JP2786756B2 - Manufacturing method of electrophotographic photoreceptor - 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 manufacturing an electrophotographic photosensitive member having a photoreceptor layer containing silicon as a base on a conductive substrate.

[0002] The present invention relates to a method for manufacturing an electrophotographic photosensitive member that can be widely used in electrophotographic technology application fields, such as an electrophotographic copying machine, a laser beam printer, an LED printer, a liquid crystal printer, and a laser plate making machine.

[0003]

2. Description of the Related Art Non-single-crystal deposited films, for example, amorphous deposited films of amorphous silicon compensated with hydrogen and / or halogen (for example, fluorine, chlorine, etc.) have been proposed for use in electrophotographic photoreceptors. Some of them have been put to practical use. Conventionally, as a method for forming such a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (photo CVD method), and a method of decomposing a source gas by plasma ( Many methods are known, such as a plasma CVD method. Among them, the 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 a deposited film in a thin film on a substrate is most suitable for a method of forming an amorphous silicon deposited film for electrophotography. , And its practical use is very advanced. Such an example is described in, for example, JP-A-54-86341.

The amorphous silicon photoreceptor is characterized by being non-polluting, having high image quality and high durability, and the amorphous silicon photoreceptor currently used practically shows its characteristics sufficiently. . However,
In order for amorphous silicon photoconductors to become more and more popular in the future, further cost reduction, further improvement in electrical characteristics, and higher durability are desired.

In recent years, environmental pollution on a global scale has become a problem, and it is necessary to promptly improve not only substances that lead to environmental pollution but also their use in the manufacturing stage. Although the amorphous silicon photoreceptor itself is pollution-free, it is necessary to reconsider from the above points, from the cleaning of the cylinder, which is the base portion of the photoreceptor, to the packing after the production, in the stage of manufacturing the same.

In view of the above, the method of cleaning a conventional amorphous silicon photosensitive member will be reviewed. It has been known that when fabricating an amorphous silicon photoreceptor, care must be taken with respect to cleaning of a substrate before fabricating a film. When a metal is used as the substrate on which the amorphous silicon photoreceptor is deposited, in order to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to always maintain high positional accuracy in order to maintain image quality. There are many. For this reason, aluminum alloys, which are particularly excellent in workability, dimensional stability, etc., are widely used. Generally, when processing these substrates, lathe processing is performed using an oil-based substance such as cutting oil. Therefore, after processing, there is always a residue of oil-based substances on the substrate,
Dust in the air is attached. If these residues remain due to insufficient cleaning, a uniform deposited film without defects cannot be formed, or sufficient electrical characteristics cannot be obtained, and image defects may occur especially when used for a long time. The problem is known. Therefore, when manufacturing an electrophotographic photosensitive member, it is necessary to pay close attention to thoroughly wash the substrate.

Under these circumstances, for example, Japanese Patent Application Laid-Open No. 61-171
Japanese Patent Application Publication No. 798 describes a technique relating to a method of processing a substrate of an electrophotographic photosensitive member. This publication discloses a technique of obtaining a good quality electrophotographic photosensitive member such as amorphous silicon by cutting a substrate using a cutting oil of a specific component. The publication also describes that after cutting, the substrate is washed with triethane (trichloroethane: C ₂ H ₃ Cl ₃ ). A photoreceptor manufactured using a substrate washed by such a method has a certain degree of characteristics, and is now widely used without any particular problem.However, an organic solvent such as trichloroethane, Its use must be avoided because it has a harmful effect not only on the human body but also on the local environment.

[0008] In order to solve this problem, in recent years, several methods for cleaning a substrate using an aqueous system have been proposed instead of the above-mentioned cleaning.

[0009] For example, Japanese Patent Application Laid-Open No. 63-264764 discloses a technique for roughening the surface of a substrate with a water jet.

Japanese Patent Laid-Open Publication No. 1-130159 discloses a technique for cleaning an electrophotographic substrate with a water jet. The publication describes amorphous silicon as well as selenium and an organic photoconductor as examples of the photoconductor, and suggests that the present technology can be applied to an amorphous silicon photoconductor. However, the gazette does not mention at all the problems at the time of the actual operation, especially the problems peculiar to the plasma CVD method.

[0011] On the other hand, the study of improving the quality of the amorphous silicon photosensitive member has been steadily advanced by studying the layer structure.

For example, Japanese Patent Application Laid-Open No. 54-145540 discloses that when amorphous silicon containing 0.1 to 30 atomic% of carbon as a chemical modifying substance is used as a photoconductive layer of an electrophotographic photosensitive member, dark resistance is high, It is shown to exhibit excellent electrophotographic properties with good light sensitivity.

JP-A-57-119357 discloses that an electrophotographic photosensitive member having excellent characteristics can be obtained by distributing a large amount of carbon atoms to the substrate side in amorphous silicon.

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

[0015] Under these circumstances, problems which have been conventionally encountered in terms of high image quality, high durability and no pollution are listed below.

First, reduction of black or white dot image defects called spots is one of the problems that have been greatly desired. At present, there is an increasing demand from the demand for high image quality to the reduction of small-sized spots, which have not been much of a problem in the past. The analysis of the cause of this spot is also progressing every day, and some knowledge can be obtained. The cause of the spots is mostly due to abnormal growth called spherical projections caused by dust or the like generated when the amorphous silicon film is deposited. In addition to the above, there is also a durable spot which increases as the durability is continued, and this is caused by scattering of toner and mixing of paper dust into the separation charger. As a manufacturer of photoconductors to reduce image defects caused by these causes, it is important to improve the cleanness of the deposited film forming equipment, improve the method of forming the deposited film, and improve the manufacturing method. It is necessary to take measures such as increasing the pressure resistance of the silicon photoconductor. In addition, since higher image quality and higher function have been demanded in recent electrophotographic copying machines, it is essential to be able to faithfully reproduce an original including a halftone such as a photograph. For this reason, electrophotographic photoreceptors are particularly desired to reduce halftone unevenness. In particular, in a full-color copying machine that has become widespread in recent years, since this unevenness becomes a subtle unevenness in color and is visually recognized clearly,
It is a big problem.

Furthermore, it is desired that the electrophotographic photosensitive member maintain high image quality and high sensitivity and greatly improve durability under any environment. The durability characteristics of the amorphous silicon photoreceptor, which it excels at, do not require replacement until the end of the life of the copying machine. ,
The possibility of being released from maintenance such as photoreceptor replacement is beginning to be seen. Therefore, new products are required to have the same or higher durability as that of the copying machine itself, and it is desired that the durability be further enhanced. Under these demands, it has conventionally been difficult, and still insufficient, to achieve both high charging performance and prevention of image deletion at a high level, and to greatly increase the durability in all environments.

At present, it is necessary to review all of the problems from the step of cleaning the conductive substrate to the step of manufacturing the electrophotographic photosensitive member, and to conduct a total study.

[0019]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a conventional electrophotographic photoreceptor having a conventional light-receiving layer composed of a material having silicon atoms as a base material as described above. It is an object of the present invention to solve the above problems and to supply a photoreceptor having excellent electrical characteristics and extremely reduced image defects at a low cost and with good yield.

That is, an object of the present invention is not to use an organic solvent in the production process, and therefore, it is excellent in environmental protection and greatly increases the yield of the produced electrophotographic photoreceptor due to poor appearance, image defects, halftone unevenness, etc. Especially excellent in the characteristics of
It is an object of the present invention to provide a method of manufacturing an electrophotographic photosensitive member that can be used in any environment at low cost.

Another object of the present invention is to provide a uniform and high-quality silicon atom as a base material having excellent adhesion between a layer provided on a conductive substrate and the conductive substrate and between layers of a layer to be laminated. An object of the present invention is to provide an electrophotographic photoreceptor having a photoreceptive layer composed of a material as described below.

Still another object of the present invention is that when applied as an electrophotographic photoreceptor, it has a sufficient charge holding ability during a charging process for forming an electrostatic image, and can easily produce high-quality images with high resolution. For producing an electrophotographic photoreceptor having a photoreceptive layer composed of ordinary silicon atom-based material and exhibiting excellent electrophotographic properties which can be applied very effectively to electrophotography. Is to provide.

[0023]

Means for Solving the Problems In order to overcome the above-mentioned problems in the conventional method of forming a deposited film, the present inventors have made intensive studies from the viewpoints of productivity, cost reduction, and environmental protection. As a result, the above object has been achieved.

The present invention has been completed on the basis of the above findings. The gist of the present invention is as follows: (a) a step of cutting the surface of a conductive substrate with a predetermined accuracy; and (b) a surface of the substrate after cutting. Is washed with water, (c) a step of bringing the washed substrate surface into contact with pure water to clean the substrate surface, and (d) a surface of the cleaned substrate containing carbon atoms and hydrogen atoms in all layers. And a first photoconductive layer composed of a non-single-crystal material having silicon atoms and carbon as a base, wherein the content of the carbon atoms is non-uniform in the layer thickness direction and is highly distributed on the conductive substrate side. (E) forming a second photoconductive layer mainly composed of silicon atoms on the formed first photoconductive layer by plasma CVD;
An electrophotographic photoreceptor comprising: a step of forming by a method D; and (f) a step of forming a surface layer containing silicon atoms as a base and containing carbon atoms and hydrogen atoms on the formed second photoconductive layer by a 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 substantially 0% in
The content of hydrogen atoms in the photoconductive layer is 1 to 40 atomic%, and the content of carbon atoms in the surface layer is 40 to 9%.
0 atomic%, contains halogen, the content of the halogen atom is 20 atomic% or less, and the sum of the content of the hydrogen atom and the halogen atom is 30 to 70 atomic%, Including containing halogen in the layer, and distributing the halogen in the first photoconductive layer so as to have a maximum value at or near the interface with the second photoconductive layer.

An example of a procedure for actually forming an electrophotographic photosensitive member according to the method of manufacturing an electrophotographic photosensitive member of the present invention using an aluminum alloy cylinder as a conductive substrate will be described below with reference to FIG. Pretreatment device, and FIG.
A description will be given using a deposited film forming apparatus by a microwave CVD method shown in (a) and (b).

In FIG. 1, a diamond tool (trade name: Miracle tool, manufactured by Tokyo Diamond) is raked on a lathe with an air damper (manufactured by PNEUMOPRECLSION INC.) For precision cutting at an angle of 5 ° with respect to the cylinder center angle. Set to get the corner. Next, the base was vacuum-chucked to the rotating flange of the lathe, and a peripheral speed of 1000 m / min and a feed speed of 0.01 were simultaneously used while spraying white kerosene from the attached nozzle and sucking chips from the attached vacuum nozzle.
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of mm / R. The substrate after the cutting is processed on the surface of the substrate by a substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 includes a processing unit 102 and a substrate transport mechanism 103. The processing unit 102 includes a substrate loading table 111, a substrate cleaning tank 121, a pure water contact tank 131, a drying tank 141, and a substrate unloading table 151. Both the cleaning tank 121 and the pure water contact tank 131 are provided with a temperature controller (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 103 includes a transfer rail 165 and a transfer arm 161.
, A chucking mechanism 163 for holding the conductive substrate 101, and a chucking mechanism 1
An air cylinder 164 for raising and lowering 63 is provided. After the cutting, the conductive substrate 101 placed on the loading table 111 is transported to the cleaning tank 121 by the transport mechanism 103. Ultrasonic treatment is performed in the cleaning solution 122 made of the aqueous solution of the surfactant in the cleaning tank 121, so that the cutting oil and the cutting powder adhering to the surface are cleaned. Next, the conductive substrate 101 is transported by the transport mechanism 103 to the pure water contact tank 131, where the resistivity is maintained at a temperature of 25 ° C.
Pure water of 5 MΩ-cm is sprayed from the nozzle 132 at a pressure of 50 kg · f / cm ² . The conductive substrate 101 after the pure water contacting step is moved to the drying tank 141 by the transport mechanism 103, and is dried by blowing high-temperature high-pressure air from the nozzle 142. The conductive substrate 101 after the drying step is carried to the carry-out stand 151 by the carrying mechanism 103.

Next, amorphous silicon is deposited on the surface of the conductive substrate having been subjected to the cutting and the pretreatment by a microwave plasma CVD method shown in FIGS. 2A and 2B. A main deposited film is formed. 2A and 2B, reference numeral 201 denotes a reaction vessel, which has a vacuum tight structure. Also, 202
Is a microwave introducing dielectric window formed of a material (for example, quartz glass, alumina ceramics or the like) capable of efficiently transmitting microwave power into the reaction vessel 201 and maintaining vacuum tightness. Reference numeral 203 denotes a waveguide for transmitting microwave power, which includes a rectangular portion extending from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted into the reaction container. The waveguide 203 is in contact with a microwave power supply (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is used to maintain the atmosphere in the reaction vessel.
03 is hermetically sealed to the inner wall of the reaction vessel at the cylindrical opening. 204 has one end opened to the reaction vessel 201,
The other end is an exhaust pipe communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive substrate 205. The power supply 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias application electrode 212, and is electrically connected to the electrode 212.

The production of an electrophotographic photosensitive member using such a deposited film forming apparatus is performed as follows. First, the inside of the reaction vessel 201 is evacuated by a vacuum pump (not shown) through the exhaust pipe 204, and the pressure in the reaction vessel 201 is reduced to 1 × 10
Adjust to ^-7 Torr or less. Then, by the heater 207,
The temperature of the base 205 is heated and maintained at a predetermined temperature. Thereafter, a source gas such as a silane gas as a source gas of amorphous silicon, a diborane gas as a doping gas, and a helium gas as a diluting gas is introduced into the reaction vessel 201 through a gas introducing means (not shown). At the same time, a microwave having a frequency of 2.45 GHz is generated by a microwave power supply (not shown),
Through 03, it is introduced into the reaction vessel 201 through the dielectric window 202. Further, the bias electrode 21 in the discharge space 206
A DC voltage is applied to the base 205 from the DC power supply 211 electrically connected to the substrate 2 to the bias electrode 212.
The discharge space 20 thus surrounded by the conductive substrate 205
At 6, the source gas is excited by microwave energy to be dissociated, and further, the bias electrode 212 and the substrate 205 are dissociated.
While the ion electric shock is constantly received on the conductive substrate 205 by the electric field during the period, a deposited film is formed on the surface of the substrate 205. At this time, the rotating shaft 20 on which the conductive substrate 205 is set
9 is rotated by a motor 210, and the conductive substrate 205 is rotated.
Is rotated around the central axis in the base generatrix direction,
A deposited film layer is formed uniformly over the entire circumference of the conductive substrate 205.

Under such conditions as 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, by such a manufacturing apparatus as shown in FIG.
3, and a light receiving member including the surface layer 504 can be manufactured. Note that reference numeral 501 denotes a base.

According to the above procedure, the production of the electrophotographic photosensitive member is continuously performed efficiently.

In the present invention, the washing solution used in the washing step is desirably water or a solution obtained by adding a surfactant to water. Surfactants used in the washing step include anionic surfactants, cationic surfactants, nonionic surfactants,
Any material such as an amphoteric surfactant or a mixture thereof may be used. The present invention is also effective when an additive such as sodium tripolyphosphate is further added.

If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film is generated on the surface of the conductive substrate, which causes peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small, and the effect of the present invention cannot be sufficiently obtained.
For this reason, the temperature of the water is 10 ° C or more, 90 ° C or less,
Preferably, the temperature is 20 ° C or more and 75 ° C or less, and optimally 30 ° C or more and 55 ° C or less.

In the present invention, the use of ultrasonic waves in the cleaning step is important for sufficiently exhibiting the effects of the present invention. The frequency of the ultrasonic wave is preferably 100 Hz or more and 10 MHz or less, more preferably 1 kHz or more and 5 MHz or less, and most preferably 10 kHz or more and 100 kHz or less. The output of the ultrasonic wave is preferably 10 W or more and 100 kW or less, more preferably 100 W or more and 10 kW or less.

The quality of the water used in the pure water contacting step of the present invention is very important, and is semiconductor grade pure water, especially ultra-L.
SI grade ultrapure water is desirable. 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 or more.
100000 or less, preferably 10
Less than 000, optimally less than 1000 are suitable for the present invention. As the amount of microorganisms, a total viable count of 1,000 or less, preferably 100 or less, and optimally 10 or less per milliliter is suitable for the present invention. Organic matter (T
OC) is 100 mg / liter or less, preferably 1 mg / liter.
0 mg or less, optimally 2 mg or less are suitable for the present invention.

As a method for obtaining the water having the above-mentioned water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to increase the water quality to be used.

When pure water is brought into contact with the surface of the conductive substrate, it is desirable to apply water pressure and spray. When the pressure of water at the time of spraying is too weak, the effect of the present invention becomes small, and when it is too strong, a pattern appears in a pear-skin pattern on the obtained electrophotographic photoreceptor image, particularly on a halftone image. I will. For this reason, the pressure of water is 2 kg / f / cm ² or more, 300 kg / f / cm ² or less, preferably 10 kg / f / cm ² or more, 200 kg / f / cm ² or less, and optimally 20 kg / f / cm ² or less. cm ² or more,
150 kg · f / cm ² or less is suitable for the present invention. However, the pressure unit Kg · f / cm ² in the present invention means a gravity kilogram per square centimeter, and 1 Kg · f / cm ² is 98066.
It is equal to 5Pa. The method of spraying pure water of the present invention includes a method of spraying high-pressure water from a nozzle with a pump,
Alternatively, there is a method in which water pumped by a pump is mixed with high-pressure air in front of a nozzle and blown by the pressure of air.

The flow rate of the pure water of the present invention is 1 liter / min per conductive substrate from the viewpoint of the effect of the present invention and economy.
Not less than 200 l / min, preferably not less than 2 l / min and not more than 100 l / min, optimally 5 l / min.
The range of not less than 1 liter / min and not more than 50 liter / min is suitable for the present invention.

If the temperature of the pure water of the present invention is too high, an oxide film is generated on the conductive substrate, which causes peeling of the deposited film and the effect of the present invention cannot be sufficiently obtained. On the other hand, if it is too low, the effect of the present invention cannot be sufficiently obtained.
For this reason, the temperature of pure water is 5 ° C. or more and 90 ° C. or less, preferably 10 ° C. or more and 55 ° C. or less, and most preferably 15 ° C. or less.
C. or higher and 40 C. or lower are suitable for the present invention.

If the treatment time of the water contact treatment is too long, an oxide film is generated on the conductive substrate, and if the treatment time is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or more and 30 minutes or less, preferably 20 seconds. More than 20 minutes, optimally more than 30 seconds, 1
0 minutes or less are suitable for the present invention.

In the present invention, it is important to cut the surface of the substrate immediately before forming the deposited film in order to remove the influence of the oxide film on the surface of the substrate when the deposited film is formed.
If the time from the cutting to the water contact treatment is too long, an oxide film is generated again on the surface of the substrate, and if the time is too short, the process is not stable. Therefore, the time is from 1 minute to 16 hours, preferably from 2 minutes to 8 hours. Hereinafter, optimally 3 minutes or more and 4 hours or less are suitable for the present invention. If the time from the water contact treatment to the introduction into the deposited film forming apparatus is too long, the effect of the present invention will be small, and if it is too short, the process will not be stable, so the time is 1 minute or more, 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.

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. Further, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least a side on which at least a light receiving layer of an electrically insulating conductive substrate such as ceramic is formed. Although a substrate whose surface is subjected to a conductive treatment can be used, a metal is preferable from the viewpoint of mechanical strength and the like.

In the present invention, it is also effective to process the surface shape after cutting the conductive substrate with a predetermined accuracy. For example, when performing image recording using coherent light such as laser light, irregularities may be provided on the surface of the conductive substrate in order to eliminate image defects due to interference fringe patterns appearing in a visible image. The irregularities provided on the surface of the conductive substrate are described in JP-A-60-168156 and JP-A-60-178.
It is produced by a known method described in, for example, JP-A-457-457 and JP-A-60-225854. Further, as another method for eliminating image defects due to interference fringe patterns when using coherent light such as laser light, a surface of a conductive substrate may be provided with a plurality of concave and convex shapes due to spherical trace depressions. That is, the surface of the conductive substrate has irregularities smaller than the resolution required for the electrophotographic photoreceptor, and the irregularities are caused by a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of a conductive substrate is disclosed in JP-A-61-2315.
It is prepared by a known method described in JP-A-61-61.

In the present invention, the first photoconductive layer comprises silicon and carbon atoms as constituents 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, in particular, charge retention properties, charge generation properties, and charge transport properties. The carbon atoms contained in the photoconductive layer form a distribution, and the distribution is substantially uniform in a 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 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 or near the surface on which the conductive substrate is provided, the adhesion to the conductive substrate and the function of preventing charge injection are deteriorated. Further, the effect of improving the charging ability due to the decrease in the capacitance is lost. If it is 50% or more, a residual potential is generated. Therefore, practically, it is 0.5 to 50 atomic%, preferably 1 to 40 atomic%, and most preferably 1 to 30 atomic%. Here, the atomic% represents a percentage based on the number of atoms. In the present invention, it is necessary that the photoconductive layer contains hydrogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, particularly the photoconductivity and the charge retention characteristics. It is indispensable to make it happen. 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 contained be adjusted according to the carbon content. Therefore, the content of hydrogen atoms on the surface on which the conductive substrate is provided is desirably 1 to 40 atomic%, more preferably 5 to 35 atomic%, and most preferably 10 to 30 atomic%. .

In the present invention, the first photoconductive layer is manufactured by a vacuum deposition film forming method, with the numerical conditions of the film forming parameters appropriately set so as to obtain desired characteristics. Specifically, a glow discharge method (such as an AC discharge CV such as a low-frequency CVD method, a high-frequency CVD method, or a microwave CVD method) is used.
D method or DC discharge CVD method). Nc-Si by glow discharge method
To form a C: H photoconductive layer, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying C that can supply carbon atoms (C) are basically used. A source gas for H supply capable of supplying hydrogen atoms (H) is introduced in a gas state at a desired ratio into a reaction vessel capable of reducing the pressure therein, and a glow discharge is generated in the reaction vessel. A layer made of nc-SiC: H may be formed on the surface of a predetermined conductive substrate provided at a predetermined position.

In the present invention, the thickness of the first photoconductive layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
0 μm, more preferably 10 to 40 μm, optimally 20
It is desirable to set it to 30 μm.

In the present invention, the second photoconductive layer is composed of amorphous silicon nc-Si: H containing silicon atoms and hydrogen atoms as constituent elements, and has desired photoconductive properties, in particular, charge generation properties and charge transport properties. Have. The second photoconductive layer according to the present invention is designed to enhance the absorption of long-wavelength light and to improve the sensitivity.
It is provided for the purpose of reducing the ghost because it is better than the photoconductive layer.

In the present invention, the second photoconductive layer is manufactured by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics.
Specifically, the glow discharge method (low-frequency CVD method, high-frequency C
AC discharge CVD such as VD method or microwave CVD method
Or a direct current discharge CVD method). In order to form the nc-Si: H photoconductive layer by the glow discharge method, basically, silicon atoms (Si) are used.
Gas for supplying Si capable of supplying hydrogen and hydrogen atoms (H)
Is introduced in a desired gas state into a reaction vessel capable of reducing the pressure therein, thereby generating a glow discharge in the reaction vessel, which is previously set at a predetermined position. Nc-Si on a given conductive substrate surface:
An H layer may be formed. In the present invention, the second
The layer thickness of the photoconductive layer is determined as desired from the viewpoint of obtaining desired electrophotographic properties and economic effects, and the photoconductive layer is preferably 0.5 to 15 μm.
, More preferably 1 to 10 μm, most preferably 1 to 5 μm
It is desirable to be.

N having properties capable of achieving the object of the present invention
In order to form a photoconductive layer composed 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.

The substances that can be used as the Si supply gas used in the present invention for producing the first and second photoconductive layers include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Silicon hydride (silanes) in a gas state such as Si ₄ H ₁₀ or the like, which can be gasified, and SiH ₄ , Si ₂ H _{6 in} terms of ease of handling at the time of forming a layer, high Si supply efficiency, and the like.
Are preferred. In addition, these S
The raw material gas for supplying i is optionally H ₂ , He, Ar,
It may be used after being diluted with a gas such as Ne.

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

Starting materials that can be effectively used as a source gas for introducing carbon atoms (C) include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
Examples thereof include an ethylene hydrocarbon having 2 to 4 carbon atoms and an acetylene hydrocarbon having 2 to 3 carbon atoms. Specifically, as the saturated hydrocarbon, methane (CH ₄ ), ethane (C ₂ H
_6), propane (C ₃ H _8), n- butane (n-C ₄ H
₁₀ ), pentane (C ₅ H ₁₂ ), and ethylene hydrocarbons such as ethylene (C ₂ H ₄ ) and propylene (C ₃ H
_6), butene -1 (C ₄ H _8), butene--2 (C ₄ H
₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅
H ₁₀ ) and acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), and butyne (C ₄ H ₆ ).

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 order to introduce a hydrogen atom into the first and second photoconductive layers in a state bonded to silicon, in addition to the above, H
₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si
₄ the silicon or silicon compound for supplying silicon hydride and Si H ₁₀ such as to coexist in the reaction vessel can be carried out also by causing generate discharge by.

To control the amount of hydrogen atoms contained in the first and second photoconductive layers, for example, the temperature of the conductive substrate, 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 to be introduced into the furnace, the discharge power, and the like.

Further, in the present invention, it is preferable that the first and second photoconductive layers contain atoms (M) for controlling conductivity as necessary. The atoms that control conductivity are
It may be contained in the photoconductive layer in an evenly distributed state without unevenness, or there may be a part contained in the layer thickness direction in a non-uniform distribution state.

Examples of the above-mentioned atoms for controlling conductivity include so-called impurities in the field of semiconductors, and atoms belonging to Group III of the periodic table giving p-type conduction characteristics (hereinafter abbreviated as “Group III atoms”). Or an atom belonging to Group V of the periodic table that provides n-type conduction characteristics (hereinafter abbreviated as “Group V atom”).

Specific examples of Group III atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). In particular, B, Al, and Ga include It is suitable. Specific examples of Group V atoms include phosphorus (P), arsenic (As), and antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of the atom (M) for controlling the conductivity contained in the photoconductive layer is preferably from 1 × 10 ^{−3 to} 5 × 10 ^−3.
x10 ⁴ atomic ppm, more preferably 1 × 10 ^{-2 to} 1 × 1
0 ⁴ atom ppm, and optimally 1x10 ^-1 ~5x10 ³ atomic ppm
It is desirable to be. In particular, when the content of carbon atoms (C) in the photoconductive layer is 1 × 10 ³ atomic ppm or less, the content of atoms (M) in the photoconductive layer is preferably 1 × 10 ^{−3 to} 1 × 10 ³ atomic ppm. And the content of carbon atoms (C) is 1 × 10 ³ atoms
When it exceeds ppm, the content of atoms (M) is preferably set to ¹ × 10 ^{-1 to} 5 × 10 ⁴ atomic ppm.

Here, the atomic ppm means a part per million based on the number of atoms.

In order to structurally introduce an atom for controlling conductivity, for example, a group III atom or a group V atom into the photoconductive layer, a material for introducing a group III atom must be used in forming the layer. A substance or a raw material for introducing a group V atom may be introduced into the reaction vessel in a gas state together with another gas for forming the photoconductive layer. As a raw material for introducing a Group III atom or a raw material for introducing a Group V atom, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is employed. Is desirable. As such a raw material for introducing a group III atom, specifically, for introducing a boron atom, B ₂ H ₆ ,
_{B 4 H 10, B 5 H} 9, B 5 H 11, B 5 H 10, B 6 H 12,
Borohydride such as _{B 6 H 14, BF 3,} BCl 3, BBr 3
And the like. In addition, AlCl
₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , Tl
Cl _{3 and the} like can also be mentioned.

In the present invention, the raw material for introducing a group V atom is effectively used for introducing a phosphorus atom, for example, hydrogen phosphide such as PH ₃ and P ₂ H ₄ , PH ₄ I, PF
_{3, PF 5, PCl 3,} PCl 5, PBr 3, PBr
_5, a halogenated phosphorus PI ₃ and the like. In addition, A
sH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF
_{5, SbH 3, SbF 3,} SbF 5, SbCl 3, Sb
Cl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group V atoms.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

Further, the photoconductive layer of the light receiving member of the present invention may contain at least one element selected from Group Ia, IIa, VIb, and VIII of the periodic table. The elements may be uniformly distributed in the photoconductive layer, or may be uniformly distributed in the photoconductive layer, but may be distributed unevenly in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary to be uniformly contained in a uniform distribution in order to make the characteristics in the in-plane direction uniform. is there.
As the Group Ia atom, specifically, lithium (L
i), sodium (Na) and potassium (K). Examples of Group IIa atoms include beryllium (B
e), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and the like.

Further, as the Group VIb atom, specifically,
Chromium (Cr), molybdenum (Mo), tungsten (W) and the like can be given.
Examples include iron (Fe), cobalt (Co), and nickel (Ni).

The temperature (Ts) of the conductive substrate is appropriately selected in an optimum range according to the layer design, but is usually preferably 20 to 500 ° C., more preferably 50 to 480.
° C, optimally 100-450 ° C.

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

Further, in the light receiving member of the present invention, a layer containing at least aluminum atoms, silicon atoms, carbon atoms and hydrogen atoms in a non-uniform distribution state in the layer thickness direction 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 made of a non-single-crystal material containing silicon atoms, carbon atoms, hydrogen atoms and, if necessary, halogen atoms as constituent elements. The surface layer contains substantially no conductivity controlling substance such as that contained in the photoconductive layer.

The carbon atoms contained in the surface layer may be uniformly distributed in the layer, or may be uniformly distributed in the thickness direction of the layer, but are non-uniformly distributed. There may be a part contained in a state. However,
In any case, it is necessary to uniformly contain the particles in a direction parallel to the surface of the conductive substrate in a plane parallel to the surface of the conductive base in order to make the characteristics uniform in the plane.

The carbon atoms contained in the entire surface region of the surface layer according to the present invention exhibit effects such as high dark resistance and high hardness. The content of carbon atoms contained in the surface layer is preferably 40 to 90 atomic%, more preferably 45 to 85 atomic%,
Most preferably, it is set to 50 to 80 atomic%.

The content (atomic%) of carbon atoms in the surface layer is defined as 100 × carbon atoms / (carbon atoms + silicon atoms).

In the present invention, hydrogen atoms and halogen atoms contained in the surface layer are nc-SiC (H, X)
This improves the quality of the film by compensating for dangling bonds existing therein, and reduces the number of carriers trapped at the interface between the photoconductive layer and the surface layer, thereby improving image deletion. Further, since the halogen atoms improve the water repellency of the surface layer, the high humidity flow due to the adsorption of water vapor is also reduced. The content of halogen atoms in the surface layer is 20 atom% or less, and the sum of the content of hydrogen atoms and halogen atoms is preferably 30 to 70 atom%, more preferably 35 to 65 atom%, and most preferably Is 40 ~
Desirably, it is 60 atomic%.

Further, in the present invention, the surface layer may contain at least one element selected from the group Ia, IIa, VIb and VIII of the periodic table. The elements may be uniformly distributed in the photoconductive layer, or may be uniformly distributed in the photoconductive layer, but may be distributed unevenly in the layer thickness direction. There may be a part containing. However, in any case, in the in-plane direction parallel to the surface of the conductive substrate, it is necessary to be uniformly contained in a uniform distribution in order to make the characteristics in the in-plane direction uniform. is there.

Specific examples of Group Ia atoms include lithium (Li), sodium (Na) and potassium (K). Examples of Group IIa atoms include beryllium (Be) and magnesium (Mg). ), Calcium (C
a), strontium (Sr), barium (Ba) and the like.

The group VIb atom is specifically:
Chromium (Cr), molybdenum (Mo), tungsten (W) and the like can be given.
Examples include iron (Fe), cobalt (Co), and nickel (Ni).

In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, and more preferably 0.0 to 30 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
The thickness is preferably 5 to 20 μm, and most preferably 0.1 to 10 μm.

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

When forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the conductive substrate are important factors that influence the characteristics of the surface layer. The temperature of the conductive substrate is appropriately selected in an optimum range.
The temperature is desirably 0 to 500C, more preferably 50 to 480C, and most preferably 100 to 450C.

[0079] While the gas pressure as appropriate optimum range of the reaction vessel is selected, preferably 1x10 ^-5 to 10 Torr, and more preferably 5x10 ^-5 ~3Torr, optimally 1x10 ^-4 ~1To
rr is desirable.

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

In the present invention, the energy for generating plasma may be any of DC, high frequency, microwave, etc. In particular, when microwave is used as energy for generating plasma, microwave is generated in adsorbed moisture. The effect of the present invention becomes more remarkable because the absorption is made and the change of the interface becomes more remarkable.

In the present invention, when microwaves are used for plasma generation, any microwave power may be used as long as discharge can be generated, but the power is preferably 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW or less. Appropriate for practicing the invention.

The present invention can be applied to any electrophotographic photosensitive member manufacturing method. In particular, a base is provided so as to surround a discharge space, and microwaves are introduced from at least one end of the base by a waveguide. There is a great effect when a deposited film is formed by the configuration.

Hereinafter, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[0085]

【Example】

<Example 1 and Comparative Example 1> Example 1 108 mm in diameter made of aluminum having a purity of 99.5%,
The surface of a cylindrical substrate having a length of 358 mm and a thickness of 5 mm was cut in the same procedure as the above-described example of the procedure of the method of manufacturing an electrophotographic photosensitive member according to the present invention.
The pretreatment of the substrate surface was performed by the surface treatment apparatus shown in Table 1 under the conditions shown in Table 1. However, in this example, a 1 wt% aqueous solution of polyethylene glycol nonyl phenyl ether was used as a surfactant. On the pretreated aluminum cylinder, using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 according to the procedure described in detail above, the electrophotography was performed by the high-frequency glow discharge method under the manufacturing conditions shown in Table 2. A photoreceptor was produced. In the present 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 this time, the carbon content at the interface between the photoconductive layer and the substrate was set to be about 30 atomic%. In addition,
For the carbon content, a calibration curve of a standard sample was prepared by elemental analysis by Rutherford backscattering method, and the absolute amount was determined by comparing the signal intensity of the standard sample and the prepared sample by Auger spectroscopy.

The surface properties of the produced electrophotographic photosensitive member were first evaluated visually, and thereafter, a copying machine NP-755 manufactured by Canon Inc.
0 was installed in an electrophotographic device modified for experiment,
The following evaluations were made on electrophotographic characteristics such as sensitivity and residual potential. The electrophotographic photoreceptor produced with cloudy surface
The surface was visually inspected for the degree of fogging.

◎: no fogging ○: partial fogging Δ: partial fogging at several places x: fogging on the entire surface Charging Ability, Sensitivity, Residual Potential Charging Ability: Install the electrophotographic photoreceptor in the experimental device, apply a high voltage of +6 kV to the charger, perform corona charging, and measure the surface potential of the dark area of the electrophotographic photoreceptor using a surface electrometer I do.

Non-uniform charging ability: The above-mentioned measurement was measured at nine locations, three each for the upper, middle, and lower portions of one electrophotographic photosensitive member, and a value obtained by subtracting the smallest potential from the largest potential among them. Is shown.

Sensitivity: The electrophotographic photosensitive member is charged to a constant dark area surface potential. Then, the light image is immediately emitted. The light image was obtained by using a xenon lamp light source and a filter.
Irradiate light excluding light in the wavelength range of 0 nm or less. At this time, the surface potential of the light portion of the electrophotographic photosensitive member is measured by a surface potentiometer. The exposure amount is adjusted so that the bright portion surface potential becomes a predetermined potential, and the exposure amount at this time is used as the sensitivity.

Sensitivity unevenness: The above-mentioned measurement was performed at nine locations, three each for the upper, middle, and lower portions of one electrophotographic photosensitive member, and a value obtained by subtracting the smallest potential from the largest potential among them. Show.

Residual potential: The electrophotographic photosensitive member is charged to a constant dark area surface potential. Then, a relatively strong light of a constant light amount is immediately irradiated. The light 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 surface potential of the light portion of the electrophotographic photosensitive member is measured by a surface potentiometer. White spots and half-tone unevenness: An electrophotographic photoreceptor was manufactured by Canon Copier NP7550
Was placed in a copier modified for experimentation, transferred by an ordinary electrophotographic process to form an image on paper, and the image was evaluated by the following procedure.

White spots: diameter 0.2 in the same area of the copy image obtained when the entire black chart made by Canon (part number: FY9-9073) is placed on the platen and copied.
The number was counted for white dots less than mm.

Halftone unevenness: Canon halftone chart (part number FY9-90)
42) is placed on a platen and a circular area having a diameter of 0.05 mm is defined as one unit on a copy image obtained when copying.
The image density at 00 points was measured, and the variation in the image density was evaluated.

In each case, ◎ indicates “particularly good”, △ indicates “good”, Δ indicates “no problem in practical use”, x indicates “no problem in practical use”. The results are shown in Table 3. Comparative Example 1 The same conductive substrate as in Example 1 was cut in the same procedure, and the cut conductive substrate was cleaned by the conventional conductive substrate cleaning apparatus shown in FIG. Was performed. The apparatus for cleaning a conductive substrate shown in FIG. 3 includes a processing tank 302 and a substrate transport mechanism 303. The processing tank 302 includes a substrate loading table 311, a substrate cleaning tank 321, and a substrate unloading table 351. The cleaning tank 321 is provided with a temperature controller (not shown) for keeping the temperature of the liquid constant. The transfer mechanism 303 includes a transfer rail 365 and a transfer arm 361.
A moving mechanism 362 that moves up, a chucking mechanism 363 that holds the base 301, and the chucking mechanism 36
3 comprises an air cylinder 364 for raising and lowering.

After cutting, the substrate 3 placed on the loading table 311
01 is transported to the cleaning tank 321 by the transport mechanism 303. Trichlorethane (trade name: Eterna VG, manufactured by Asahi Kasei Kogyo Co., Ltd.) 322 in the cleaning tank 321 performs cleaning for removing cutting oil and chips adhering to the surface.

After the cleaning, the substrate 301 is carried to the carry-out table 351 by the carrying mechanism 303. In the same manner as in Example 1, the pre-treated substrate of the conventional substrate was treated in the same manner as in Example 1.
Under the conditions shown in FIG. 6, a so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate 601, a charge transport layer 602, a charge generation layer 603, and a surface layer 604 was produced as shown in FIG. The evaluation of the obtained electrophotographic photosensitive member was performed 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 shows that the surface of the photoreceptor has excellent characteristics with respect to fogging, uneven charging ability, sensitivity, and halftone. <Example 2 and Comparative Example 2> Example 2 On the substrate subjected to the same pretreatment of the substrate as in Example 1 by 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 photosensitive member 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 An electrophotographic photoreceptor manufacturing apparatus shown in FIGS. 2A and 2B was used on a conductive substrate subjected to the same pretreatment as in Comparative Example 1 using the substrate surface treatment apparatus shown in FIG. A so-called function-separated electrophotographic photosensitive member having a three-layer structure of a substrate, a first photoconductive layer, a second photoconductive layer, and a surface layer was produced by a microwave glow discharge method under the conditions shown in Table 7. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 2. as a result,
Exactly the same results as in Comparative Example 2 were obtained. <Example 3 and Comparative Example 3> Example 3 An apparatus for manufacturing an electrophotographic photosensitive member shown in FIG. 4 was used on a substrate which had been subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. According to the procedure described in detail above, an electrophotographic photosensitive member was produced by the high-frequency glow discharge method under the production conditions shown in Table 8. In this embodiment, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS. 8 and 9, the flow rate of CH ₄ introduced at the time of forming the photoconductive layer is changed, and A photoreceptor was produced. In any pattern, the carbon content on the substrate side surface of the photoconductive layer is
It was adjusted to 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 value was obtained by comparing the standard sample and the prepared sample with the signal intensity by Auger spectroscopy.

The surface of the produced electrophotographic photosensitive member was clouded, and the copying machine NP-7550 manufactured by Canon was installed in an electrophotographic apparatus modified for experiments. The same charging ability, sensitivity, residual potential, etc. as in Example 1 were used. The method was evaluated. Table 9 shows the results.
Shown in Comparative Example 3 Example 3 was formed on a substrate subjected to pretreatment in the same manner as in Comparative Example 1.
An electrophotographic photoreceptor was produced in the same manner as in Example 1 with the carbon content patterns 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.

In the carbon amount change pattern of the photoconductive layer according to the present invention, particularly good results were obtained with respect to the fogging of the surface, uneven charging ability, uneven sensitivity, and uneven halftone as compared with the result of Comparative Example 3. You can see that. Example 4 and Comparative Example 4 Example 4 The electrophotographic photosensitive member shown in FIGS. 2A and 2B was applied on a substrate which had been subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. An electrophotographic photoreceptor was produced in the same manner as in Example 3 except that a microwave glow discharge method was used using a body production apparatus, under the production conditions shown in Table 10. In the present embodiment, in order to change the change pattern of the carbon content in the photoconductive layer as shown in FIGS.
The flow rate of H ₄ was varied. In any of the patterns, the carbon content on the surface of the photoconductive layer on the substrate side is about 30 atomic%.
It was made to become. For the carbon content, a calibration curve of a standard sample was prepared by elemental analysis using Rutherford backscattering method, and the absolute value was obtained by comparing the standard sample and the prepared sample with the signal intensity by Auger spectroscopy. The produced electrophotographic photoreceptor obtained exactly the same results as in Example 3. Comparative Example 4 An electrophotograph was performed on the substrate pretreated in the same manner as in Comparative Example 1 using the substrate surface treatment apparatus shown in FIG. 3 in the same manner as in Example 4 with the carbon content patterns shown in FIGS. A photoreceptor was produced. When the obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 4, the same results as in Comparative Example 3 were obtained. <Embodiment 5> The procedure described in detail above, using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG. 4 on a substrate subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. The electrophotographic photoreceptor was manufactured by the high frequency glow discharge method under the manufacturing conditions shown in Table 2. In this embodiment, the change pattern of the carbon content in the photoconductive layer is shown in FIG.
It was changed by changing the flow rate of ₄ . Then, the carbon content of the photoconductive layer on the substrate side surface was identified by Auger spectroscopy in the same manner as described above.

The number of fogging and the number of spherical projections on the surface of the produced electrophotographic photosensitive member, as well as the copy machine NP-75 manufactured by Canon
50 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, and image quality were evaluated. Each item is
Evaluation was made by the following method. Surface haze Evaluation was performed in the same manner as in Example 1. Number of spherical projections The entire surface of the produced electrophotographic photosensitive member was observed with an optical microscope, and the number of spherical projections having a diameter of 20 μm or more in an area of 100 cm ² was examined. The results were obtained for each electrophotographic photoreceptor, and those having the largest number of spherical projections were defined as 100% for relative comparison. The results were classified as follows.

◎ is less than 60% は is 80 to 60% △ is 100 to 80% Chargeability / sensitivity / uneven sensitivity / residual potential Evaluation was made in the same manner as in Example 1. Uneven white dots and halftone unevenness Uneven white dots and halftone unevenness: evaluated in the same manner as in Example 1.

Table 11 summarizes the results thus obtained. According to the results, the carbon content of the photoconductive layer on the substrate side is 0.5 to 50 atomic%, and the characteristics are improved. Further, 1 to 30 atomic% gives a very good result. <Embodiment 6> FIG. 2 (a) shows the results of the pretreatment performed in the same manner as in the embodiment 1 on the substrate by the substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photoreceptor manufacturing apparatus shown in (b), the electrophotographic photoreceptor was produced by the microwave glow discharge method under the production conditions shown in Table 6 according to the procedure described in detail above. In the present embodiment, the change pattern of the carbon content in the photoconductive layer is shown in FIG. 7, and the carbon content of the substrate-side surface is changed by changing the flow rate of CH ₄ introduced during formation of the photoconductive layer for each photoconductor. Was changed.

As a result of evaluation in the same manner as in Example 5, exactly the same results as in Table 11 were obtained. <Embodiment 7> Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 4 on a substrate which had been subjected to the same pretreatment as in Embodiment 1, according to the procedure described in detail above, a high frequency glow discharge method was used to prepare Table 12 An electrophotographic photoreceptor was manufactured under the following manufacturing conditions.
In this embodiment, the flow rate of SiF ₄ introduced during the formation of the photoconductive layer was changed in order to change the fluorine content in the photoconductive layer as shown in FIG. (I) The produced electrophotographic photoreceptor was copied by Canon copier NP
-7550 was installed in an electrophotographic device modified for experiments,
White spots, halftone unevenness before the accelerated durability test,
The electrophotographic characteristics such as ghost were evaluated. Each item was evaluated in the same manner as in Examples 1 and 5. The evaluation of ghost was performed as follows.

Ghost: A ghost test chart (part number: FY9-9040) manufactured by Canon Inc.
1. A ghost chart recognized on a halftone copy in a copy image obtained by placing a black circle of 5 mm attached on the front end of the image on the platen and overlaying a halftone chart made by Canon on top of that. The difference between the reflection density of 5 mm and the reflection density of the halftone portion was measured. In each case, ◎ indicates “particularly good”, ○ indicates “good”, Δ indicates “no problem in practical use”, and × indicates “problem in practical use”.

Table 13 summarizes the results. (II) Next, the produced electrophotographic photosensitive member was installed in an electrophotographic apparatus in which a copying machine NP-7550 manufactured by Canon was modified for experiments, and an accelerated durability test corresponding to 3 million sheets was performed. Then, evaluation of electrophotographic characteristics such as white spots, halftone unevenness, and ghost was performed in the same manner as in (I). Table 1 shows the results.
4 collectively.

From the results shown in Tables 13 and 14, an electrophotographic photosensitive member excellent in image characteristics and durability was produced by setting the fluorine content in the photoconductive layer to 95 atomic ppm or less. It has been shown that it is possible. <Embodiment 8> FIG. 2 (a) shows the results of the pretreatment performed in the same manner as in Embodiment 1 on the base by the substrate surface treatment apparatus shown in FIG.
Using the electrophotographic photoreceptor manufacturing apparatus shown in (b), an electrophotographic photoreceptor was produced by the microwave glow discharge method under the production conditions shown in Table 15 in the same manner as in Example 7. Then, the produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 7. The results were exactly the same as in Tables 13 and 14. <Embodiment 9> On a substrate subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. 1, a table was formed by a high-frequency glow discharge method using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under 16 manufacturing conditions. In this experiment, the flow rate of CH ₄ introduced during the formation of the surface layer was changed so as to change the amount of carbon contained in the surface layer.

The produced electrophotographic photosensitive member was placed in an electrophotographic apparatus in which a copying machine NP-8580 manufactured by Canon was remodeled for an experiment, and the charging ability, uneven charging ability, residual potential, image evaluation before endurance, 3 million sheets The image evaluation after the considerable accelerated durability test was performed by the following method.

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

Residual potential: Performed in the same manner as in Example 1.

Evaluation of image after endurance: Five levels of limit samples were prepared for each of white spots and scratches, and the total evaluation results were classified into the following four levels.

◎ indicates “particularly good” ○ indicates “good” Δ indicates “no problem in practical use” X indicates “problem in practical use” The following results are shown in Table 17. As is clear from the table, when the carbon content is 40 to 90 atomic%, remarkable improvements in charging ability and durability are observed. <Embodiment 10> A substrate subjected to the same pretreatment as in Embodiment 1 by the substrate surface treatment apparatus shown in FIG.
Using the apparatus for manufacturing an electrophotographic photosensitive member shown in (a) and (b), a microwave glow discharge method was used in the same manner as in Example 9,
An electrophotographic photosensitive member was manufactured under the manufacturing conditions shown in Table 18. In this experiment, the flow rate of CH ₄ introduced during the formation of the surface layer was changed so as to change the amount of carbon contained in the surface layer.

The prepared electrophotographic photosensitive member was evaluated in the same procedure as in Example 9. As a result, exactly the same results as in Table 17 were obtained. <Embodiment 11> On a substrate subjected to the same pretreatment as in Example 1 by the substrate surface treatment apparatus shown in FIG. 1, a table was formed by a high-frequency glow discharge method using the electrophotographic photosensitive member manufacturing apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under 19 manufacturing conditions.
In this experiment, H ₂ introduced during the formation of the surface layer was changed so as to change the amount of hydrogen atoms and the amount of fluorine atoms contained in the surface layer.
And / or the flow rate of SiF ₄ was varied.

The produced electrophotographic photosensitive member was installed in an electrophotographic apparatus in which a copying machine NP-8580 manufactured by Canon was modified for experiments, and three items of residual potential, sensitivity, and image deletion were evaluated.

Residual potential: Performed in the same manner as in Example 1.

Sensitivity: Performed in the same manner as in Example 1.

Irregularity of sensitivity: Performed in the same manner as in Example 1.

Image flow: A test chart made by Canon (part number FY9-9058) consisting of whole characters is placed on a white platen, placed on a document table, irradiated with an exposure amount twice as large as a normal exposure amount, and a copy is taken. The obtained copy image was observed, and it was evaluated whether fine lines on the image were connected without interruption. However, at this time, when there was unevenness in the image, the evaluation was performed in the entire image area, and the result of the worst part was shown.

◎: good ○: partial interruption

{Circle around (1)} Although there are many breaks, they can be recognized as characters,
No problem in practical use.

Table 20 shows the obtained results. As is clear from Table 20, the sum of the hydrogen content and the fluorine content in the surface layer was 30 to 70 atomic% and the fluorine content was 20%.
It was found that by setting the content in the range of at most atomic%, good results were obtained in both the residual potential and the sensitivity, and furthermore, the image deletion at the time of strong exposure could be largely suppressed. <Embodiment 12> A substrate pretreated in the same manner as in Embodiment 1 by the substrate surface treatment apparatus shown in FIG.
An electrophotographic photoreceptor was produced by the microwave glow discharge method under the production conditions shown in Table 21 by using the apparatus for producing an electrophotographic photoreceptor shown in (a) and (b). The He flow rate was 2000 sc together with the H ₂ flow rate.
cm and the internal pressure was kept constant. The produced electrophotographic photosensitive member was evaluated in the same procedure as in Example 10. As a result, exactly the same results as in Table 20 were obtained. <Example 13> An electrophotograph shown in FIGS. 2 (a) and 2 (b) was formed on a substrate which had been subjected to the same pretreatment as in Example 1 under the conditions shown in Table 22 by the substrate surface treatment apparatus shown in FIG. Using a photoreceptor manufacturing apparatus, an electrophotographic photoreceptor was manufactured by microwave glow discharge under the conditions shown in Table 23. In this embodiment, the value of SiF ₄ / SiH ₄ is set to 10 to 50 so that the fluorine content in the photoconductive layer has a distribution shown in FIGS.
By changing the flow rate smoothly within the ppm range, four types of electrophotographic photoreceptors were produced. Also, an electrophotographic photosensitive member was prepared under the same conditions except that fluorine was not contained. The following five types of electrophotographic photosensitive members were evaluated as follows.

Surface fogging, charging ability, sensitivity, residual potential, white spots, halftone unevenness, ghost: Evaluation similar to that in Example 1. Temperature characteristics: The produced electrophotographic photoreceptor was tested using a copying machine NP7550 manufactured by Canon Inc. The electrophotographic photosensitive member surface temperature was changed to 30-45 ° C, a high voltage of +6 kV was applied to the charger, corona charging was performed, and the surface potential of the dark area was measured with a surface voltmeter. I do. Approximate the change in the surface temperature of the dark area with respect to the surface temperature of the photoconductor with a straight line,
The slope is referred to as “temperature characteristic” and is expressed in units of [V / deg].

A: Very excellent.

…: Excellent.

Δ: There is no practical problem.

X: Not practical.

Table 24 shows the above results. From the table, it can be seen that when the photoconductive layer contains fluorine and is distributed in the film thickness direction, all electrophotographic characteristics including ghost and temperature characteristics are improved.

[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]

As described above, according to the present invention, in a method for producing an electrophotographic photosensitive member including a step of forming a functional film on a metal substrate, particularly, the layer of the present invention is formed on a metal substrate. In an electrophotographic photoreceptor manufacturing method including a step of forming an electrophotographic photoreceptor film having amorphous silicon as a base by a plasma CVD method, the surface of the conductive substrate is formed before the step of forming the light receiving layer. Since the step of cutting the layer with a predetermined precision, the step of cleaning the cut conductive substrate surface and the step of contacting the cleaned conductive substrate surface with pure water after this cutting step are performed. In addition, it is possible to manufacture an electrophotographic photoreceptor that provides a uniform high-quality image at low cost and stably without fear of environmental pollution by an organic solvent or the like.

Further, according to the present invention, the photoconductive layer is formed by continuously changing carbon atoms from the conductive substrate.
It is possible to smoothly connect the important functions of the electrophotographic photoreceptor, that is, the generation of charges (photocarriers) and the transport of the generated charges. This prevents poor running of charges due to a difference in optical energy gap between the charge generation layer and the charge transport layer, which is a problem in the type light receiving member, and contributes to improvement in photosensitivity and reduction in residual potential.

Further, since the first photoconductive layer contains carbon, the dielectric constant of the photoreceptor layer can be reduced, so that the capacitance per layer thickness can be reduced, which is high. Significant improvements in charging performance and photosensitivity
Further, the withstand voltage against a high voltage is improved.

By providing a layer containing a large amount of carbon on the side of the conductive substrate, the injection of charges from the conductive substrate is prevented, thereby improving the charging ability. Further, the adhesion between the conductive substrate and the photoconductive layer is improved. And the occurrence of minute defects can be suppressed. By improving the adhesion of the film, even if a large amount of images are formed continuously, damage to the cleaning blade and the separation claw is small, and the cleaning property and the separation property of the transfer paper are improved. Therefore, the durability of the image forming apparatus can be significantly improved. Further, the durability against a high voltage is also improved due to the decrease in the dielectric constant, so that "leak spots" caused by dielectric breakdown of a part of the light receiving member are further 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 excellent.

Further, according to the present invention, the yield in the case of poor appearance such as clouding of the surface of the photoreceptor after manufacturing can be greatly increased, and in particular, the unevenness of the electric characteristics such as uneven charging ability, uneven sensitivity and halftone can be significantly suppressed.

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

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one example of a substrate surface treatment apparatus used for carrying out the method for producing an electrophotographic photosensitive member of the present invention.

FIG. 2A is a schematic longitudinal sectional view showing an example of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method, and FIG. 2B is a transverse sectional view of the same.

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

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

FIG. 5 is an explanatory view showing a layer structure formed in the method for producing an electrophotographic photosensitive member of the present invention.

FIG. 6 is an explanatory diagram showing a layer configuration of a conventional electrophotographic photosensitive member.

FIG. 7 is a graph showing a change pattern of the carbon content of the photoconductive layer of the product of the present invention.

FIG. 8 is a graph showing a change pattern of the carbon content of the photoconductive layer of the product of the present invention.

FIG. 9 is a graph showing a change pattern of the carbon content of the photoconductive layer of the product of the present invention.

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

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

FIG. 12 is a graph showing a change pattern of a fluorine content of a photoconductive layer according to an embodiment of the present invention.

FIG. 13 is a graph showing a change pattern of the fluorine content of the photoconductive layer according to the embodiment of the present invention.

FIG. 14 is a graph showing a change pattern of a fluorine content of a photoconductive layer according to an embodiment of the present invention.

FIG. 15 is a graph showing a change pattern of the fluorine content of the photoconductive layer according to the embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Substrate 102 Processing tank 103 Substrate transfer 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 discharge table 161 Transport arm 162 Moving mechanism 163 Chucking mechanism 164 Air cylinder 165 Rail Reference Signs List 201 Reaction vessel 202 Microwave introduction window 203 Waveguide 204 Exhaust pipe 205 Cylindrical substrate 206 Discharge space 207 Heater 209 Rotating axis 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 discharge table 361 Transfer arm 362 Moving mechanism 363 Chucking machine 364 Air cylinder 365 Rail 400 Deposited film forming apparatus 4 1 Reaction Vessel 402 Cylindrical Substrate 403 Heater for Heating Cylindrical Substrate 404 Source Gas Introducing Tube 405 High Frequency Matching Box 406 Source Gas Introducing Pipe 407 Reaction Vessel Leak Valve 408 Main Exhaust Valve 409 Vacuum Gauge 410 Source Gas Supply Unit 411-416 Mass Flow Controllers 417 to 422 Source gas cylinders 423 to 428 Source gas cylinder valves 429 to 424 Source gas inflow valves 435 to 440 Source gas outflow valves 441 to 446 Pressure regulators 447 Valves 501, 601 Base 502 First photoconductive layer 503 Second light Conductive layer 504, 604 Surface layer 505, 605 Photoreceptor layer 602 Charge transport layer 603 Charge generation layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 5/10 G03G 5/10 B (72) Inventor ▲ Taka ▼ Yasuyoshi I 3-3-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 5/08 G03G 5 / Ten

Claims (5)

(57) [Claims] (A) a step of cutting the surface of a conductive substrate with a predetermined precision; (b) a step of cleaning the substrate surface after cutting with water; and (c) a step of bringing the cleaned substrate surface into contact with pure water. (D) cleaning the surface of the substrate, wherein the cleaned substrate surface contains carbon atoms and hydrogen atoms in all layers, the content of the carbon atoms is non-uniform in the layer thickness direction, and the conductive substrate Forming a first photoconductive layer made of a non-single-crystal material having a high distribution of silicon atoms and carbon on its side by a plasma CVD method, (e) forming the first photoconductive layer Forming a second photoconductive layer having silicon atoms as a base thereon by a plasma CVD method; (f) containing a silicon atom as a base and containing carbon atoms and hydrogen atoms on the formed second photoconductive layer; Plasma CVD method for surface layer A step of further forming method of an electrophotographic photoreceptor characterized by having each of the above steps. 2. The method according to claim 1, 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 the interface with or near the interface with the second photoconductive layer. 2. The method 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 atom%. 3. The method according to claim 1, wherein the content of carbon atoms in the surface layer is 10%.
40 to 90 atomic% as a value represented by 0 × carbon atoms / (carbon atoms + silicon atoms) and containing halogen,
3. The method according to claim 2, wherein the content of the halogen atom is 20 atom% or less, and the sum of the content of the hydrogen atom and the content of the halogen atom is 30 to 70 atom%. 4. The method according to claim 1, wherein the first photoconductive layer contains a halogen. 5. The electrophotographic photosensitive member according to claim 4, wherein the halogen in the first photoconductive layer is distributed so as to have a maximum value at or near the interface with the second photoconductive layer. Production method.