JPH06273957A - Electrophotographic photoreceptor and manufacturing method thereof - Google Patents

Abstract

(57) [Summary] [Problem] To provide an electrophotographic photoreceptor having high image quality, halftone unevenness, etc., stability that can be used in any environment, and high resource saving, and a method for producing the same. In the method for producing an electrophotographic photosensitive member having a light receiving layer on a cylindrical support, the cylindrical support 102
A first step of applying an external force in a direction to expand the support, and after the first step, cutting and / or cutting the surface of the support.
Or a second step of polishing, and a third step of depositing a light-receiving layer containing amorphous silicon as a main component on the support after the second step.
As a means for applying an external force in the direction of expanding the tube, a hollow member 103 having elasticity is put inside the circular tubular support,
A method of manufacturing an electrophotographic photosensitive member, comprising injecting air into the hollow member and expanding the support 102 by the air pressure 104.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor having a photoreceptive layer containing silicon as a base material on a conductive support, and a method for producing the photoreceptor.

The present invention relates to an electrophotographic photoconductor 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, and a method for producing the photoconductor.

[0003]

2. Description of the Related Art Conventionally, non-single crystal deposited films, such as amorphous silicon (hereinafter referred to as nc-Si) compensated with hydrogen and / or halogen (for example, fluorine, chlorine, etc.), etc. have been used for electrophotographic photoreceptors. The following amorphous deposited films have been proposed, and some of them have been put to practical use.

As a method of forming such a deposited film, conventionally,
There are many methods such as a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (optical CVD method), a method of decomposing a source gas by plasma (plasma CVD method). Are known.
Among them, the plasma CVD method, that is, the method of decomposing a source gas by direct current, high frequency or microwave glow discharge or the like to form a thin film deposition film on a substrate is a method for forming an nc-Si deposition film for electrophotography. It is the best choice and is now very practically used. Such an example is, for example, JP-A-5
It is described in Japanese Patent Publication 4-86341.

This nc-Si photoconductor is non-polluting,
Further, it has high Vickers hardness, high image quality, and high durability, and the nc-Si photoconductor currently put into practical use sufficiently shows such features. However, in order for the nc-Si photoconductor to become more and more popular in the future, further cost reduction, further improvement of electric characteristics, and further high durability are desired.

Against this background, the study on high quality of the nc-Si photosensitive member has been steadily progressed by examining the layer structure.

For example, in Japanese Patent Laid-Open No. 54-145540, a dark resistance is increased by using amorphous silicon containing 0.1 to 30 atomic% of carbon as a chemical modifier as a photoconductive layer of an electrophotographic photoreceptor. It has been shown that it exhibits excellent electrophotographic characteristics with good photosensitivity.

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

[0009]

With such a technique,
Although the performance of electrophotographic photoreceptors has been improved, there is still room for improvement.

Particularly, in recent electrophotographic copying machines, higher image quality and higher functionality are desired. Therefore, it is necessary to faithfully reproduce a document including halftone such as a photograph, and it is desired to further reduce the unevenness of characteristics or the image defect in the electrophotographic photosensitive member. Further, in a full-color copying machine which has become widespread in recent years, since copying such as a photograph is mainly performed, this unevenness or an image defect becomes visually more obvious than copying a character image, which is a big problem. There is.

One of the causes of this image defect is abnormal growth of a deposited film called a spherical protrusion existing in the deposited film. It has been confirmed that the cause of the abnormal growth is that the surface condition of the support during formation of the deposited film has a great influence. For example, dust that adheres to the surface of the support in the manufacturing process, or minute scratches that have occurred on the surface of the support during cutting and / or polishing of the support, or minute protrusions that remain on the surface are deposited as nuclei. It has been elucidated to promote abnormal growth of the film. That is, in particular, a photoreceptive layer is controlled and deposited at the atomic level on the support by plasma CVD or the like.
Since the Si electrophotographic photosensitive member strongly reflects the information on the surface of the support, its strict management is required.

Further, in recent years, global-scale environmental pollution has become a problem, and it is desired to reduce not only substances that cause environmental pollution, but also industrial waste that requires enormous energy and cost for its treatment. . Although the nc-Si photoconductor itself is non-polluting, a product that has reached the end of its life as an electrophotographic device or a product that has become defective in the manufacturing stage becomes industrial waste.

In order to deal with these problems, it is necessary not only to pay attention to the light-receiving layer as in the prior art but to conduct a total study including the support and the light-receiving layer. Is.

[Object of the Invention] The present invention has been made in view of the above points, and provides an electrophotographic photosensitive member having a conventional light-receiving layer composed of a material having a silicon atom as a base as described above. It is an object of the present invention to solve various problems, to supply a photoconductor having excellent electrical characteristics and greatly reducing image defects at a low cost and a high yield.

That is, the main object of the present invention is to obtain a total examination of an electrophotographic photosensitive member including a support and a light-receiving layer, whereby it is particularly excellent in characteristics such as image defects and halftone unevenness, and the environment for use is selected. The present invention provides a method of manufacturing a photoreceptor at a lower cost by reducing the amount of industrial waste by significantly improving the yield in the manufacturing process and enabling the regeneration of a used photoreceptor. It is a thing.

Another object of the present invention is to provide a uniform and high-quality silicon atom with excellent adhesion between the layer provided on the conductive support and the conductive support or between the layers of the laminated layers. Another object of the present invention is to provide an electrophotographic photosensitive member having a light-receiving layer composed of a non-single crystal material as a base material.

Still another object of the present invention is that when it is applied as an electrophotographic photosensitive member, it has sufficient charge retention capacity during charging processing for electrostatic image formation, and produces a clear halftone. A light composed of a non-single-crystal material having a silicon atom as a base material, which can easily obtain a high-quality image with high resolution and exhibits excellent electrophotographic characteristics to which ordinary electrophotography can be applied very effectively. Another object of the present invention is to provide a method for producing an electrophotographic photosensitive member having a receiving layer.

[0018]

Means and Actions for Solving the Problems The present inventors have
In order to overcome the above-mentioned problems in the conventional deposited film forming method, various characteristics required for the support and the light receiving layer were fundamentally reviewed, and further results were obtained as a result of earnest study from the viewpoint of productivity and cost reduction. It is a thing.

The present invention has been completed on the basis of the above findings, and the gist of the present invention is, at least in an electrophotographic photosensitive member having a support and a light-receiving layer, after expanding the support, It is characterized in that a photoreceptor layer is deposited after cutting and / or polishing the surface of the support.

The reason why the objective effect of the present invention is obtained by cutting and / or polishing after expanding the support of the present invention is considered as follows.

The light-receiving layer composed of a non-single crystal strongly reflects the information on the surface of the support as described above, and therefore its management is required to be very strict. For example, even if it is possible to obtain a macroscopically smooth and uniform surface property by simply cutting or polishing a support (hereinafter referred to as a blank tube) that has not been subjected to surface processing (cutting / polishing) as in the past. Microscopically, there were cases where it was not always smooth and homogeneous. That is, fine scratches and fine irregularities may remain on the support during cutting / polishing. This is considered to be related to the material and surface property of the support.

In the present invention, support is carried out by work hardening of expanding the support (that is, hardening is performed by causing dislocation in the crystal structure of the support by an external force and increasing the dislocation density according to the external force). It is considered that the effect of the present invention can be obtained by modifying the surface properties of the body and improving the workability during cutting / polishing to suppress the generation of minute scratches and irregularities after the surface of the support is processed. ing.

The experimental examples conducted by the present inventors will be described below.

In each of the experimental examples and examples in the present specification, a light receiving member was manufactured by a microwave discharge method unless otherwise specified. The outline and the manufacturing procedure are shown below.

An example of the procedure for actually forming an electrophotographic photosensitive member by the method for manufacturing an electrophotographic photosensitive member of the present invention using an aluminum alloy cylinder as a conductive support member is shown in FIG. , And FIG. 2A and FIG.
The deposition film forming apparatus by the microwave CVD method shown in FIG.

First, the aluminum alloy cylinder blank is set in the pipe expanding apparatus shown in FIG. Here, 101 is the main body of the tube expanding apparatus, 102 is an aluminum alloy cylinder tube, 103 is urethane rubber for tube expanding, and 104 is pressure applied to urethane rubber 103 for tube expanding. Next, compressed air is introduced into the urethane rubber 103 for pipe expansion located inside the cylinder, and a pressure 104 of about 300 kg · f / cm ² is applied to the cylinder 102 to expand the pipe.

Lathe with air damper for precision cutting of expanded aluminum alloy cylinder base pipe (PNEUMO
PRECISION INC. (Made / not shown), a diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, the support was vacuum chucked to the rotary flange of this lathe, and white kerosene spray was sprayed from the attached nozzle, and cutting powder was suctioned from the vacuum nozzle also attached, while the peripheral speed was 1000 m / min and the feed speed was 0.01 mm / Under the condition of R, mirror cutting is performed so that the outer diameter is 108 mm. The surface of the support after the cutting is processed by a support cleaning device (not shown).

Next, the photoconductive member deposited film by the microwave plasma CVD method shown in FIGS. 2 (a) and 2 (b) is formed on the surface of the conductive support after the tube expanding process, the cutting process and the cleaning process. A deposition film mainly composed of nc-Si is formed by the forming apparatus.

Here, FIG. 2A is a schematic vertical sectional view of a manufacturing apparatus by the microwave discharge method, and FIG. 2B is an X- line of FIG.
It is a schematic cross-sectional view in an X-ray. In FIG. 2A and FIG. 2B, 201 is a reaction vessel having a vacuum airtight structure. Further, reference numeral 202 denotes a microwave introduction dielectric window formed of a material (eg, quartz glass, alumina ceramics, etc.) 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 from the microwave power source to the vicinity of the reaction container and a cylindrical portion inserted in the reaction container. The waveguide 203 is connected to a microwave power source (not shown) together with a stub tuner (not shown) and an isolator (not shown). The dielectric window 202 is hermetically sealed to the inner wall of the cylindrical portion of the waveguide 203 in order to maintain the atmosphere in the reaction vessel. Reference numeral 204 is an exhaust pipe having one end opened to the reaction vessel 201 and the other end communicating with an exhaust device (not shown). Reference numeral 206 denotes a discharge space surrounded by the conductive support 205. A power supply (not shown) is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 210, and is electrically connected to the electrode 210.

The electrophotographic photosensitive member is manufactured by using the deposited film forming apparatus as follows. First, the reaction vessel 201 is evacuated through an exhaust pipe 204 by a vacuum pump (not shown), and the pressure in the reaction vessel 201 is adjusted to 1 × 10 ^−7.
Adjust to less than Torr. Then, the heater 207 heats and holds the temperature of the support 205 at a predetermined temperature.
Therefore, the raw material gas is passed through a gas introduction means (not shown) to nc
A raw material gas such as a silane gas as a Si source gas, a diborane gas as a doping gas, and a helium gas as a diluent gas is introduced into the reaction vessel 201. Simultaneously with it, a microwave power source (not shown) is used for frequency 2.4.
A microwave of 5 GHz is generated and introduced into the reaction vessel 201 through the waveguide 203 and the dielectric window 202. Further, a direct current power supply (not shown) electrically connected to the bias electrode 210 in the discharge space 206 applies a direct current voltage to the support 205 on the bias electrode 210.
Thus, the discharge space 2 surrounded by the conductive support 205
At 06, the source gas is excited by the energy of the microwave and is difficult to be solved, and further, the bias electrode 210 and the support 2
While a constant electric field is applied to the conductive support 205 by the electric field between the layers 05, a deposited film is formed on the surface of the support 205. At this time, the rotating shaft 208 on which the conductive support 205 is installed is rotated by the motor 209, and the conductive support 205 is rotated around the central axis of the support generatrix direction, so that the entire circumference of the conductive support 205 is obtained. A deposited film layer is formed uniformly across the surface.

The light-receiving member of the present invention can be manufactured by such a manufacturing apparatus.

[Experimental Example 1] An aluminum alloy cylinder raw tube having a purity of 99.95% was used as a support according to the above-described cylinder expanding processing procedure, cutting procedure, and cleaning procedure of the present invention. The surface of the support was observed by an optical microscope to examine the surface condition.

Further, ink was applied to the surface of the support, and the cleanliness of the surface of the support was evaluated from the cissing state of the ink.

All the evaluation results were very good, and it was confirmed that the support tube expansion + cutting of the present invention gives a very good surface property as a support.

[Experimental Example 2] An aluminum alloy cylinder raw tube having a purity of 99.95% was used as a support according to the above-described cylinder expanding processing procedure, cutting procedure, and cleaning procedure of the present invention.
Then, using the deposited film forming apparatus shown in FIGS. 2A and 2B, the charge injection element layer and the photoconductive layer are formed on the support according to the manufacturing conditions of Table 1 by the above-described deposited film forming method of the present invention. , An nc-Si film having a three-layer structure of a surface layer was deposited. In this way, 12 supports having the nc-Si film deposited thereon were manufactured. The surface of the prepared support was observed with an optical microscope, and the top, middle, and bottom of the support were each 3 cm ² × 3 cm.
The number of spherical protrusions having a size of 10 to 40 μm existing on ² sides was counted, and the average value was obtained.

Further, as a comparative experiment, the same nc was used according to the same procedure as this experimental example except that the conventional support was used as the support.
-Twelve substrates with Si films deposited were prepared. Similarly, spherical protrusions were counted on the prepared support and an average value was obtained.

As a result of the above evaluation, the number of spherical projections existing on the support using the method of the present invention is reduced by 30 to 40% with respect to the number of spherical projections existing on the conventional support. Was confirmed.

[Experimental Example 3] An experiment was conducted under the following conditions to examine the adhesion of the deposited film of the electrophotographic photosensitive member of the present invention.

An aluminum alloy cylinder tube having a purity of 99.95% was used as a support according to the above-described cylinder expanding process, cutting process and cleaning process of the present invention, and then, as shown in FIG.
Using the deposited film forming apparatus shown in (a) and FIG. 2 (b), the charge injection blocking layer, the photoconductive layer, and the surface of the deposited film forming method of the present invention described above according to the manufacturing conditions of Table 1 as in Experimental Example 2 were used. An nc-Si photosensitive drum having a three-layer structure was prepared. In the process of manufacturing the photosensitive drum, the discharge was intentionally stopped when half the film thickness of each layer was deposited and when the layer interface of each layer was formed.
The operation of restarting the discharge after 0 seconds was performed. In this way, 120 nc-Si photosensitive drums were manufactured. The film peeling condition of the produced nc-Si photosensitive drum was observed and evaluated.

Further, as a comparative experiment, the same nc was used according to the same procedure as this experimental example except that the conventional support was used as the support.
120 Si photosensitive drums were produced. Produced nc-
The same evaluation was performed on the Si photosensitive drum.

The results are shown in Table 2.

As is clear from Table 2, the nc-S of the present invention is
It has been confirmed that the i photosensitive drum has excellent film adhesion as compared with the conventional nc-Si photosensitive drum.

From the above experimental results, the nc-S of the present invention is obtained.
It can be seen that the surface of the support of the i-photosensitive drum is excellent as an electrophotographic photosensitive member, and the adhesion to the deposited film is excellent.

Further, according to the present invention, the function of the deposited film on the surface of the used electrophotographic photosensitive member is not normal due to the life or the addition of scratches or the like due to handling, or the function of the electrophotographic photosensitive member is unsatisfactory at the manufacturing stage. It is also possible to recycle a non-defective electrophotographic photosensitive member.

For example, in the case of a used photoconductor, the photoreceptive layer may be removed, the tube may be expanded, and the treatment may be performed according to the above-mentioned steps. Alternatively, after expanding the tube, the light-receiving layer may be removed and the same treatment may be performed. For removal of the light receiving layer, for example, a mechanical removal method using a cutting tool, a chemical removal method such as wet and dry etching, or the like may be appropriately combined with an optimal method in terms of workability or cost. Good.

Also, for defective products which have been defective in the manufacturing stage, those in which the photoreceptive layer has already been deposited are reproduced in the same manner as the used photoconductor, and the photoreceptive layer is not deposited. If the body itself has a flaw or the like, the tube may be expanded to a depth not less than the flaw and then cut and / or polished to perform the same treatment as described above.

In the present invention, however, it is important to carry out additional machining especially for expanding the tube of the support which has been used or whose inner diameter has been processed, while paying attention to the following points.

FIG. 3 is an explanatory view of the structure around the photoconductor of an electrophotographic apparatus in which the electrophotographic photoconductor is used. Here, 301 is an electrophotographic photosensitive member, 302 is a primary charger, 303 is a developing device, 304 is a transfer charger, 305 is a separation charger, and 306.
Is a cleaning roller, and 307 is a cleaning blade. As is clear from this figure, functional components for performing an electrophotographic process are accurately positioned and fixed around the photoconductor around the photoconductor. For example, the developing unit 303 is assembled with a uniform gap of 0.2 to 0.4 mm with respect to the photoconductor 301, and the precision of the uniformity of the gap requires a high precision of 1/10 of the gap amount. To be done.

In order to meet this requirement, when the electrophotographic photosensitive member is mounted on the main body of the electrophotographic apparatus, the end portion of the support, which is the fitting portion between the photosensitive member and the electrophotographic apparatus, that is, the flange mounting portion is provided. By processing with high precision, the core of the photoconductor at the time of use is eliminated.

Therefore, in particular, when the photosensitive member having the inner diameter of the support member processed or the support member is expanded and used, it is necessary to perform an additional process in order to maintain the accuracy of the fitting portion. That is, the support after pipe expansion has an inner diameter dimension and shape that change with the pipe expansion, so that the fitting portion of the support is processed before pipe expansion (used photoconductor / in the manufacturing stage. For defective products), the required accuracy when the electrophotographic apparatus is mounted can be met only by performing additional processing on the fitting portion.

At this time, regarding the additional machining, if the outer diameter dimension is the same and the mounting inner diameter of the flange or gear is large,
Alternatively, by making the mounting inner diameter and the mounting interval of the flange and the gear equal to those of the model of the model in which the mounting interval of the flange and the gear is short, it is possible to use the electrophotographic photosensitive member for the different models.

On the contrary, by supplementing the fitting portion with a jig such as a spacer, it is possible to mount the same model or a different model on the electrophotographic apparatus.

The conductive support used in the present invention is, for example, Al, Cr, Mo, Au, In, Nb, T.
Examples thereof include metals such as e, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Among them, aluminum is preferable in the present invention from the viewpoint of manufacturing and handling, since it has appropriate strength and excellent workability. When aluminum is used as the support material, it is preferable to contain 1 to 10% by weight of magnesium in order to improve machinability. Further, as the purity of aluminum before containing magnesium, 98% by weight or more, preferably 99% by weight or more is effective in the present invention.

Although the thickness of the support varies depending on the material used, it is specified in terms of strength and processability that can withstand use, dimensional accuracy (deformation amount) during manufacturing, and cost. For example, when an aluminum support is used, the mechanical strength at the time of use, the dimensional accuracy at the manufacturing stage, the dimensional accuracy (deformation amount) at the time of manufacturing, and the light accumulated on the support. The thickness is preferably 2.5 mm or more in consideration of the internal stress with the receiving layer, the adhesiveness due to strain, and the like.

The ratio of the minimum wall thickness of the support end (fitting portion) to the maximum wall thickness of the support center is preferably 0.2 or more, more preferably 0.3 or more, and most preferably. 0.
It is 5 or more.

In the present invention, the amount of pipe expansion of the support varies depending on the material used. For example, in the case of aluminum, the amount of pipe expansion is 5 mm when the thickness of the support is 108 mm and the outside diameter is 108 mm. If the amount is too small, the effect of the present invention cannot be obtained, and if the amount of tube expansion is too large, the support may be distorted or cracked. Therefore, the outer diameter is preferably 0.01% to 5%, more preferably 0.02%. ~ 3%, optimally 0.03% ~
2%.

In the present invention, the tube expanding method is not particularly limited, but examples thereof include a method of applying pressure from the inside of the support, a method of expanding the tube by centrifugal force, and a method of combining these.

The method of applying pressure to the support is not particularly limited, and any method such as air pressure, hydraulic pressure, water pressure by a fluid such as gas, liquid, powder, or a mixture thereof may be selected as appropriate. And use it.

The pressure applied to the support may be appropriately selected depending on the material of the support. For example, when the support is aluminum, it is preferably 50 kg · f /
cm ² or more, more preferably 100 kg · f / cm ² or more, most preferably 200 kg · f / cm ² or more is suitable for the present invention. However, the pressure unit in the present invention is kg · f /
cm ² means gravitational kilogram per square centimeter, and 1 kg · f / cm ² is equal to 98066.5 Pa.

Further, in the present invention, it is also effective to process the surface shape after cutting the conductive support with a predetermined accuracy.

For example, when image recording is performed using coherent light such as laser light, unevenness may be provided on the surface of the conductive support in order to eliminate image defects due to interference fringe patterns appearing in a visible image. Good. The irregularities provided on the surface of the conductive support are described in JP-A-60-168156 and JP-A-60-168156.
It is produced by a known method described in JP-A-178457 and JP-A-60-225854. In addition, as another method for eliminating the image defect due to the interference fringe pattern when using coherent light such as laser light, a concavo-convex shape due to a plurality of spherical trace depressions may be provided on the surface of the conductive support. That is, the surface of the electrically conductive support has irregularities smaller than the resolution required for the electrophotographic photoreceptor, and the irregularities are due to a plurality of spherical trace dents. The unevenness due to the plurality of spherical trace depressions provided on the surface of the conductive support is produced by a known method described in JP-A-61-231561.

In the present invention, the washing step of the support is an important step which influences the surface property. Regarding the washing of the support, for example, as described in JP-A-61-171798, triethane (trichloroethane: C) is used.
It is also possible to wash with ₂ H ₃ Cl ₃ ). However, an organic solvent such as trichloroethane has a bad effect not only on the human body but also on the local environment, and therefore its use must be avoided. For these reasons, the method of cleaning the substrate with an aqueous system is more preferable.

That is, regarding washing, the washing liquid used in the washing step is preferably water or a mixture of water and a surfactant. The water quality can be any. The surfactant used in the washing step may be any of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof. The present invention is effective even if an additive such as sodium tripolyphosphate is added.

If the temperature of the water used in the cleaning step of the present invention is too high, an oxide film will be generated on the surface of the conductive substrate, which may cause peeling of the deposited film. On the other hand, if it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower, and most preferably 30 ° C.
C. or higher and 55.degree. C. or lower are suitable for the present invention.

In the present invention, the use of ultrasonic waves in the cleaning step is important for obtaining the full effect of the present invention. The frequency of ultrasonic waves is preferably 100 Hz or higher and 10 MHz
The following is more effective, 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 ultrasonic waves is preferably 10 W or more, 100 k
W or less, more preferably 100 W or more and 10 kW or less is effective.

The quality of the water used in the pure water contact step of the present invention is very important, and semiconductor grade pure water, especially ultra LSI grade ultra pure water is desirable. Specifically, the resistivity at a water temperature of 25 ° C. is 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
The above is 100,000 or less, preferably 10,000 or less, and most preferably 1,000 or less in 1 ml. As the amount of microorganisms, a total viable cell count of 1,000 or less, preferably 100 or less, and optimally 10 or less per 1 ml is suitable for the present invention. The amount of organic matter (TOC) is 100 mg or less, preferably 10 mg or less, and most preferably 2 mg or less per 1 liter, which is suitable for the present invention.

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

When bringing pure water into contact with the surface of the electroconductive substrate, it is desirable to apply water pressure and spray it. When the water pressure is sprayed, the effect of the present invention becomes small if it is too weak, and if it is too strong, a pear-like pattern occurs on the image of the obtained electrophotographic photosensitive member, especially on a halftone image. I will end up. Therefore, the pressure of water is 2 kgf / c
m ² or more and 300 kg · f / cm ² or less, preferably 1
0 kg · f / cm ² or more, 200 kg · f / cm ² or less, optimally 20 kg · f / cm ² or more, 150 kg ·
A value of f / cm ² or less is suitable for the present invention.

As the method for spraying pure water of the present invention, a method of spraying water whose pressure is increased by a pump or a method of mixing water pumped up by a pump with high-pressure air before the nozzle and spraying it by the pressure of air is used. There are ways.

The flow rate of the pure water of the present invention is 1 liter / m 2 per conductive substrate in view of the effect of the present invention and economy.
in or more and 200 liters / min or less, preferably 2
Liter / min or more, 100 liter / min or less,
Optimally 5 liters / min or more, 50 liters / mi
n or less is suitable for the present invention.

If the temperature of the pure water of the present invention is too high, an oxide film will be formed on the conductive substrate, which may cause peeling of the deposited film and the effect of the present invention cannot be sufficiently obtained. If it is too low, the effect of the present invention cannot be sufficiently obtained.
Therefore, the temperature of pure water is 5 ° C or higher and 90 ° C or lower,
It is preferably 10 ° C or higher and 55 ° C or lower, and most preferably 15 ° C or higher and 40 ° C or lower.

If the treatment time of the water contact treatment is too long, an oxide film is formed on the conductive substrate, and if it is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or more and 30 minutes or less, preferably 20 seconds. Above, 20 minutes or less, optimally over 30 seconds, 1
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 the formation of the deposited film in order to remove the influence of the oxide film on the surface of the substrate during the formation of the deposited film.

If the time from cutting to the contact with water is too long, an oxide film will be formed again on the surface of the substrate, and if it is too short, the process will not be stable. Therefore, the time is 1 minute or more and 16 hours or less, preferably 2 minutes or more. , 8 hours or less, optimally 3 minutes or more, 4
Times below are suitable for the present invention.

If the time from the water contact treatment to the deposition film forming apparatus is too long, the effect of the present invention becomes small, and if it is too short, the process is not stable. Therefore, the time is 1 minute or more and 8 hours or less, preferably. 2 minutes to 4 hours, optimally 3
Minutes or more and 2 hours or less are suitable for the present invention.

Further, in the light receiving member of the present invention, the light receiving layer may contain a substance having conductivity, if necessary.

Specific examples of the halogen atom (X) contained in the light-receiving layer of the present invention include fluorine, chlorine, bromine and iodine, with fluorine and chlorine being particularly preferable. . The amount of halogen atoms (X) contained in the light-receiving layer or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is usually 1 to 40a.
It is desirable to be tmic%, preferably 5 to 30 atmic%.

The layer thickness of the light receiving layer in the light receiving member of the present invention is one of the important factors for efficiently achieving the object of the present invention. As will be given, it is necessary to pay sufficient attention when designing the light receiving member, and it is usually 1 to 100 μm, preferably 1 to 80 μm, more preferably 2 to 50 μm.

In the present invention, in order to effectively achieve the object, the photoconductive layer formed on the support has the following semiconductor characteristics and exhibits photoconductivity with respect to irradiation light. nc-Si: (H, X). p-type nc-Si: (H, X) ... containing only an acceptor. Alternatively, it contains both a donor and an acceptor and has a high relative concentration of the acceptor. p ⁻ -type nc-Si: (H, X) ... Type having a low acceptor concentration (Na) or a low relative acceptor concentration. n-type nc-Si: (H, X) ... containing only a donor. Alternatively, a substance containing both a donor and an acceptor and having a high relative concentration of the donor. n ⁻ type nc-Si: (H, X) ... Type having a low donor concentration (Nd) or a low relative acceptor concentration. i-type nc-Si: (H, X) ... Na≈Nd≈0 or Na≈Nd.

In the light-receiving member of the present invention, the light-receiving layer may contain a substance for controlling conductivity in the whole layer region or a part of the layer region in a uniform or non-uniform distribution state.

As the substance for controlling the conductivity, so-called impurities in the field of semiconductors can be cited, and an atom belonging to Group III of the Periodic Table giving p-type conductivity [hereinafter simply referred to as (Group III atom)], Alternatively, an atom belonging to Group V of the periodic table that gives n-type conductivity [hereinafter simply referred to as (Group V atom)] is used. Specifically, as the group III atom, B (boron), Al (aluminum), Ga
(Gallium), In (Indium), Tl (Thallium)
Etc., but particularly preferred are B,
Ga. Further, as the group V atom, P (phosphorus), A
Examples thereof include s (arsenic), Sb (antimony), Bi (bismuth), etc., and particularly preferable ones are P and S.
b.

When the photoreceptive layer of the present invention contains a group III atom or a group V atom which is a substance for controlling conductivity, it is contained in the entire layer region or in a part of the layer region. Varies depending on the intended purpose and the expected effect, as will be described later, and hence the amount to be contained also varies.

That is, when the main purpose is to control the conductivity type and / or the conductivity of the light-receiving layer, it is contained in the entire region of the light-receiving layer. In this case, a group III atom or a group V atom is contained. The content of group atoms may be relatively small, usually 1
× 10 ⁻³ to 1 × 10 ³ atomic ppm, preferably 5 × 10 ^{−2 to} 5 × 10 ² atomic pp
m, optimally 1 × 10 ⁻¹ to 2 × 10 ² atomic p
pm.

To function as a charge injection blocking layer, a group III atom or a group V atom is contained in a part of the layer region in contact with the support in a relatively high concentration and in a uniform distribution state, or It is carried out by making the distribution concentration of the group III atom or the group V atom in the layer thickness direction high so as to be high on the side in contact with the support. A partial layer region containing a group III atom or a group V atom or a region containing a high concentration serves as a charge injection blocking layer. That is, when the group III atom is contained, the movement of electrons injected from the support side into the photoreceptive layer is more efficient when the free surface of the photoreceptive layer is subjected to + polarization electrification treatment. Can be blocked by the V
When a group atom is contained, the free surface of the photoreceptor layer is
It is possible to more efficiently block the movement of holes injected from the support side into the light-receiving layer when subjected to the electrification treatment with polarity. The content in this case is relatively large.
Specifically, in general, 30 to 5 × 10 ⁴ atomic
ppm, but preferably 50 to 1 × 10 ⁴ ato
mic ppm, optimally 1 × 10 ^{2 to} 5 × 10 ³ a
It is tomic ppm. In order to efficiently exhibit the effect, the relationship of t / t + t0 ≦ 0.4 may be established when a part of the layer region is t and the layer thickness of the other light receiving layer is t0. Desirably, more preferably, the value of the relational expression is 0.35 or less, and optimally 0.3 or less. The layer thickness of the layer region is generally 3 × 10 ^{−3 to} 10 μm, but preferably 4 × 10 3.
^{-3 to} 8 μm, optimally 5 × 10 ^{-3 to} 5 μm.

As described above, the action and effect of each of the distribution states of the group III atoms or the group V atoms have been described individually.
For obtaining a light receiving member that can achieve the desired purpose,
It goes without saying that the distribution state of these Group III atoms or Group V atoms and the amount of Group III atoms or Group V atoms to be contained in the light-receiving layer are appropriately combined and used. Absent. For example, when a charge injection blocking layer is provided at the end of the light receiving layer on the side of the support, the polarity of the substance that controls the conductivity contained in the charge injection blocking layer in the light receiving layer other than the charge injection blocking layer is May contain a substance that controls conduction of another polarity, or may contain a substance that controls conductivity of the same polarity in a much smaller amount than that contained in the charge blocking layer. .

Further, in the light receiving member of the present invention,
A so-called barrier layer made of an electrically insulating material may be provided as the layer structure provided at the end portion on the support side, and both the barrier layer and the charge injection blocking layer may be used as the constituent layers.
As a material for forming such a barrier layer, Al ₂ O ₃ ,
Examples thereof include inorganic electrical insulating materials such as SiO ₂ and Si ₃ N ₄ and organic electrical insulating materials such as polycarbonate.

Further, in the light receiving member of the present invention,
The layer structure provided at the end on the support side has a narrow optical band gap, so-called IR, for the purpose of suppressing an interference phenomenon that occurs when coherent monochromatic light such as laser light is used.
An absorption layer may be provided, and both the absorption layer and the charge injection blocking layer may be constituent layers. As such an absorption layer, for example, nc-SiGe: (H, where germanium atom (Ge) is added to the nc-Si: (H, X) layer is used.
X).

Next, the method for forming the light receiving layer of the present invention will be described.

Any of the amorphous materials constituting the light receiving layer of the present invention is a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD method), a method of decomposing a raw material gas by light (optical CVD method), A method of decomposing the raw material gas by direct current or high frequency, microwave glow discharge, etc., and decomposing the raw material gas by plasma generated thereby (plasma C
VD method) or the like. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load of capital investment, manufacturing scale, and characteristics desired for the light receiving member to be manufactured. The plasma CVD method is preferable because it is relatively easy to control the conditions for manufacturing the compound, and carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. The plasma CVD method and the sputtering method may be used together in the same system.

For example, by plasma CVD, nc
In order to form a layer composed of —Si: (H, X), basically, a raw material gas for supplying Si, which can supply silicon atoms (Si), and a gas for introducing hydrogen atoms (H) and / or Alternatively, a source gas for introducing a halogen atom (X) is introduced into a deposition chamber where the inside can be decompressed to cause glow discharge in the deposition chamber, and nc- is formed on the surface of a predetermined support previously set at a predetermined position. A layer of Si: (H, X) is formed.

As the source gas for supplying Si, Si is used.
Examples thereof include H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , and the like, and gasified silicon hydrides (silanes) that can be gasified. From the viewpoint of goodness, SiH ₄ and Si ₂ H ₆ are preferable.

As the raw material gas for introducing the halogen atom, many halogen compounds can be mentioned. For example, a halogen gas, a halide, an interhalogen compound, a silane derivative substituted with halogen, or the like can be gasified or gasified. Halogen compounds are preferred. Specifically, fluorine,
Chlorine, bromine, iodine halogen gas, BrF, ClF,
ClF ₃ , BrF ₅ , BrF ₃ , IF ₇ , ICl, IB
interhalogen compounds such as r, SiF ₄ , Si ₂ F ₆ ,
Examples thereof include silicon halide such as SiCl ₄ and SiBr ₄ . In the case of using a silicon halide gas state or a gasifiable substance as described above, a layer composed of nc-Si containing a halogen atom is formed without separately using a raw material gas for supplying Si. It is particularly effective because it can.

As the source gas for supplying the hydrogen atoms, hydrogen gas, halides such as HF, HCl, HBr and HI, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si _{4 are used.}
Hydrogenated silicon such as H ₁₀ or SiH ₂ F ₂ , SiH
₂ I ₂ , Si ₂ Cl ₂ , SiHCl ₃ , SiH ₂ B
A gas state of halogen-substituted silicon hydride such as r ₂ or SiHBr ₃ or a gasifiable one can be used. When these raw material gases are used, it is necessary to control electrical or photoconductive characteristics. It is effective because the content of hydrogen atoms (H), which is extremely effective, can be easily controlled.

By the way, when the hydrogen halide or the halogen-substituted silicon hydride is used, the hydrogen atom (H) is also introduced at the same time as the introduction of the halogen atom.
Especially effective.

The amount of the starting material used for introducing the hydrogen atom (H) and / or the halogen atom (X) contained in the nc-Si layer to be introduced into the deposition chamber and the discharge power are controlled. Be seen.

To form a layer of nc-Si: (H, X) by the reactive sputtering method or the ion plating method, for example, in the case of the sputtering method, for introducing a halogen atom, the above-mentioned halogen is used. A gas of the compound or the silicon compound containing the halogen atom may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

For example, in the case of the reactive sputtering method, a Si target is used and a gas for introducing a halogen atom and a hydrogen gas are introduced into the deposition chamber together with an inert gas such as He or Ar as required. A layer of nc-Si: (H, X) is formed on the support by forming a plasma atmosphere and sputtering the Si target.

Using plasma CVD method, sputtering method, or ion plating method, nc-Si:
To form a layer composed of an amorphous material in which (H, X) further contains a Group III atom or a Group V atom, an oxygen atom, a carbon atom or a nitrogen atom, nc-Si: (H ,
When forming the layer of X), a starting material for introducing a group III atom or a group V atom, a starting material for introducing an oxygen atom, a starting material for introducing a carbon atom, or a starting material for introducing a nitrogen atom is used. , With the aforementioned starting materials for forming nc-Si: (H, X) and their controlled inclusion in the layers to be formed.

For example, using a plasma CVD method, a sputtering method, or an ion plating method,
Nc-Si containing a group atom or a group V atom: (H,
To form a layer or layer region composed of X), a group III atom or a group V atom for introducing a group III atom or a group V atom at the time of forming the layer composed of nc-Si: (H, X) described above is formed. The starting materials are used in conjunction with the starting materials for the formation of nc-Si: (H, X), with controlled inclusion of their amount in the layers formed.

As a starting 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 ₆ H ₁₀ , B ₆ H ₁₂ , B
Boron hydride such as ₆ H ₁₄ , BF ₂ , BCl ₃ , BBr ₃
And the like. In addition, AlC
l ₃ , CaCl ₃ , Ga (CH ₃ ) ₂ , InCl ₃ , T
lCl _{3 and the} like can also be mentioned.

As the starting material for introducing the Group V atom, specifically, for introducing a phosphorus atom, PH ₃ , P ₂ H ₆ or other hydrogenated phosphorus, PH ₄ I, PF ₃ , PF ₅ , PCl ₃ , P
Examples thereof include phosphorus halides such as Cl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl
₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , Sb
F ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiC
l ₃ , BiBr _{5 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

When the plasma CVD method is used to form the layer or layer region containing oxygen atoms, oxygen atoms are introduced into the starting materials selected for forming the light-receiving layer as desired. Starting material for is added.
As such a starting material for introducing oxygen atoms, almost any material can be used as long as it is a gaseous substance containing at least oxygen atoms as constituent atoms or a substance that can be gasified.

For example, a source gas containing silicon atoms (Si) as constituent atoms, a source gas containing oxygen atoms (O) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X) are added. A raw material gas to be a constituent atom is mixed at a desired mixing ratio and used, or a silicon atom (S
A raw material gas containing i) as a constituent atom and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms are also mixed at a desired mixing ratio, or silicon atoms (Si ) As a constituent atom, and an oxygen atom (O)
And a source gas containing hydrogen atoms (H) as constituent atoms, which are also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms, silicon atoms (Si), and oxygen. It is possible to mix and use a raw material gas having three atoms (O) and hydrogen atoms (H) as constituent atoms.

In addition to this, silicon atoms (Si),
A raw material gas containing hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms.

Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (N)
O ₂ ), dinitrogen monoxide (N ₂ O), dinitrogen trioxide (N ₂
O ₃ ), nitrous oxide (N ₂ O ₄ ), nitrous oxide (N
₂ O ₅ ), nitric oxide (NO ₃ ), silicon atom (S
i), an oxygen atom (O), and a hydrogen atom (H) as three constituent atoms. For example, disiloxane (H ₃ SiOSi)
H ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH
₃ ) and other lower siloxanes.

To form a layer or layer region containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or SiO ₂ wafer, or Si is used.
The target may be a wafer containing a mixture of SiO ₂ and SiO _2, and these may be sputtered in various gas atmospheres.

For example, when a Si wafer is used as a target, a raw material gas for introducing oxygen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas, if necessary, for sputtering. Then, the Si wafer may be sputtered by introducing these gas plasmas into the deposition chamber.

[0108] Also in another, as a separate target Si and SiO _2, or by using a single target of a mixture of Si and SiO _2, in an atmosphere of diluent gas as a gas for sputtering, or It can be formed by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the above-described example of the plasma CVD method can be used as an effective gas in the case of sputtering.

When the plasma CVD method is used to form the layer or layer region containing a nitrogen atom, one selected from the above-mentioned starting materials for forming the light-receiving layer for introducing a nitrogen atom is used. Starting material is added. As such a starting material for introducing nitrogen atoms, almost any material can be used as long as it is a gaseous or gasifiable substance containing at least nitrogen atoms as constituent atoms.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing nitrogen atoms (N) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X) are added. A raw material gas to be a constituent atom is mixed at a desired mixing ratio and used, or a silicon atom (S
A raw material gas containing i) as a constituent atom and a raw material gas containing nitrogen atoms (N) and hydrogen atoms (H) as constituent atoms can also be mixed at a desired mixing ratio and used.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N) as constituent atoms.

A starting material effectively used as a raw material gas for introducing a nitrogen atom (N) used when forming a layer or a layer region containing a nitrogen atom has N as a constituent atom or N and H As constituent atoms, for example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH
₄ N ₃ ), and the like, and nitrogen compounds such as nitrogen and nitrides and azides that can be gasified or gasified. In addition to this, in addition to the introduction of the nitrogen atom (N), the introduction of the halogen atom (X) is also possible, so that nitrogen trifluoride (F
Nitrogen halide compounds such as ₃ N) and dinitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned.

In order to form a layer or layer region containing a nitrogen atom by the sputtering method, a monocrystalline or polycrystalline Si wafer or Si ₃ N ₄ wafer, or a mixture of Si and Si ₃ N ₄ is contained. The target wafer may be used to sputter them in various gas atmospheres.

For example, when a Si wafer is used as a target, a raw material gas for introducing a nitrogen atom and, if necessary, a hydrogen atom and / or a halogen atom is diluted with a diluting gas, if necessary, for sputtering. Is introduced into the deposition chamber of S to form a gas plasma of these gases,
The i-wafer may be sputtered.

Separately, Si and Si ₃ N ₄ are used as separate targets, or by using one target in which Si and Si ₃ N ₄ are mixed, a diluent gas as a gas for sputtering is used. It can be formed by sputtering in an atmosphere or in a gas atmosphere containing at least a hydrogen atom (H) and / or a halogen atom (X) as constituent atoms. As the raw material gas for introducing nitrogen atoms, the gas for introducing nitrogen atoms in the raw material gas shown in the above-mentioned example of plasma CVD can be used as an effective gas also in the case of sputtering.

Further, for example, nc-S containing a carbon atom
To form the i: (H, X) layer by the plasma CVD method, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, and if necessary, A raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms is mixed and used at a desired mixing ratio, or a raw material gas containing carbon atoms (Si) as constituent atoms and carbon atoms. (C) and a source gas containing hydrogen atoms (H) as constituent atoms are also mixed in a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms and a silicon atom (Si ), A carbon atom (C) and a hydrogen atom (H) as constituent atoms, or a silicon atom (Si).
And a source gas containing hydrogen atoms (H) as constituent atoms and a source gas containing carbon atoms (C) as constituent atoms are mixed and used.

Nc-Si by sputtering method:
To form a light-receiving layer composed of (H, X), a single crystal or polycrystal Si wafer or C (graphite) wafer, or a wafer containing Si and C mixed, is used as a target. These are performed by sputtering in a desired gas atmosphere.

For example, when a Si wafer is used as a target, a raw material gas for introducing carbon atoms, hydrogen atoms and / or halogen atoms may be added as needed.
The Si wafer may be sputtered by diluting it with a diluting gas such as r or He and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases.

When Si and C are used as separate targets, or when they are used as a single target in which Si and C are mixed, a sputtering gas is used to introduce hydrogen atoms and / or halogen atoms. The gas may be diluted with a diluent gas, if necessary, and then introduced into a deposition chamber for sputtering to form gas plasma for sputtering. As the source gas for introducing each atom used in the sputtering method, the source gas used in the plasma CVD method described above can be used as it is.

Effectively used as such a source gas is SiH ₄ , Si ₂ having Si and H as constituent atoms.
Silane such as H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ (Silan
e) Hydrogenated silicon gas such as kind, C and H as constituent atoms, for example, saturated hydrocarbon having 1 to 4 carbon atoms, 2 carbon atoms
To ethylene-based hydrocarbons, acetylene-based hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as the saturated hydrocarbon,
(C₃H₈), Propane (C₃H ₈), N-butane
(N-C_FourH_Ten), Pentane (C_FiveH₁₂), Ethylene
As the hydrocarbon, ethylene (C₂H_Four),propylene
(C₃H₆), Butene-1 (C_FourH₈), Butene-2
(C_FourH₈), Isobutylene (C_FourH₈), Penten
(C_FiveH_Ten), As acetylene hydrocarbons, acetyl
Ren (C₂H₂), Methylacetylene (C₃H_Four),
Chin (C_FourH₆), Etc.

Examples of the raw material gas containing Si, C and H as constituent atoms include alkyl silicide such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . In addition to these source gases, H ₂ can of course be used as the source gas for introducing H.

When the photoreceptive layer according to the present invention is formed by the plasma CVD method, the sputtering method, or the ion plating method, oxygen atoms, carbon atoms and nitrogen atoms introduced into nc-Si: (H, X) or nitrogen atoms or The content of the group III atom or the group V atom is controlled by controlling the gas flow rate and the gas flow rate ratio of the starting material introduced into the deposition chamber.

The conditions such as the temperature of the support, the gas pressure in the deposition chamber and the discharge power at the time of forming the light receiving layer are important factors for obtaining the light receiving member having the desired characteristics, and the layer to be formed. The function is selected appropriately. Furthermore, these layer forming conditions may differ depending on the type and amount of each of the above-mentioned atoms contained in the light-receiving layer, so the layer formation conditions are determined in consideration of the type of atoms to be contained or the amount thereof. There is a need.

Specifically, the support temperature is usually 50 to 4
The temperature is set to 00 ° C, and particularly preferably set to 100 to 350 ° C. The discharge power condition is usually 10 W to 5000 W, and particularly preferably 20 W to 20 W per one support.
It is set to about 00W. The gas pressure in the deposition chamber is RFC
In the VD method, it is usually 0.01 to 1 Torr, particularly preferably 0.1 to 0.5 Torr, microwave CVD.
According to the method, the pressure is 0.2 mTorr to 100 mTorr, and particularly preferably about 1 mTorr to 50 mTorr.

However, the specific conditions for the temperature of the support, the discharge power, and the gas pressure in the deposition chamber for forming these layers are usually difficult to determine individually. Therefore, in order to form the nc-Si material layer having the desired characteristics, it is desirable to determine the optimum conditions for forming the layer based on the mutual and organic relationships.

In order to make the distribution of oxygen atoms, carbon atoms, nitrogen atoms, group III atoms or group V atoms, or hydrogen atoms and / or halogen atoms contained in the light-receiving layer of the present invention uniform. It is necessary to keep the above conditions constant when forming the light receiving layer.

In the present invention, in the form of the light-receiving layer, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or group III atoms or group V atoms contained in the layer is adjusted in the layer thickness direction. In order to form a photoreceptive layer having a desired state of distribution in the layer thickness direction by changing the above, if a plasma CVD method is used, oxygen atoms, carbon atoms, nitrogen atoms, or group III atoms or group V atoms are used. The gas flow rate when introducing the gas of the starting material for introducing the group atom into the deposition chamber is appropriately changed according to the desired rate of change, and other conditions are kept constant. Then, in order to change the gas flow rate, specifically, by gradually changing the opening of a predetermined needle valve provided in the middle of the gas flow path system, for example, by some commonly used method such as manual operation or an external drive motor. You can perform the operation. At this time, the change rate of the flow rate does not have to be a curve type, and the flow rate can be controlled according to a previously designed change rate curve by using a microcomputer or the like to obtain a desired content rate curve.

When the light-receiving layer is formed by the sputtering method, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or group III atoms or group V atoms in the layer thickness direction is changed in the layer thickness direction. In order to form a desired state of distribution in the layer thickness direction, as in the case of using the plasma CVD method, a starting material for introducing oxygen atoms, carbon atoms, nitrogen atoms, or group III atoms or group V atoms is used. The substance may be used in a gas state, and the gas flow rate when introducing the gas into the deposition chamber may be changed according to a desired rate of change.

In the electrophotographic light-receiving member of the present invention, for the purpose of further improving the adhesion of the deposited film between the support and the photoconductive layer, for example, Si ₃ N ₄ , SiO ₂ and S are used.
at least one of iO, a hydrogen atom and a halogen atom,
An adhesion layer made of an nc-Si material containing at least one of nitrogen atom and oxygen atom and silicon atom may be provided.

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

[0132]

【Example】

[Example 1] An aluminum alloy cylinder raw tube having a purity of 99.95% was used as a support according to the above-described cylinder expanding processing procedure, cutting procedure, and cleaning procedure of the present invention, and then, as shown in Figs. 2 (a) and 2 (b). Nc- comprising a two-layer structure of a charge injection blocking layer and a photoconductive layer according to the manufacturing conditions of Table 3 according to the above-described deposited film forming method of the present invention using the deposited film forming apparatus shown in FIG.
A Si photosensitive drum was produced. Nc produced in this way
The electrophotographic characteristics of the -Si photosensitive drum were evaluated as follows.

The prepared photosensitive drum was put in a copying machine NP7550 manufactured by Canon Inc., and an image was formed on a transfer paper by a usual copying process. The following evaluation was performed on the 500,000th image sample. However, at this time, charging was performed by applying a voltage of 6 kV to the charger. Image defects (white spots / black spots) White spots: The number of white spots with a diameter of 0.1 mm or more in the same area of an image sample obtained by placing an all-black original on the original plate and making a copy, and evaluated as follows. I went.

∘: Particularly good ○: Good Δ: No problem in practical use ×: Problem in practical use Black spot: Full white image Original sample placed on the platen and copied to have a diameter of 0. The number of black spots of 1 mm or more was counted and the following evaluations were performed.

[0135] ◎ ... particularly good ○ ... good △ ... practical problems without × ... practical problems there reproducibility of fine lines: a white background to observe the image samples obtained when you copy Place the normal document consisting of the entire character on the document table Then, it was evaluated whether the thin lines on the image were connected without interruption. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown.

∘ ∙ ∘ ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙ ∑ Image density at 100 points was measured with a circular area of 05 mm as one unit, and variations in the image density were evaluated.

⊚ Particularly good ○ ∙ Good Δ ∙ No problem in practical use ×… Problem in practical use White background fog: An image sample obtained by copying a normal manuscript consisting entirely of characters on a white background on a manuscript table was observed. The fogging on the white background was evaluated.

⊚ Particularly good ∘ Good ∘ No practical problem × Practical problem

<Comparative Example 1> An nc-Si photosensitive drum was manufactured in the same manner as in Example 1 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

The results are shown in Table 4 together with the results of Example 1.

Example 2 An aluminum alloy cylinder raw tube having a purity of 99.95% was used, and a support was prepared in the same manner as in Example 1 according to the cylinder expanding processing procedure, cutting procedure and cleaning procedure, and then as shown in FIG. Using the deposited film forming apparatus shown in FIG. 2B, an nc-Si photosensitive drum having a two-layer structure of a photoconductive layer and a surface layer was manufactured under the manufacturing conditions shown in Table 5. The electrophotographic characteristics of the produced nc-Si photosensitive drum were evaluated in the same manner as in Example 1.

The results of Example 1 and Comparative Example 1 are shown in Table 4.

<Comparative Example 2> An nc-Si photosensitive drum was manufactured in the same manner as in Example 2 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

Table 4 together with the results of Examples 1 and 2 and Comparative Example 1.
Shown in.

Example 3 An aluminum alloy cylinder raw tube having a purity of 99.95% was used to form a support in the same manner as in Example 1 according to the cylinder expanding processing procedure, cutting procedure, and cleaning procedure, and then, as shown in FIG. Using the deposited film forming apparatus shown in FIG. 2B, a blocking type nc- having a three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared according to the fabrication conditions shown in Table 6.
A Si photosensitive drum was produced. The electrophotographic characteristics of the produced nc-Si photosensitive drum were evaluated in the same manner as in Example 1.

Table 1 shows the results of Examples 1 and 2 and Comparative Examples 1 and 2.

<Comparative Example 3> An nc-Si photosensitive drum was manufactured in the same manner as in Example 3 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

Table 4 shows the results of Examples 1, 2 and 3 and Comparative Examples 1 and 2.

[Example 4] Using an aluminum alloy cylinder raw tube having a purity of 99.95%, a support was made in the same manner as in Example 1 according to the cylinder expanding process, cutting process, and cleaning process, and then, as shown in Fig. 2 (a). A blocking type nc-Si photosensitive drum having a four-layer structure of an IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared according to the manufacturing conditions shown in Table 7 by using the deposited film forming apparatus shown in FIG. It was made. Produced nc-
The electrophotographic characteristics of the Si photosensitive drum were evaluated in the same manner as in Example 1.

Examples 1 and 2 and 3 are shown in Table 4 together with the results of Comparative Examples 1, 2 and 3.

<Comparative Example 4> An nc-Si photosensitive drum was produced in the same manner as in Example 4 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

Table 4 shows the results of Examples 1, 2, 3 and 4 as well as Comparative Examples 1, 2, and 3.

Example 5 An aluminum alloy cylinder raw tube having a purity of 99.95% was used to form a support in the same manner as in Example 1 according to the cylinder expansion processing procedure, cutting procedure, and cleaning procedure, and then, as shown in FIG. 2B, using the deposition film forming apparatus shown in FIG. A drum was made. The electrophotographic characteristics of the produced nc-Si photosensitive drum were evaluated in the same manner as in Example 1.

Examples 1, 2, 3, 4 Comparative Examples 1, 2, 3,
It is shown in Table 4 together with the result of 4.

<Comparative Example 5> An nc-Si photosensitive drum was manufactured in the same manner as in Example 5 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

Examples 1, 2, 3, 4, 5 Comparative Examples 1, 2,
It is shown in Table 4 together with the results of 3 and 4.

Example 6 An aluminum alloy cylinder raw tube having a purity of 99.95% was used to form a support in the same manner as in Example 1 according to the cylinder expanding processing procedure, cutting procedure, and cleaning procedure, and then, as shown in FIG. Nc comprising a two-layer structure of a first photoconductive region, a second photoconductive region, and a surface layer using the deposited film forming apparatus shown in FIG.
-Si photosensitive drum was produced. The electrophotographic characteristics of the produced nc-Si photosensitive drum were evaluated in the same manner as in Example 1.

Examples 1, 2, 3, 4, 5 Comparative Examples 1, 2,
It is shown in Table 4 together with the results of 3, 4, and 5.

<Comparative Example 6> An nc-Si photosensitive drum was manufactured in the same manner as in Example 6 except that the aluminum alloy cylinder raw tube having a purity of 99.95% was not expanded. The produced nc-Si photosensitive drum was evaluated in the same manner as in Example 1.

Examples 1, 2, 3, 4, 5, 6 Comparative Example 1,
It is shown in Table 4 together with the results of 2, 3, 4, and 5.

As shown in Table 4, in any of the items, very good results were obtained in the present invention.

[Embodiment 7] An RF plasma CV is used as a light receiving layer.
It was formed using the D method. FIG. 4 shows an apparatus for manufacturing a light receiving member by the RF plasma CVD method used in the present invention.

In the figure, 402, 403, 404, 405,
Raw gas for forming each layer of the present invention is sealed in the gas cylinder 406. As an example, for example, 402 is SiH ₄ gas (purity 99.999%) cylinder, 403 is H ₂ . Diluted B ₂ H ₆ gas (purity 9
9.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 4
04 is a CH ₄ gas (purity 99.999%) cylinder, 40
5 is SiF ₄ gas (purity 99.999%) cylinder, 40
6 is an H ₂ gas (purity 99.999%) cylinder.

To allow these gases to flow into the reaction chamber 401, the valves 422-42 of the gas cylinders 402-406 are used.
6. Confirm that the leak valve 435 is closed, and check the inflow valves 412 to 416 and the outflow valve 417.
˜421, and confirming that the auxiliary valves 432 and 433 are opened, first, the main valve 434 is opened to exhaust the reaction chamber 401 and the gas pipe. Next, when the reading of the vacuum gauge 436 reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valves 432 and 433 and the outflow valves 417 to 421 are closed.

An example of forming the light receiving layer on the base cylinder 437 will be described. SiH from gas cylinder 402
₄ gas, B ₂ H ₆ / H ₂ gas from the gas cylinder 403, CH ₄ gas from the gas cylinder 404, and valve 42
2, 423, 424, 426 open and outlet pressure gauge 42
The pressure of 7, 428, 429, 431 was adjusted to 1 kg / cm ² , and the inflow valves 412, 413, 414, 416 were gradually opened, and the mass flow controllers 407, 40
8, 409, 411. Subsequently, the outflow valves 417, 418, 419, 421 and the auxiliary valve 43.
2, 433 are gradually opened to allow the gas to flow into the reaction chamber 401. SiH ₄ gas flow rate at this time, B ₂ H ₆ / H
₂ gas flow rate, CH ₄ gas flow rate, and H ₂ outlet valve so that the ratio of gas flow rate becomes a desired value 417,418,41
9, 421 are adjusted, and the opening of the main valve 434 is adjusted while observing the reading of the vacuum gauge 436 so that the pressure in the reaction chamber 401 becomes a desired value. The temperature of the base cylinder 437 is set to 40 to 40 by the heater 438.
After confirming that the temperature is set in the range of 0 ℃,
A power source 440 is set to a desired power to cause glow discharge in the reaction chamber 401, and a microcomputer (not shown) is used to follow a predesigned rate-of-change line and the SiH ₄ gas flow rate, B ₂ H ₆ / H ₂ gas flow rate, CH
A layer composed of nc-Si (H, X) containing carbon atoms and boron atoms is first formed on the base cylinder 437 while controlling the ₄ gas flow rate and the H ₂ gas flow rate.

After a lapse of a predetermined time, the valves 418, 413 and 426 for introducing the B ₂ H ₆ / H ₂ gas into the reaction chamber 401 are closed, and only SiH ₄ gas, CH ₄ gas and H ₂ gas are supplied. By introducing into the reaction chamber 401, nc-Si containing carbon atoms but not containing boron atoms is formed on the layer composed of nc-Si (H, X) containing carbon atoms and boron atoms. A layer composed of (H, X) can be formed.

Needless to say, all the outflow valves other than the gas outflow valves necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the same as the reaction chamber 401. In order to avoid remaining in the gas pipe from the outflow valves 417 to 421 to the inside of the reaction chamber 401, the outflow valves 417 to 421 are closed, the auxiliary valves 432 and 433 are opened, and the main valve 434 is fully opened. Is once evacuated to a high vacuum, if necessary.

Using the apparatus, as in Examples 1 to 6,
A blocking type nc-Si photosensitive drum having a three-layer structure of a charge injection blocking layer, a photoconductive layer, and a surface layer, and a four layer structure of a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer was prepared and implemented. When evaluated in the same manner as in Example 1, good results were obtained as in Examples 1 to 6.

[Embodiment 8] An aluminum alloy cylinder raw tube having a purity of 99.95% was used to form a support in the same manner as in Example 1 according to the cylinder expanding processing procedure, cutting procedure and cleaning procedure, and then Se as a light receiving layer. When an electrophotographic photosensitive drum was produced using the —Te-based photosensitive member and the organic photosensitive member and evaluated in the same manner as in Example 1, good results were obtained in the same manner as in Example 1.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

[0173]

[Table 4]

[0174]

[Table 5]

[0175]

[Table 6]

[0176]

[Table 7]

[0177]

[Table 8]

[0178]

[Table 9]

[0179]

INDUSTRIAL APPLICABILITY According to the present invention, in an electrophotographic photosensitive member having at least a support and a photoreceptive layer, after the support is expanded, the surface of the support is cut and / or polished, and then the photoreceptive layer is received. By depositing the layers, it is possible to provide a photoconductor that is particularly excellent in characteristics such as image defects and halftone unevenness and that can be used in any environment.

Further, according to the present invention, the yield in the manufacturing process is significantly improved, and the used photoconductor can be regenerated, so that the industrial waste is reduced and the photoconductor can be manufactured at a lower cost. Became possible.

[Brief description of drawings]

FIG. 1 is a schematic view of a tube expanding device of the present invention.

FIG. 2A is a schematic side sectional view of a device for manufacturing a light receiving member by a microwave discharge method according to the present invention, and FIG. 2B is a sectional view taken along line XX in FIG.

FIG. 3 is a diagram illustrating a configuration around a photoconductor of an electrophotographic apparatus.

FIG. 4 is a schematic side sectional view of an apparatus for manufacturing a light receiving member by the RF discharge method according to the present invention.

[Explanation of symbols]

 About FIG. 1 101 Tube expanding device main body 102 Aluminum alloy cylinder tube 103 Urethane rubber 104 Pressure About FIG. 209 Motor 210 Bias Electrode About FIG. 3 301 Electrophotographic Photosensitive Member 302 Primary Charger 303 Developer 304 Transfer Charger 305 Separation Charger 306 Cleaning Roller 307 Cleaning Blade About FIG. 401 Reaction Chamber 402-406 Gas Cylinder 407-411 Mass Flow Controller 412 -416 Inflow valve 417-421 Outflow valve 422-426 Valve 427-431 Pressure regulator 431,433 Auxiliary valve 434 Main valve 4 35 Leak valve 436 Vacuum gauge 437 Base cylinder 438 Heating heater 439 Motor 440 High frequency power source

Claims (5)

[Claims] 1. A method of manufacturing an electrophotographic photosensitive member, comprising forming a light receiving layer on a support, the first step of applying an external force to the support in a direction of expanding the area of the support, and the first step. After the step of, the second step of cutting and / or polishing the surface of the support, and the third step of depositing a light receiving layer on the support after the second step. And a method for manufacturing an electrophotographic photosensitive member. 2. A method for producing an electrophotographic photosensitive member having a light receiving layer on a circular tubular support, the first step of applying an external force to the circular tubular support in a direction of expanding the support, A second step of cutting and / or polishing the surface of the support after the first step, and a photoreceptive layer containing amorphous silicon as a main component on the support after the second step. A third step of
A method for manufacturing an electrophotographic photosensitive member, comprising: 3. As a means for applying an external force in the direction of expanding the support, a hollow member having elasticity is put inside the support having a tubular shape, a fluid is injected into the hollow member, and a pressure of the fluid is applied. The method for producing an electrophotographic photosensitive member according to claim 2, wherein the support is expanded by the method. 4. The electrophotographic photosensitive member is obtained by removing one that has been already used in an electrophotographic apparatus, and at least the first to third steps are performed on the electrophotographic photosensitive member. The method for producing an electrophotographic photosensitive member according to claim 1 or 2, wherein the electrophotographic photosensitive member is reused after being carried out. 5. An electrophotographic photosensitive member having a photoreceptive layer on a support, wherein after an external force is applied to the support in the direction of expanding the area of the support, the surface of the support is cut and / or cut. Alternatively, the electrophotographic photosensitive member is characterized by being polished and then having a light-receiving layer formed on the support.