacturing an electrophotographic photoreceptor according to claim 4, wherein the distribution has a maximum value at or near the interface with the second photoconductive layer.