JPH0667450A - Electrophotographic sensitive body having photoreceptive layer constituted of non-single crystalline silicon having columnar structure region and its production - Google Patents

Abstract

PURPOSE:To provide the electrophotographic sensitive body with which stable images having extremely good quality are obtainable and to provide the electrophotographic sensitive body which does not generate interference fringes on the images even if coherent light, such as semiconductor laser beam, is used without using other remedies for the interference fringes. CONSTITUTION:The photoreceptive layer 4 of the electrophotographic sensitive body consisting of a base body 102 for the electrophotographic sensitive body and the photoreceptive layer 4 which is provided on the base body 102 and is constituted of a non-single crystalline material contg. silicon atoms has regions 110 of columnar structures substantially parallel with the layer thickness direction of the layer 4 at 5 to 500pieces/cm<2> density with plural nuclei 111 existing within the layer 4 as start points.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member constituted by arranging a light receiving layer made of non-single crystal silicon having a columnar structure region on a substrate and a method for manufacturing the same.

[0002]

2. Description of the Related Art Materials constituting a photoconductive layer of an electrophotographic photosensitive member have high sensitivity, high SN ratio, absorption spectrum characteristics suited to the spectrum characteristics of electromagnetic waves to be irradiated, and fast photoresponsiveness. Various characteristics are required, such as having a high dark resistance value, excellent mechanical durability, and being non-polluting to the human body during use.
An electrophotographic photoreceptor using hydrogenated amorphous silicon, which is a material having these various characteristics, for a photoconductive layer is described in, for example, Japanese Patent Application Laid-Open No. 54-86341. An electrophotographic photoreceptor using such amorphous silicon for the photoconductive layer is currently put into practical use.

JP-A-56-62254 and JP-A-57-119356 disclose techniques for improving electrophotographic characteristics by using hydrogenated amorphous silicon containing carbon atoms as an electrophotographic photoreceptor. It is disclosed.

By the way, as a film forming method for forming an amorphous silicon film constituting such an electrophotographic photosensitive member, a sputtering method, a method of decomposing a raw material gas by heat (thermal CVD method), and a method of decomposing a raw material gas by light are used. (Optical CVD method), a method of decomposing a raw material gas by plasma (plasma CVD method), and the like have been proposed. Among these film forming methods, the plasma CVD method is currently widely used, and various apparatuses for it have been proposed. Among such plasma CVD methods, the so-called microwave plasma CVD method using microwave glow discharge decomposition has received industrial attention.

The microwave plasma CVD method has an advantage that a high deposition rate and a high source gas utilization efficiency can be obtained as compared with other methods. An example of a microwave plasma CVD technique that takes advantage of these advantages is described in US Pat. No. 4,504,518. The technique described in this specification is to form a good quality deposited film at a high deposition rate by a microwave plasma CVD method under a low pressure of 0.1 Torr or less.

Further, a technique for improving the utilization efficiency of the raw material gas by the microwave plasma CVD method is disclosed in Japanese Patent Laid-Open No. Sho 60.
No. 186849. The technique disclosed in this publication is generally arranged so that a substrate is arranged so as to surround a means for introducing microwave energy to form an internal chamber (that is, a discharge space) so as to enhance the efficiency of raw material gas utilization. It was done.

Further, in Japanese Patent Application Laid-Open No. 61-283116, an electrode (bias electrode) for controlling plasma potential is provided in the discharge space, and a desired voltage is applied to this bias electrode to ion-impact the deposited film. A technique for improving the characteristics of the deposited film by forming the deposited film while controlling the temperature is disclosed.

A method of manufacturing an electrophotographic photosensitive member based on such microwave plasma CVD technology is disclosed in US Pat.
No. 9,359. The method of manufacturing an electrophotographic photosensitive member described in the specification of US Pat. No. 5,129,359 is carried out, for example, by a deposited film forming apparatus shown in a vertical sectional view of FIG. 12 and a lateral sectional view of FIG. .

In FIGS. 12 and 13, reference numeral 601 denotes a reaction vessel having a vacuum airtight structure. 602 efficiently transmits microwave power into the reaction vessel 601,
Further, it is a microwave introduction dielectric window formed of a material (eg, quartz glass, alumina ceramics, etc.) capable of maintaining vacuum airtightness. Reference numeral 603 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 603 is connected to a microwave power source (not shown) via a stub tuner (not shown) and an isolator (not shown). Reference numeral 604 represents an exhaust pipe. One end of the exhaust pipe opens into the reaction vessel 601, and the other end communicates with an exhaust device (not shown). 60
Reference numeral 6 denotes a discharge space surrounded by the base 605. Power supply 6
Reference numeral 11 denotes a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 612.

The conventional electrophotographic photosensitive member is manufactured by the film forming apparatus having the above-described structure as follows. First, the inside of the reaction container 601 is evacuated through a gas exhaust pipe 604 by a vacuum pump (not shown), and the inside of the reaction container 601 is 1 ×.
Adjust to a pressure below 10 ^-7 Torr. Then the heater
The substrate 605 is heated and held at a temperature of about 200 ° C. to 300 ° C. by 607. Therefore, a raw material gas such as silane gas or hydrogen gas is supplied to the reaction vessel 6 through a gas introducing means (not shown).
It is introduced in 01. Simultaneously with this, a microwave of frequency 2.45 GHz is generated by the microwave power source 608 and introduced into the reaction vessel 601 through the waveguide 603 and the dielectric window 602. Further, a bias power supply 611 connected to the bias electrode 612 in the discharge space 606 applies a bias voltage to the substrate 605 via the bias electrode 612. Thus, in the discharge space 606 surrounded by the base 605, the source gas is excited by the energy of the microwaves and dissociated, and further the electric field between the bias electrode 611 and the base 605 causes the base 60 to steadily flow.
A deposited film is formed on the surface of the substrate 605 while receiving an ion bombardment on the substrate 5. During this film formation, the substrate 605 is attached to the rotary shaft 60.
9 is rotated by a motor 610.

[0011]

According to this method, it is possible to obtain an electrophotographic photosensitive member having practical characteristics and uniformity at a low cost to some extent. However, such conventional electrophotographic photoreceptors still have problems to be improved. That is, especially in the region where the film formation speed is high during film formation, the requirements for optical and electrical characteristics with uniform film quality are satisfied, and the deposited film with few defects is constantly stabilized by the electrophotographic process during image formation. However, it is difficult to obtain a high yield (high yield).

One of these problems is the problem of so-called uneven sensitivity. The sensitivity unevenness does not cause much problem in the case of a line copy (copy of an original consisting of only characters). However, recently, as the number of occasions for copying originals such as photographs such as hoods has increased, and high-speed copying has been demanded, the problem of sensitivity unevenness has become non-negligible. This is a problem that must be particularly emphasized in the case where strict uniformity of image density is required as in color copying, which has been rapidly increasing in demand in recent years.

Another problem is that of resolution. The resolution of a copied image depends on the characteristics of the electrophotographic photosensitive member to be used, as well as on the processes such as development and fixing. In response to these process developments such as the recent finer toner particles, electrophotographic photoreceptors have been required to have a resolution higher than the conventional characteristics.

A method for solving these problems is described in European Patent Publication No. EP 0454456A1. In this publication, a trace amount of fluorine atoms (1 to 95 atom ppm) is contained in a non-single-crystal silicon carbide photoconductive layer, and the content of oxygen atoms is controlled so that the internal strain in the photoconductive layer can be effectively reduced. Described above, a light-receiving member that suppresses the occurrence of "potty", "mottle" and "ghost" in a copy image and also suppresses the occurrence of "spherical protrusions" on the surface of the light-receiving part layer is described. ing. This technique reduces the spherical protrusions on the surface of the light receiving layer of the light receiving member to stabilize and improve the copy image quality. However, it is impossible to completely eliminate the spherical projection when the non-single-crystal silicon carbide photoconductive layer contains a predetermined amount of fluorine atoms and oxygen atoms. By the way, when the inventors of the present invention continuously copied an original containing a halftone at a high speed of 50 sheets / min or more over a long period using the light receiving member, the occurrence of uneven sensitivity was found. A decrease in resolution was observed. It is considered that this is due to the spherical projections on the surface of the light receiving member.

Further, JP-A-62-84965 and JP-A-62-188665 disclose techniques for correcting unevenness of the layer thickness of the photoconductor by polishing the surface of the electrophotographic photoconductor. There is. However, in these publications, there is no mention of the relationship between image defects and surface polishing, and even when high-speed copying is required today, high resolution and high sensitivity can be obtained by controlling layer thickness unevenness. It is very difficult to obtain stable duplicate images.

In particular, in high-speed copying, in order to stably obtain a high-resolution, high-sensitivity copied image, the problem of reflection of light used for exposure must be solved. When an amorphous silicon type photoconductor is used as a photoconductor of a digital copying machine using a semiconductor laser as a light source for exposure, a near infrared ray whose energy is lower than the energy band gap of amorphous silicon. Since the laser is used, the laser light cannot be completely absorbed in the amorphous silicon film. For this reason, laser light is not only absorbed but also partially transmitted or reflected, so that the laser light reflected on the surface of the photoconductor and the interface between the amorphous silicon film and the substrate or the amorphous silicon. The laser lights reflected at the laminated interface of the films interfere with each other,
Interference fringes will occur.

A technique for solving the problem of interference fringes is disclosed in US Pat. No. 4,808,504. The electrophotographic photoreceptor disclosed in the specification is provided with unevenness due to a plurality of spherical trace depressions on the surface of the substrate on which the photosensitive layer is arranged, and the interference fringes generated on the entire photoreceptor are dispersed in the respective trace depressions. To prevent the generation of interference fringes.

The electrophotographic photosensitive member which is designed to prevent the occurrence of interference fringes is evaluated as effective. However, regarding this electrophotographic photosensitive member, in order to provide the surface of the substrate with irregularities due to the plurality of spherical trace depressions, for example, a step of dropping a plurality of rigid true spheres onto the surface of the substrate is required. There is a problem in that the cost of the electrophotographic photosensitive member is greatly increased from the viewpoint of the manufacturing process.

A main object of the present invention is to provide an improved electrophotographic photosensitive member which does not have the above-mentioned problems of sensitivity unevenness and deterioration of resolution in the conventional electrophotographic photosensitive member. Another object of the present invention is a substrate for an electrophotographic photosensitive member, and an electrophotographic photosensitive member containing a silicon atom, which is provided on the substrate, wherein the layer composed of the non-single-crystal material comprises:
Regions having a columnar structure substantially parallel to the layer thickness direction of the layer from the nucleus located inside the layer are 5 / cm ^{2 to} 500 / c.
Another object of the present invention is to provide an electrophotographic photosensitive member characterized by having a density of m ² . Still another object of the present invention is to provide a method for producing the improved electrophotographic photosensitive member by a microwave plasma CVD method with stable yield and at low cost.

[0020]

In order to solve the above-mentioned problems in the conventional electrophotographic photosensitive member and achieve the above object, the present inventors have made a non-single crystal material (amorphous silicon) constituting the photosensitive layer. A region having a columnar structure was positively formed in the inside of the container for study. As a result, the present inventors have summarized, (1) inside a layer formed of a non-single crystal material formed on a substrate, a region having a columnar structure substantially parallel to the layer thickness direction of the layer. When a plurality of columnar structures are arranged, the flow of charges in the direction perpendicular to the layer thickness direction of the layer composed of the non-single crystal material is eliminated, and the resolution is improved. Reflection of incident light from the surface of the photoconductor, reflection from the interface of the stacked deposition films, or reflection from the surface of the substrate is dispersed to reduce unevenness of reflection (that is, reduce the difference in light absorption amount). I got the knowledge that.

The present invention has been completed based on the above findings obtained by the present inventors. The gist of the present invention is as described below. That is, the electrophotographic photosensitive member of the present invention is a substrate for an electrophotographic photosensitive member and an electrophotographic photosensitive member containing a silicon atom, which is provided on the substrate, and is a layer formed of the non-single crystal material. Has a columnar structure region which is substantially parallel to the layer thickness direction of the layer with a nucleus located inside the layer as a starting point at a density of 5 / cm ^{2 to} 500 / cm ^2. It is a thing. The present invention includes a method for manufacturing the electrophotographic photosensitive member having the above structure. The method for producing an electrophotographic photosensitive member of the present invention, a gas containing silicon atoms is introduced into a reaction vessel capable of being depressurized, microwave energy is supplied to the gas, and a discharge space in the reaction vessel is introduced. In a method for producing an electrophotographic photoreceptor, plasma is generated, and a layer composed of a non-single-crystal material containing silicon atoms is formed on a substrate arranged in the reaction vessel to produce an electrophotographic photoreceptor. After forming a part of the layer composed of the non-single-crystal material, on the surface of the partly formed layer, after stably adsorbing the nucleus serving as the starting point for forming the region of the columnar structure,
The further forming a layer formed of a non-single-crystal material, the nucleus region of the 5 / cm ² to 500 / cm ² of substantially parallel-grown columnar structure said layer in the layer thickness direction as a starting point It is characterized by being formed with a density.

According to the electrophotographic photosensitive member of the present invention having the above-mentioned structure, a plurality of regions having a columnar structure, which are substantially parallel to the layer thickness direction of the layer, are arranged inside the layer composed of the non-single crystal material. As a result, the flow of charges in a direction perpendicular to the layer thickness direction of the layer made of the non-single crystal material in the region of the columnar structure is suppressed, whereby image deletion does not occur, and resolution is improved. Further, the region of the columnar structure disperses the reflection of incident light from the surface of the photoconductor, the reflection from the interface of the stacked deposition films, or the reflection from the surface of the substrate. As a result, the unevenness of reflection is reduced (that is, the difference in the amount of absorbed light is reduced), and as a result, the occurrence of uneven sensitivity is reduced.

Further, according to the method of manufacturing an electrophotographic photosensitive member of the present invention, it is possible to manufacture an electrophotographic photosensitive member having the above-mentioned constitution with stable yield and at low cost.

The present inventors have found that most of the current electrophotographic photoreceptors have a plurality of layers having different functions such as a charge generating function, a charge transporting function, a surface protecting function, a charge injection blocking function, etc. laminated on a substrate. Focusing on the fact that it is configured, the cause of uneven sensitivity in such an electrophotographic photosensitive member was examined. As a result, we obtained the following findings. That is, since the plurality of stacked deposition layers have slightly different refractive indexes, the incident light is reflected at the interface between the layers. In addition to this reflection, reflection from the surface of the photoconductor and reflection from the surface of the substrate also occur, and all of these reflected lights interfere with each other due to the difference in their path lengths, and strengthen or cancel each other. Even if the film quality is the same, the path length of the light varies depending on the part of the photoconductor due to the difference in the layer thickness and the incident angle of the light. Depends on This causes uneven reflection, which causes uneven sensitivity of the photoconductor.

Further, the cause of the deterioration of the resolution of the electrophotographic photosensitive member will be examined. As a result, in the electrophotographic photosensitive member, the charges held on the surfaces of the substrate and the photosensitive layer, which are present in the exposed area, disappear during the exposure, but depending on the charges generated in the photosensitive layer during the exposure, the non-exposed portion is exposed. The electric field of the electric charge remaining in the film causes a lateral flow (that is, a flow in a direction perpendicular to the layer thickness direction), which causes a reduction in resolution.

Based on the findings described above, the present inventors
The above-described unevenness in sensitivity and deterioration in resolution are caused by a plurality of columnar structure regions substantially parallel to the layer thickness direction inside the layer formed of the non-single crystal material formed on the substrate. I thought that it could be prevented if they were placed.
The present inventors conducted the following experiments to confirm whether this idea is valid.

Experiment 1 Si powder was sprinkled on the surface of the Al substrate as a nucleus serving as a starting point of the above-mentioned columnar structure region, and then a deposited film (photoreceptive layer) was formed on the surface of the Al substrate to form a photoreceptor. Obtained. The deposited film was observed by SEM. Also, using the obtained photoreceptor,
Images were formed and examined for electrophotographic properties.

As the film forming apparatus, the apparatus shown in FIGS. 7 and 8 was used. The apparatus shown in FIGS. 7 and 8 has the same configuration as the apparatus shown in FIGS. 12 and 13 except for the points described below. That is, the introduction port 213 is provided as a nucleus introduction port serving as a starting point of the columnar structure region,
Further, the apparatus is different from the apparatus shown in FIGS. 12 and 13 in that a mechanism for revolving in addition to the rotation of the base body 205 is provided. 7 and 8, 201 is a reaction container,
Reference numeral 202 denotes a microwave introducing dielectric window formed of alumina ceramics capable of efficiently transmitting microwave power into the reaction vessel 201 and maintaining vacuum tightness, and 203 is a waveguide for transmitting microwave power. . The waveguide 203 is connected to a microwave power source (not shown) via a stub tuner (not shown) and an isolator (not shown). An exhaust pipe 204 has one end opening into the reaction vessel 201 and the other end communicating with an exhaust device (not shown), 20
6 is a discharge space surrounded by the base 205, and 211 is a DC power supply (bias power supply) for applying a DC voltage to the bias electrode 212. 214 is a seal member, 216
Is a revolution plate, and 215 is a motor for rotating the revolution plate 216. The light receiving layer was formed as follows.

That is, a reaction in which a substrate 205 made of Al is arranged.
The inside of the container 201 is evacuated through the exhaust pipe 204, and the reaction volume
1 x 10 inside the vessel 201^-7The pressure was adjusted to Torr. One
Then, the heater 207 is energized and the substrate 205 is heated to 250 ° C.
Heated and held at temperature. Base 205 by motor-210
The substrate 205 is rotated by the motor 215 while rotating.
Was revolved around. Here, Si powder having an average particle diameter of 10 μm
Pressure 2 × 10^FourAr gas with Pa and flow rate of 1000 sccm
Reaction volume through the inlet 213 for 2 minutes.
Introduced into the container 201, Si powder on the surface of the substrate 205
Sprayed. Next, Si is introduced through a gas introducing means (not shown).
H_FourGas, He gas, CH_FourGas, SiF _FourEach gas
350sccm, 100sccm, 50sccm,
Introduced into the reaction vessel 201 at a flow rate of 1 sccm, the reaction
The pressure inside the container 201 was adjusted to 4.0 mTorr. This
By the way, the microwave power source 208 causes the frequency
2.45 GHz, 1000 W microwaves waveguide 20
It was introduced into the reaction vessel 201 via At the same time
Applying a bias voltage of 70V to the bias electrode 212
It was The discharge space 206 thus surrounded by the substrate 205
In the above, the above-mentioned film forming source gas is microwave energy.
It is excited by a gear and dissociated, and the bias electrode 212 and the
Do not constantly receive ion bombardment by the electric field between the body 205
Amorph containing hydrogen and fluorine on the substrate 205
The silicon carbide film (a-SiC: H: F) is 20 μm thick
Formed only by. Amorphous silicon carbide thus obtained
The element film is cut out from a part of the Al substrate 205 and observed by SEM.
A sample was prepared for SEM observation. Where it did
The free surface of the photoreceptor layer from the Si nuclei on the surface of the substrate 205.
There are multiple cracks on the surface, and the film quality is poor.
It was confirmed to be a thing. Also, on the surface of the light receiving layer
Had many protrusions, the polishing apparatus shown in FIG.
Was used to polish the protrusions. Polishing device shown in FIG.
Mount the electrophotographic photoreceptor on the shaft and rotate it.
A polishing tape is applied to the surface of the rotating electrophotographic photoconductor.
This is a form in which pressure is applied and polishing is performed. Polishing is as follows
I went like this.

First, the polishing unit 302 in the main body 301 of the polishing apparatus was raised and fixed by the clamp 303, and then the electrophotographic photosensitive member 305 was combined with the support 304 and fixed to the shaft 306. Then clamp 303
Is loosened, the polishing unit 302 is lowered, and the polishing tape 308 is attached to the electrophotographic photosensitive member 3 by the pressing roller-307.
It was crimped to 05. As the polishing tape 308, a polyester film coated with silicon carbide powder having an average particle diameter of 8 μm was used. The pressing roller 307 used had a surface coated with urethane rubber (JIS hardness: 80). At this time, the spring 309 for pressure contact is adjusted to adjust the pressure contact roller-3.
07 via the polishing tape 308 to the electrophotographic photoreceptor 305.
The pressure to be pressure-bonded to was set to a linear pressure of 40 g / cm, and the contact width (hereinafter abbreviated as "nip width") was set to 0.5 mm.

Next, the motors 310 and 311 whose rotation speeds are variable were rotated to perform polishing. The polishing tape 308 was fed at a feed rate of 10 mm / min, and the electrophotographic photosensitive member 305 as a member to be polished was rotated at a speed of 300 mm / sec, and polishing was performed for 5 minutes.

The photoconductor thus obtained was mounted on a copying machine, which was a Canon NP9330 copying machine modified for experiments, to form an image. Although the original could be copied in the early stage of copying, the condition of the copied image suddenly deteriorated as the copying was repeated, and the characters on the original could not be recognized. The characteristics of the photoconductor prepared here are very poor because the adsorption of Si nuclei on the Al substrate is not stable, which causes cracks in the deposited film formed on the Si nuclei. Probably because it happened.

Experiment 2 In the experiment, in consideration of the results obtained in Experiment 1, Si
The dispersion of the nuclei on the Al substrate was performed after forming a slight deposited film on the Al substrate. That is, the step of spraying Si nuclei on the Al substrate in Experiment 1 was performed in the same manner as in Experiment 1 except that a slight deposition film was formed on the Al substrate. Specifically, it carried out as follows. Reaction vessel 201
After evacuating the inside under reduced pressure, the Al substrate 205 was heated and held at a temperature of 250 ° C. While rotating the base body 205 around its axis,
SiH ₄ gas, He gas, CH ₄ gas, and SiF ₄ gas are used as film forming source gases at 350 sccm and 100 sc, respectively.
cm, 50 sccm, 1 sccm at the reaction vessel 20
1, and the inside of the reaction vessel 201 is 4.0 mTorr.
The pressure was adjusted to. At such a place, a microwave having a frequency of 2.45 GHz and 1000 W was introduced into the reaction vessel 201 through the waveguide 203 by the microwave power source 208. At the same time, a bias voltage of 70 V was applied to the bias electrode 212. This operation is carried out by performing an amorphous silicon carbide film (a-Si) containing hydrogen and fluorine on the substrate 205.
After C: H: F) was continuously formed to a thickness of 5 μm, the microwave power source 205 was turned off to stop the supply of the raw material gas. Next, Si having an average particle size of 10 μm
The powder is A at a pressure of 2 × 10 ⁴ Pa and a flow rate of 1000 sccm.
It was introduced into the reaction vessel 201 together with the r gas through the introduction port 213 for 2 minutes, and Si powder was sprinkled on the amorphous silicon carbide film (a-SiC: H: F) having a thickness of 5 μm. After that, the above-mentioned source gas is again introduced into the reaction vessel 201, and microwave power is applied and the bias electrode 2 is supplied.
The above-described film forming operation of applying a bias voltage to the amorphous silicon carbide film (a) having a thickness of 15 μm (a) is repeated.
-SiC: H: F) was laminated. Thus, an electrophotographic photosensitive member was obtained. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Experiment 1. As a result of SEM observation, the initially formed amorphous silicon carbide film (a-SiC: H: 5 μm thick) was formed.
It was observed that columnar regions, which are apparently parallel to each other in the film thickness direction, were formed from the Si nuclei scattered on F). These columnar regions were not generated from all Si nuclei, and some Si nuclei did not generate columnar regions. After the surface of the photoconductor was polished in the same manner as in Experiment 1 using the polishing apparatus shown in FIG. 9, image formation was performed in the same manner as in Experiment 1. As a result, an image significantly superior to the copy image obtained in Experiment 1 was obtained, but the number of copies was 5
A drastic reduction in the number of copied images (particularly a decrease in resolution and an increase in white spots) was observed after the number of sheets exceeded 10,000. In the photoconductor after copying 50,000 sheets, in order to observe how the deposited film constituting the photoreceptive layer of the photoconductor was changed, the deposited film was cut out from a part of the Al substrate and used for SEM observation. A sample was prepared and SEM observation was performed. As a result, the initially formed amorphous silicon carbide film (a-Si) having a thickness of 5 μm was formed.
C: H: F) has columnar regions formed apparently parallel to each other in the film thickness direction from the Si nuclei scattered, but there is another rough region where no deposited film exists near the Si nuclei. It was confirmed that it was doing. It is considered that the occurrence of this rough area caused a decrease in resolution and an increase in white spots. It is considered that the rough region is caused by the fact that some Si nuclei scattered on the deposited film did not adsorb to the deposited film in a stable state.

Experiment 3 In this experiment, the Si powder to be the core was precharged so that the Si nucleus could be adsorbed on the amorphous silicon carbide film (a-SiC: H: F) in a stable state.
The Si nuclei were adsorbed on the amorphous silicon carbide film (a-SiC: H: F) by utilizing the electric fields of both the Si powder and the substrate. The film forming operation in this experiment was performed by using a modified deposition film forming apparatus shown in FIGS. 7 and 8. Specifically, a value of 0.
Arrange a charger composed of 5 mm diameter tungsten wire,
By applying a DC voltage to this charger, corona discharge was generated to charge the Si powder. In addition to this, a DC bias voltage can be applied to the substrate 205. The film formation in this experiment was performed by spraying Si nuclei in Experiment 2 by charging Si particles with a charger and
The same procedure as in Experiment 2 was performed except that a bias voltage was applied to the substrate 205 and the electric field generated between the two was used. Specifically, it carried out as follows. After evacuating the inside of the reaction vessel 201 under reduced pressure, the Al substrate 205 is heated to 250 ° C.
It was heated and held at the temperature of. The Al substrate 205 is rotated and revolved, and SiH ₄ gas, He gas, CH ₄ gas, SiF are used.
_{The four} source gases for film formation were 350 sccm,
It was introduced into the reaction container 201 at a flow rate of 100 sccm, 50 sccm, and 1 sccm, and the inside of the reaction container 201 was set to 4.0.
The pressure was adjusted to mTorr. In such a place, the microwave power source 208 is used to generate a frequency of 2.45 GHz, 100
The reaction vessel 20 receives 0 W microwaves through the waveguide 203.
Introduced in 1. At the same time, the bias electrode 212 is
A bias voltage of 0V was applied. This film forming process is
After the amorphous silicon carbide film (a-SiC: H: F) containing hydrogen and fluorine having a thickness of 5 μm is formed on the substrate 205, the microwave power source 205 is turned off, and the film forming source gas is formed. Supply was stopped. Next, a DC voltage of 5 kV was applied to a charger provided in the vicinity of the inlet 213 to generate corona discharge to charge the Si powder, and a DC voltage of -100 V was applied to the Al substrate 205. Si powder pressure 2 × 10 ⁴ Pa, flow rate 1
2 from the inlet 213 together with Ar gas of 000 sccm
It was introduced into the reaction vessel 201 over a period of time. Al base 2
After stopping the application of the DC voltage to 05, the above-mentioned film forming raw material gas is introduced into the reaction vessel 201, and the microwave power is applied and the bias voltage is applied to the bias electrode 212. Repeat the operation to a thickness of 15μ
m amorphous silicon carbide film (a-SiC: H: F) was laminated. Thus, an electrophotographic photosensitive member was obtained. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Experiment 2.
As a result of SEM observation, columnar regions are apparently parallel to the thickness direction of the deposited film from all Si nuclei scattered on the initially formed amorphous silicon carbide film (a-SiC: H: F) having a thickness of 5 μm. It was observed to have formed. After polishing the surface of the photoconductor in the same manner as in Experiment 2 using the polishing apparatus shown in FIG. 9, image formation was performed in the same manner as in Experiment 2. As a result, an image superior to the copied image obtained in Experiment 2 was obtained, and no deterioration of the copied image was observed even after 100,000 copies were made. The reason why a very excellent copied image was obtained here is that the Si nuclei are adsorbed on the deposited film in a stable state, and the columnar regions are apparently parallel to each other in the film thickness direction from the Si nuclei as a starting point. Is considered to have been formed.

Experiment 4 In the present experiment, in view of the results obtained in Experiment 3, various densities of the columnar structure regions formed in the deposited film were changed to study to obtain a preferable density. In this experiment,
A plurality of types of electrophotographic photoconductors having the structure shown in 1 were produced. In FIG. 1, reference numeral 102 is a substrate, and 104 is a layer having a function as a photoconductive layer composed of a non-single crystal (amorphous, microcrystalline, or polycrystalline) having silicon atoms as a matrix. 103 is a charge injection blocking layer, and 105 is a surface protective layer. 110 indicates a columnar structure, and 111 indicates a nucleus of the columnar structure. In each case, the deposited film was formed using the apparatus used in Experiment 3 as follows. Reaction vessel 2
After evacuating the interior of 01 under reduced pressure, the Al substrate 205 was heated and maintained at a temperature of 250 ° C. The Al substrate 205 is rotated and revolved, and the film forming raw material gases of SiH ₄ gas, He gas, B ₂ H ₆ gas and NO gas are respectively 350 sccm, 10
It was introduced into the reaction vessel 201 at a flow rate of 00 ppm and 10 sccm, and the pressure inside the reaction vessel 201 was adjusted to 4.0 mTorr. In such a place, the microwave power source 208
Then, a microwave having a frequency of 2.45 GHz and 1000 W was introduced into the reaction vessel 201 through the waveguide 203. At the same time, a bias voltage of 70 V was applied to the bias electrode 212. Thus, the charge injection blocking layer 103 was formed. This film forming process is continued to form 3 μ on the Al substrate 205.
An m-thick a-Si: H: N: B film was formed. Then B ₂
The supply of H ₆ gas and NO gas was stopped, and CH ₄ and SiF ₄ gas were introduced into the reaction vessel 201 at a flow rate of 50 sccm and 1 sccm, respectively, in addition to the above-mentioned SiH ₄ gas and He gas, and 5 μm of a-SiC: After forming the H: F film, the microwave power supply 205 was turned off to stop the supply of the film forming source gas. In each case, the charging device provided near the inlet 213 is then
A DC voltage of kV is applied to generate a corona discharge to charge the Si powder, and a pressure of 2 × 10 ⁴ Pa is applied to the Si powder in a state where a DC voltage of −100 V is applied to the Al substrate 205.
The Ar gas having a flow rate of 800 sccm was introduced into the reaction container 201 through the introduction port 213 for different introduction times, that is, 10 seconds to 5 minutes. After the application of the DC voltage to the Al substrate 205 is stopped, the above-mentioned film forming material gas is introduced into the reaction vessel 201, and the microwave power is applied and the bias voltage is applied to the bias electrode 212. By repeating the film forming operation, a-SiC having a thickness of 15 μm:
H: F was laminated. Thus, the photoconductive layer 104 was formed. Next, under the film forming conditions shown in Table 1, 0.5 μm thick aS
A surface layer 105 made of an iC: H film was formed. 10 above
The conditions for forming the three layers, the 104 layers, and the 105 layers are summarized in Table 1. The surface of each of the obtained photoconductors was polished in the same manner as in Experiment 2 using the polishing apparatus shown in FIG. Each of the obtained photoconductors is manufactured by Canon Inc.
The NP9330 copying machine manufactured by NP9330 was mounted on a copying machine modified for experiments, and image formation and evaluation were performed. The obtained evaluation results are summarized in Table 2. Each evaluation item shown in Table 2 was evaluated according to the following evaluation criteria.

(1) Sensitivity unevenness: An image sample obtained when an original halftone original was placed on an original table and copied was observed to evaluate unevenness of light and shade.

The surface of the photoconductor is divided into three parts in the axial direction and three parts in the circumferential direction.
The image was divided into nine areas so as to correspond to the equally divided surface, and the average of image densities in the respective areas was compared and evaluated. ◎ ・ ・ ・ ・ No difference in image density in the nine areas. ○: There is a slight difference in image density in the areas 1 and 2. Δ: The image density is different over the entire surface, but the degree is slight. × ... There is a difference in image density over the entire surface that causes a problem.

(2) Resolution: An image sample obtained by copying an ordinary document consisting of characters all over a white background on a platen was observed to evaluate whether any characters on the image could be reproduced without being crushed.

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. ◎ ・ ・ ・ ・ Good. ○ ・ ・ ・ ・ Partially crushed. △ ・ ・ ・ ・ Although there are many crushes, it can be recognized as characters. × ・ ・ ・ ・ Some characters cannot be recognized.

(3) Interference fringe: An image sample obtained by copying an entire halftone original document and an entire black original document on the original plate is observed, and striped unevenness of light and shade corresponding to the uneven thickness of the photoconductor is observed. Was evaluated. ⊚: No interference fringes are observed in any of the images. ○ ・ ・ ・ ・ When observed in detail, slight interference fringes are observed in some of the halftone images. B: No interference fringes are observed on the black image in the halftone image. × ... Interference fringes are conspicuous on any image.

(4) Roughness: The original half-tone original and the normal original consisting of full-faced characters on a white background are alternately placed on the original plate and the image sample obtained by copying is observed to determine the degree of roughness. evaluated. ◎ ・ ・ ・ ・ No roughness is observed in any of the images. ○ .... There is a part of the halftone image that is slightly shaky. △ ・ ・ ・ ・ The halftone image has a noticeable roughness, but it has no effect on the original with full-scale characters. × ・ ・ ・ ・ Some characters cannot be recognized.

[0042]

[Table 1]

[0043]

[Table 2] As is clear from the results shown in Table 2, when the columnar structure was formed in the deposited film at a density in the range of 5 pieces / cm ^{2 to} 500 pieces / cm ² , sensitivity unevenness, resolution, interference fringes, and roughness were observed. It is understood that each gives an electrophotographic photoreceptor that exhibits very good properties.

From the results of Experiments 1 to 4 described above, the following was found.

After forming a layer made of a non-single-crystal material on a substrate, a nucleus serving as a starting point for growing on the surface of the layer to form a columnar structure region is adsorbed in a stable state, A layer composed of a single crystal material is further formed, and the region of the columnar structure which is substantially parallel to the layer thickness direction of the layer is 5 / cm ^{2 to} 5
The light receiving member formed with a density of 00 pieces / cm ² has sensitivity unevenness, resolution, interference fringes, and roughness,
Shows very good properties.

The electrophotographic photosensitive member of the present invention comprises an electrophotographic photosensitive member comprising a substrate for the electrophotographic photosensitive member and a photoreceptive layer provided on the substrate and made of a non-single crystal material containing silicon atoms. a photoreceptor, the light receiving layer, 5 / cm ² to 500 regions of substantially parallel columnar structure said layer in the layer thickness direction a plurality of nuclei located within the layer as a starting point / C
It is characterized by having a density of m ² .

In the method for producing an electrophotographic photosensitive member of the present invention, a gas containing silicon atoms is introduced into a reaction vessel that can be depressurized, and microwave energy is supplied to the gas to cause discharge in the reaction vessel. A method for producing an electrophotographic photosensitive member by causing a plasma to be generated in a space, and forming a photoreceptive layer composed of a non-single-crystal material containing silicon atoms on a substrate arranged in the reaction container. , (I) a part of the light-receiving layer is formed, and (ii) a plurality of nuclei serving as starting points for forming a region having a columnar structure are stably attached to the surface of the formed layer, (iii) The step (i) is performed on the surface of the layer on which the plurality of nuclei are attached, and 5 regions / cm of a columnar structure region that is substantially parallel to the growth direction of the layer starting from the plurality of nuclei are formed.
² to 500 / cm as a feature origin that formed in the ^second density region of substantially parallel columnar structures the layer growth direction 5 pieces / cm ² to be formed at a density of 500 pieces / cm ² It is characterized by.

The electrophotographic photosensitive member of the present invention will be described with reference to FIG. FIG. 1 is a diagram schematically showing a cross section of the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 102 denotes a substrate, 10
Reference numeral 4 is a layer having a function as a photoconductive layer which is composed of a non-single crystal (amorphous, microcrystalline, or polycrystalline) having silicon atoms as a matrix. Reference numeral 110 denotes a columnar structure region, and 111 denotes a columnar structure nucleus. 103 indicates a charge injection blocking layer, and 105 indicates a surface protective layer. The charge injection blocking layer 103 and the surface protective layer 105 are not necessarily required and can be appropriately provided according to the characteristics of the electrophotographic photosensitive member to be obtained.

The electrophotographic photosensitive member of the present invention is excellent in image characteristics without the problems such as the unevenness in sensitivity and the deterioration of resolution which are seen in conventional photosensitive members. This point will be described with reference to FIG. FIG. 6 shows that when light is incident on the photoconductive layer 104 made of a non-single crystal having silicon atoms as a matrix,
It is a figure showing how light advances. In FIG. 6, the columnar structure region 110 and the columnar structure nucleus 111 form an interface in the non-single-crystal layer 104. Since the refractive index in the region 110 having the columnar structure is different from the refractive index in the region of the non-single crystal layer 104, the incident light I ₁ is repeatedly reflected at the interface between the two, and the reflected light of R _{1 to} R ₆ , for example, is reflected. Occur. Since the reflected lights R _{1 to} R ₆ have different path lengths, they interfere with each other and strengthen or cancel each other, but the presence of the columnar region 110 increases the chance of light reflection. As a result, the interference between the reflected lights is dispersed, and the lights do not intensify or cancel each other at a specific position.

Further, in the electrophotographic photosensitive member of the present invention, due to the existence of the columnar structure region 110, the lateral flow caused by the electric charge generated in the photoconductive layer at the time of exposure being attracted by the electric field of the electric charge remaining in the non-exposed portion is caused. Can be stopped.

In the electrophotographic photosensitive member of the present invention, FIG.
As shown in, a non-single crystal 104 having a silicon atom as a base is
For example, a plurality of layers such as 104 (A), 104 (B), and 104 (C) may be laminated and configured. Also,
As shown in FIG. 3, each of the 103 layer and the 105 layer may be formed by laminating a plurality of different layers. 10
In addition to the above, each of the 3 layer and the 105 layer has a function such as a light absorption layer for preventing reflection of light from the substrate, a charge transport layer for transporting charges, or a charge generation layer for generating charges. You can In a preferred embodiment,
103 layer as a light absorption layer and / or a charge injection blocking layer,
The layer 105 is a charge generation layer and / or a surface layer. 103
The layers 105 and 105 are each composed of a silicon atom as a base, carbon, germanium, nitrogen, oxygen, hydrogen, fluorine, boron,
It is composed of one selected from non-single crystal materials including amorphous materials and polycrystalline materials containing one or more selected from phosphorus. The shape of the columnar structure region is preferably a circle, an ellipse, or a shape close to a shape in which they are overlapped, as a shape when cut horizontally with respect to the surface of the photoconductor. The cross-sectional shape when cut perpendicularly to the surface of the photoreceptor is preferably rectangular, triangular, trapezoidal, or a combination thereof.

The size of the columnar structure region is preferably 1 μm or more and 300 μm or less, more preferably 5 μm or more and 100 μm or less in diameter (or major axis) when viewed from the surface side of the photoreceptor. If it is smaller than this, the effect of the present invention is not seen, while if it is larger, desired electrophotographic characteristics are not exhibited. The density of the columnar structure is 5 μm or more in diameter (or major axis) and 100 μm
The following are 5 or more and 500 or less, preferably 10 or more and 300 or less, and optimally 10 or more and 100 or less per cm ² . If the density of the columnar structure is smaller than these ranges, the effect of the present invention will not be obtained, while if it is large, the image characteristics such as roughness of the image will be deteriorated.

Any nucleus may be used as a starting point for generating a columnar structure region as long as it is a fine particle, but a crystalline powder such as a single crystal or a polycrystal containing a silicon atom is particularly preferable. However, non-single crystal powders can also be used.

The origin of generation of the columnar structure region is 1 μm or more, more preferably 3 μm upward in the layer thickness direction from the lower interface position of the light receiving layer forming the columnar structure region.
It is set to be at least μm, optimally at 5 μm or more.

As a preferable method of scattering and attaching the nuclei, which are the starting points for generating the columnar structure regions, onto the deposited film, after charging the nuclei particles, a rare gas such as helium, neon or argon, Hydrogen gas or silane gas, methane gas, and other source gases are introduced into the reaction vessel and sprayed onto the deposited film, and the particles serving as nuclei are deposited on the deposited film by using the electric fields of both the substrate and the charged powder. The method of attaching is mentioned.

As a method of charging the core particles,
A desirable method is one in which electric charge is applied by means such as corona discharge, spark discharge or glow discharge.
When the corona discharge is used, a corona discharge is generated by applying a DC voltage of 4 to 8 kV to a charger composed of a charging wire such as a stainless wire or a tungsten wire having a diameter of about 0.1 to 0.5 mm. The flow rate and blowing pressure of the gas introduced into the reaction vessel together with the core particles vary depending on the size and amount of the powder particles, the area of the target membrane, the spraying time, etc. Flow rate of the gas is 100 scc
It is preferable that the pressure is 10 ⁴ Pa to 10 ⁵ Pa and the pressure is m to 100 slm. When the adhesion is performed using an electric field between the charged particles and the substrate, the electric field strength is 1 V / cm to 1
It is preferably set to 00 V / cm.

The non-single-crystal layer 104 containing silicon atoms in the present invention contains 2.0 atom% of carbon atoms with respect to silicon atoms.
As described above, it is preferable that the content is 25 atomic% or less, and the content of fluorine atom is 2.0 ppm or more and 90 ppm or less with respect to the silicon atom.

The raw material gas used for forming the non-single-crystal layer 104 containing silicon atoms is silane (disilane) or the like, and methane (C
H ₄ ), ethane (C ₂ H ₅ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), hydrocarbons such as propane (C ₃ H ₈ ), or a mixed gas thereof. Further, a gas containing simultaneously silicon atoms and carbon atoms such as tetramethylsilane (Si (CH ₃ ) ₄ ) is also effective as a raw material gas.

As a gas used for adding a fluorine atom into the non-single-crystal layer 104 containing a silicon atom, a fluoride such as silicon tetrafluoride (SiF ₄ ) or (CF ₄ ) or a mixed gas thereof is used. Is mentioned.

When carbon is contained in the 104 layer, it is 10
It is preferable to contain 2 at% or more and 20 at% or less, and optimally 3 at% or more and 10 at% or less with respect to the amount of silicon atoms in the four layers.

When the 104 layer contains a fluorine atom,
2ppm or more with respect to the amount of silicon atoms in the 104 layer, 90
It is desirable that the content be less than or equal to ppm, and optimally, more than or equal to 3 ppm and less than or equal to 80 ppm.

The thickness of 104 layers is 30% or more, 100% or less, and more preferably 50% of the total thickness of the deposited film on the substrate.
As described above, the range of 100% or less is preferable.

In the present invention, the microwave plasma CV is used.
When the 104 layers are formed by the D method, it is effective to form the layers with a bias voltage applied in the discharge space, and it is preferable that an electric field be applied at least in the direction in which the cations collide with the substrate. When the bias voltage is not applied at all, the effect of the present invention is remarkably reduced, but when the bias voltage is applied, the voltage of the DC component is 1 V or more, 5 or more.
It is desirable that the voltage is 00 V or less, preferably 5 V or more and 100 V or less.

As the method for forming the 103 layer and the 105 layer, vacuum vapor deposition, sputtering, thermal CVD, plasma CVD or the like can be appropriately selected and used.

The base material is, for example, stainless steel,
Al, Cr, Mo, Au, In, Nb, Te, V, T
Metals such as i, Pt, Pd, and Fe, alloys of these, synthetic resins such as polycarbonate whose surface is conductively treated, glass, ceramics, paper, and the like can be used.

The substrate may have any shape, but a cylindrical one is particularly suitable for the method of forming a deposited film in which a plurality of substrates surround the discharge space. There is no particular limitation on the size of the substrate, but in practice, the diameter is 20 mm or more, 500 mm
Hereafter, the length is preferably 10 mm or more and 1000 mm or less.

In the deposited film forming method having a structure in which the discharge space is surrounded by a plurality of substrates, the distance between the substrates is 1 mm or more and 50
mm or less is preferable. The number of bases may be any as long as a discharge space can be formed, but 3 or more, and more preferably 4 or more are suitable.

In the present invention, the layer made of a non-single crystal containing silicon atoms is particularly preferably amorphous silicon containing hydrogen or an amorphous material mainly containing silicon containing other atoms.

In the electrophotographic photoreceptor of the present invention, the total thickness of the deposited film deposited on the substrate is 5 μm or more and 100 μm or less, more preferably 10 μm or more and 70 μm or less, and most preferably 15 μm or more and 50 μm or less. desirable.

A plasma CVD method is particularly preferable as a method of forming a deposited film constituting an electrophotographic photosensitive member. And
In the case of plasma CVD method, DC discharge method, RF discharge method,
A microwave discharge method or the like can be used, but a discharge method using microwaves is particularly preferable.

When using microwaves, in particular, as shown in FIGS. 7 and 8, a base is provided so as to surround the discharge space, and microwaves are introduced into the discharge space by a waveguide from at least one end side of the base. The configuration method is desirable. At this time, the material of the dielectric window for introducing the microwave is alumina (Al ₂ O ₃ ), aluminum nitride (AlN),
Materials with low microwave loss such as boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon and polystyrene are usually used.

In the present invention, the pressure of the discharge space during the formation of the deposited film is preferably 100 mtorr or more and 5 torr or less, preferably 200 mtorr or more and 2 torr or less when DC power or RF power is used as the discharge power. When microwaves are used as the discharge power, a pressure of 0.5 mtorr or more and 100 mtorr or less, preferably 1 mtorr or more and 20 mtorr or less is desirable in view of the stability of discharge and the uniformity of the deposited film.

The substrate temperature at the time of forming the deposited film can be in the range of 100 ° C. or higher and 500 ° C. or lower, but particularly 150 ° C. or higher and 450 ° C. or lower, preferably 200 ° C. or higher and 400 ° C.
The optimum temperature is 230 ° C or higher and 350 ° C or lower.

The heating method of the substrate may be any heating element having a vacuum specification, and more specifically, electric resistance heating elements such as a wound heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, an infrared lamp. Examples of the heat radiation lamp include a heating element, a heating element using a heat exchange means with a liquid, a gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a method of providing a heating-dedicated container separately from the reaction container and heating and then transporting the substrate into the reaction container in a vacuum can also be used. Further, it is possible to control the substrate temperature by the microwave itself used for discharging (for example, by changing the intensity as necessary). Any of the above means can be used alone or in combination.

The discharge power during formation of the deposited film is 20 W or more and 2 kW or less, preferably 50 W or more and 1 kW or less when DC power or RF power is used as discharge power, and 100 W or more when used as microwave discharge power. 10 kW or less, preferably 500 W or more and 2 kW or less.

In the polishing process used in the present invention, an abrasive is used.
The effect is particularly great when the coated abrasive tape is used. Good
A suitable abrasive is silica (SiO₂), Alumina (A
l₂O ₃), Iron oxide (Fe₂O₃), Silicon carbide (SiC),
Carbon nitride (C₃N_Four), Fine powder of cerium oxide (CeO), etc.
There is an end. The average particle size of the abrasive is small
If it is too much, the polishing rate will decrease and the polishing time will increase substantially.
If it is too large, the polishing speed will be very high,
It also affects the parts other than the columnar structure. Concrete
Specifically, the thickness is preferably 1 μm or more and 20 μm or less.

The base material to which the fine powder of the abrasive is applied may be any film-shaped base material, such as polyamide, polyester, polyurethane, polyurea, polyolefin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyfluoride. Examples thereof include organic polymers such as ethylene oxide, polyacrylonitrile, polyvinyl alcohol, and polyvinylidene cyanide; metal thin films such as stainless steel; and paper. Among them, the organic polymer film is most suitable because of its weight and strength, inexpensive mass production, and resistance to environmental changes.

The pressure roller used in the polishing apparatus may be made of any material. However, when the pressure roller is stiffer than necessary, scratches due to the polishing tape are generated on the electrophotographic photosensitive member, which is the member to be polished, and If it is softer than necessary, the pressure contact pressure will not be transmitted to the polishing tape and the polishing rate will be substantially reduced. Therefore, it is desirable to coat the surface with a material such as silicon rubber or urethane. Furthermore,
A roller capable of providing an appropriate amount of nip width between the polishing tape and the electrophotographic photosensitive member according to the contact pressure is preferable. At this time, the nip width is 0.01 mm
It is preferably 3 mm or less. The contact pressure is preferably 10 g / cm or more and 500 g / cm or less as a linear pressure.

Instead of the pressure contact roller, a convex pressure contact member may be used.

A method of using an abrasive dispersed in a solvent is also effective. At this time, silica (SiO
₂ ), alumina (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), silicon carbide (SiC), carbon nitride (C ₃ N ₄ ), cerium oxide (CeO), and other fine powders. As for the average particle diameter of the abrasive, if the average particle diameter is too small, the polishing rate decreases, and the polishing time is substantially increased. If the average particle diameter is too large, the polishing rate becomes very high. It also affects the part. Specifically, the thickness is preferably 1 μm or more and 20 μm or less.

As the solvent, any liquid may be used as long as it can disperse the abrasive, but water is particularly preferable from the viewpoint of easy handling. The concentration of the abrasive is preferably 5% or more and 50% or less in terms of volume ratio in order to optimize the fluidity and the polishing rate. The member for holding the solution in which the abrasive is dispersed may be any member as long as it can hold the solvent, but in practice, a fibrous material such as cloth or paper is particularly preferable.

The holding member may have any shape,
Examples thereof include those having a curved surface that encloses a roller-shaped, flat-shaped, or cylindrical electrophotographic photosensitive member. At this time, the nip width is preferably 0.1 mm or more and 100 mm or less. Pressing pressure is 1g / cm ² or more, 1000g
/ Cm ² or less is desirable.

In any of the polishing methods, the rotation speed of the electrophotographic photosensitive member as the material to be polished is 1 mm / sec or more, 1000
mm / sec or less is desirable. Polishing time is 10 seconds or more,
60 minutes or less, preferably 1 minute or more and 10 minutes or less is suitable for carrying out the present invention.

It is desirable to observe the sectional structure of the deposited film by using an optical microscope, an electron microscope or the like after polishing the cut surface of the photoconductor as necessary by buffing or the like.

[0086]

EXAMPLES The electrophotographic photoreceptor and the method for producing the same according to the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Using the film forming apparatus used in Experiment 4, plural kinds of amorphous silicon type electrophotographic photoconductors having a three-layer structure shown in FIG. 1 were produced. Each electrophotographic photosensitive member was produced by the same method as in Experiment 4, except that the formation conditions of the photoconductive layer 104 were partially changed as described below, that is, in each case, when forming 104 layers. Although only one point is shown in Table 1 for the CH ₄ flow rate of the above, various changes were made to obtain an average particle diameter of 10 μm during the Si powder adhesion step.
m Si powder, pressure 2.5 × 10 ⁴ Pa, flow rate 1000
An electrophotographic photosensitive member was produced in the same manner as in Experiment 4 except that it was introduced into the reaction container 201 through the introduction port 213 for 2 minutes together with Ar gas of sccm.

Each of the electrophotographic photosensitive members thus obtained was evaluated in the same manner as in Experiment 4. Table 3 shows the obtained evaluation results. The evaluation criteria of "white spot" in Table 3 are as follows.

White spot: Evaluation was performed by the number of white spots within the same area of the image sample obtained when a black original was placed on the original plate and copied. ◎ ・ ・ ・ ・ Good. ○ ・ ・ ・ ・ There are some small white spots. △ ・ ・ ・ ・ There are white dots on the entire surface, but there is no problem in recognizing the characters. × ・ ・ ・ ・ There are many white dots as the characters are hard to read.

[0090]

[Table 3] As is clear from the results shown in Table 3, the electrophotographic photosensitive member of the present invention is particularly effective when the 104 layer contains carbon atoms in the range of 2.0 atom% to 25 atom%. Recognize.

[0091]Example 2 Using the film deposition system used in Experiment 4, it is shown in FIG.
Amorphous silicon-based electrophotographic photoreceptor with a three-layer structure
Several types were formed. Each electrophotographic photoreceptor has a photoconductive layer
Other than partially changing the formation conditions of 104 as described below
Was made in the same way as in Experiment 4, ie
In each case, SiF when forming 104 layers_FourFlow of
In Table 1, only one point is shown,
The average particle size during the Si powder attachment step 10
Pressure of 2.5 × 10 μm Si powder ^FourPa, flow rate 100
2 minutes from inlet 213 with 0 sccm Ar gas
Experiment 4 except that it was introduced into the reaction vessel 201 over
An electrophotographic photosensitive member was prepared in the same manner as described above. This
Image formation using the electrophotographic photoreceptor obtained in this way
Was performed in Experiment 4 for sensitivity unevenness and resolution.
Evaluation was carried out in the same manner as. Table 4 shows the obtained evaluation results.
Show. As can be understood from Table 4, the electrophotographic photosensitive material of the present invention
The body has fluorine atoms in the 104 layers from 2.0 ppm to 90 p
It is particularly effective when contained in the range of pm. Incidentally, this
The tendency is the same when the carbon content in the 104 layer is changed.
It was

[0092]

[Table 4] Example 3 Using the film forming apparatus used in Experiment 4, a plurality of types of amorphous silicon-based electrophotographic photosensitive members having a three-layer structure shown in FIG. 4 were prepared. The conditions for forming the three layers are as shown in Table 5. In this example, a photosensitive member was manufactured by changing the layer thicknesses of the 104 (B) layer and the 105 layer, and the obtained photosensitive members were evaluated. Here, the total thickness of the deposited film forming the photoconductor is 20 μm, 30 μm, 40 μm,
Considered as. As for the conditions for forming the 104 (A) layer, CH ₄ gas and S were added so that carbon atoms were contained at 14 atom% and fluorine atoms were contained at 70 ppm with respect to silicon atoms.
iF ₆ gas was introduced into the reaction vessel. Regarding the conditions for forming the 104 (B) layer, carbon atoms are contained in an amount of 7 atom% and fluorine atoms are contained in an amount of 30 ppm with respect to silicon atoms.
₄ gas and SiF ₆ gas were introduced into the reaction vessel. The process of spraying the growth nuclei, which is the starting point of the growth of the columnar structure, onto the deposited film is
After forming the 104 (B) layer to a thickness of 5 μm, the same method as that described in Experiment 4 was performed. The obtained results are shown in Table 6. From Table 6, it can be seen that the electrophotographic photoreceptor of the present invention is particularly useful when the layer thickness of 104 layers is in the range of 30% or more and less than 100% of the total thickness of the deposited film constituting the photoreceptor.
This tendency was the same even when the carbon amount and the fluorine amount in the 104 layer were changed.

[0093]

[Table 5]

[0094]

[Table 6] Example 4 Under the conditions shown in Table 7, Si powder having an average particle diameter of 10 μm in the Si powder adhesion step was introduced together with Ar gas at a pressure of 2.5 × 10 ⁴ Pa and a flow rate of 1000 sccm for 2 minutes from the inlet 213. A plurality of types of electrophotographic photoconductors were prepared in the same manner as in Experiment 4 except that the electrophotographic photosensitive member was introduced into the reaction container 201. For each of the obtained electrophotographic photoreceptors,
Evaluation was carried out in the same way as in Experiment 4. Table 8 shows the obtained evaluation results. "Reproducibility of fine lines" in Table 8
The evaluation criteria of "cleaning property", "durability" and "service property" are as follows.

Fine line reproducibility: An image sample obtained by copying an ordinary document consisting of all letters on a white background on a platen was observed to evaluate whether fine 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. ◎ ・ ・ ・ ・ Good. ○ ・ ・ ・ ・ Partially discontinued. △ ・ ・ ・ ・ There are many breaks, but they can be recognized as characters. × ・ ・ ・ ・ Some characters cannot be recognized.

Cleanability: A black original, a halftone original, and a full-text original were copied 10 sheets each to evaluate the cleaning ability with a cleaner. ◎ ・ ・ ・ ・ Good. ○ ・ ・ ・ ・ Some small cleaning defects were found, but they were cured after cleaning the blade. △ ・ ・ ・ ・ Small streaky cleaning defects were observed, but there was no problem in practical use. × ・ ・ ・ ・ Whole surface cleaning failure.

Durability: The electrophotographic photosensitive member evaluated as described above was put in a copying machine, and after 10,000 sheets of paper had passed, the evaluation was made as follows. ◎ ・ ・ ・ ・ Each item is equivalent to the initial stage. ○ ・ ・ ・ ・ A slight deterioration was observed in any one of the items compared to the initial stage. △ ・ ・ ・ ・ A considerable deterioration was observed in any of the items compared to the initial stage, but there was no practical problem. × ・ ・ ・ ・ Deterioration that is a hindrance to practical use was recognized.

Serviceability: Continuous paper passing was carried out until cleaning failure due to blade scratches or paper separation failure due to separation claw abrasion occurred, and the number of passed paper sheets was compared with the servicing record of servicemen in the market. ◎ ・ ・ ・ ・ The number of other regular replacement parts was more than compensated. ○ ・ ・ ・ ・ The number of sheets was enough for regular inspection. △ ・ ・ ・ ・ The number of sheets that could have been called by a service person other than during regular inspections. × ・ ・ ・ ・ The number of services was difficult.

[0099]

[Table 7]

[0100]

[Table 8] Comparative Example 1 An amorphous silicon electrophotographic photosensitive member having no columnar structure region was prepared under the conditions shown in Table 9 using the film forming apparatus shown in FIGS. 12 and 13. The obtained photoreceptor was used and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 8.

[0101]

[Table 9] Comparative Example 2 An amorphous silicon electrophotographic photosensitive member having the configuration shown in FIG. 11 was produced under the conditions shown in Table 10 using the RF plasma CVD method. In FIG. 11, 502 is an Al substrate,
Reference numeral 503 is a charge injection blocking layer, 504 is a photoconductive layer, and 504 is a surface protective layer. Here, an amorphous silicon film was formed on the Al substrate 705 by the procedure usually performed using the film forming apparatus shown in FIG. 14 to manufacture an electrophotographic photosensitive member. In FIG. 14, 701 is a vacuum container, 702 is an RF power source, 703 is a source gas introduction port,
706 is a discharge space, 707 is a support, 708 insulator, 7
Reference numeral 09 is a rotary shaft. The surface of the obtained photoreceptor was polished by using a polishing device 801 shown in FIG. The photoconductor 805 is set on the rotary shaft 806 and the motor 8 is set.
It was rotated by 11. Particle size 2 on rotating photoconductor 805
A polishing cloth 807 coated with a normal heptane liquid in which μm silica powder was dispersed was pressed to polish for 10 minutes. 8
Reference numeral 02 is a pressing mechanism. The electrophotographic photosensitive member thus obtained was evaluated in the same manner as in Example 4.
The evaluation results are shown in Table 8.

[0102]

[Table 10] Example 5 Using the film forming apparatus used in Experiment 4, an electrophotographic photosensitive member having a four-layer structure shown in FIG. 5 was produced under the conditions shown in Table 11. The process of spraying Si powder, which is the nucleus of columnar structure growth,
After depositing 104 layers of 5 μm, Si powder having an average particle diameter of 12 μm is applied at a pressure of 2.5 × 10 ⁴ Pa and a flow rate of 800 sccc.
m of Ar gas was introduced into the reaction vessel 201 through the introduction port 213 for 2 minutes. The detailed procedure was similar to that shown in Experiment 4. The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 4. As a result, it was confirmed to have excellent properties as in Example 4.

[0103]

[Table 11] Example 6 Using an acetylene gas instead of methane gas as a carbon atom supply gas, and using the film forming apparatus used in Experiment 4, according to the conditions shown in Table 12, an electrophotography of the three-layer structure shown in FIG. A photoconductor was prepared. Si as the nucleus of columnar structure growth
In the powder adhesion step, the Si powder adhesion step that serves as a nucleus of columnar structure growth is performed by depositing 104 layers of 5 μm, and then applying Si powder having an average particle diameter of 8 μm at a pressure of 2.5 × 10 ⁴ Pa and a flow rate of 800 sccm. It was introduced together with Ar gas into the reaction vessel 201 through the introduction port 213 for 3 minutes. The detailed procedure was similar to that shown in Experiment 4.
The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 4. As a result, evaluation was performed in the same manner as in Example 4. As a result, it was confirmed to have excellent properties as in Example 4.

[0104]

[Table 12] Example 7 Using the film forming apparatus used in Experiment 4, a deposited film was formed on the substrate by the same process as in Example 4 according to the conditions shown in Table 7. After forming the deposited film, the surface of the photoconductor was polished using the polishing apparatus shown in FIG. The polishing apparatus shown in FIG. 10 has a form in which an electrophotographic photosensitive member is attached to a shaft, is rotated, and a polishing liquid 413 is supplied to the surface of the rotating electrophotographic photosensitive member to perform polishing.

First, the polishing unit 402 in the main body 401 of the polishing apparatus is lifted up and fixed by the clamp 403.
The electrophotographic photosensitive member 405 was combined with the support 404 and fixed to the shaft 406. Then, the clamp 403 was loosened, the polishing unit 402 was lowered, and the polishing roller 407 was pressure-bonded to the electrophotographic photosensitive member 405. A cloth was used as the material of the surface of the polishing roller 407. At this time, the pressure difference spring 409 is adjusted so that the pressure for pressing the polishing roller 407 to the electrophotographic photosensitive member 405 is 10 g / cm ² ,
The nip width was 10 mm.

A polishing liquid 41 stored in the upper tank 408 and using silicon carbide having an average particle diameter of 8 μm as an abrasive.
3, while adjusting the flow rate with the valve 414, the injection pipe 415
Was dripped onto the polishing roller 407. Simultaneously with the dropping of the polishing liquid, the motors 410 and 411 were rotated to perform polishing. The rotation speed of the polishing roller 407 is 10 mm.
/ Min, the rotation speed of the electrophotographic photosensitive member 405 as the member to be polished was 300 mm / sec, and polishing was performed for 5 minutes. The surface of the electrophotographic photosensitive member that has been polished as described above is washed with ion-exchanged water to remove the polishing liquid remaining on the surface, and then left in a drying chamber at a temperature of 40 ° C. for 1 hour. Then, the water on the surface was removed.

The electrophotographic photosensitive member thus obtained was evaluated in the same procedure as in Example 4. As a result, as in the case of Example 4, it was confirmed that the electrophotographic photosensitive member was excellent.

[Brief description of drawings]

FIG. 1 is a schematic view schematically showing an example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic view schematically showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic view schematically showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a schematic view schematically showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 5 is a schematic view schematically showing an example of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic view schematically showing a light incident path and a light reflection path in the electrophotographic photosensitive member of the present invention.

FIG. 7 is a schematic view showing an example of a film forming apparatus that can be used to manufacture the electrophotographic photosensitive member of the present invention.

FIG. 8 is a schematic view showing an example of a film forming apparatus that can be used to manufacture the electrophotographic photosensitive member of the present invention.

FIG. 9 is a schematic view showing a polishing apparatus.

FIG. 10 is a schematic view showing a polishing apparatus.

FIG. 11 is a schematic view schematically showing a conventional electrophotographic photosensitive member.

FIG. 12 is a schematic view showing an example of a microwave plasma CVD apparatus.

FIG. 13 is a schematic diagram showing an example of a microwave plasma CVD apparatus.

FIG. 14 is a schematic view showing an RF plasma CVD apparatus.

FIG. 15 is a schematic view showing a polishing apparatus.

[Explanation of symbols]

 101 Cross Section of Electrophotographic Photosensitive Member According to the Present Invention 102,502 Substrate 103 Charge Injection Blocking Layer 104 Photoconductive Layer 105 Surface Protective Layer 110 Columnar Structure Region 111 Columnar Structure Core 201, 601, 701 Reaction Vessel 202, 602 Microwave Introduction Tube 203,603 Waveguide 204,604,704 Exhaust tube 205,605,705 Base 206,606,706 Discharge space 207,607,707 Heater 209,609,709 Rotating shaft 210,610,710 Motor 211 DC power supply 212 Bias electrode 213 Particle introduction port 301,401,801 Polishing device 302,402 Polishing unit 303,403 Clamp 304,404 Support 305,405,805 Electrophotographic photoreceptor 306,406,806 Shaft 307 Pressing roller 308 Polishing tape 309,409 Spring 310,410 Motor 311,411,811 Motor 407 Polishing roller 408 Tank 413 Polishing liquid 414 Valve 415 Injection tube 501 Cross section of conventional electrophotographic photoreceptor 503 Charge injection blocking layer 504 Photoconductive layer 505 Surface protection Layer 702 RF electrode 703 Raw material gas introduction pipe 708 Insulating insulator 802 Pressing mechanism 807 Polishing cloth

Claims (15)

[Claims] 1. An electrophotographic photosensitive member comprising a substrate for an electrophotographic photosensitive member and a photoreceptive layer formed on the substrate and made of a non-single-crystal material containing a silicon atom, wherein The light-receiving layer has a columnar structure region 5 which is substantially parallel to the layer thickness direction of the layer starting from a plurality of nuclei located inside the layer.
An electrophotographic photosensitive member characterized by having a density of pieces / cm ² to 500 / cm ^2. 2. The electrophotographic photosensitive member according to claim 1, wherein the material forming the nucleus is a crystalline material. 3. The electrophotographic photosensitive member according to claim 1, wherein the diameter of the region of the columnar structure is in the range of 1 μm to 300 μm. 4. The electrophotographic photosensitive member according to claim 1, wherein the nucleus is provided at a position 1 μm or more from an interface position of the light receiving layer on the substrate side. 5. The non-single-crystal material forming the light receiving layer contains carbon atoms of 2.0 atom% to 2 with respect to silicon atoms.
The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is contained in the range of 5 atom%. 6. The non-single-crystal material constituting the light-receiving layer contains fluorine atoms of 2.0 ppm to 90 relative to silicon atoms.
The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is contained in a range of ppm. 7. A gas containing silicon atoms is introduced into a reaction vessel capable of reducing the pressure, and microwave energy is supplied to the gas.
To generate a plasma in the discharge space in the reaction vessel to form a photoreceptive layer made of a non-single-crystal material containing silicon atoms on the substrate arranged in the reaction vessel. A method for producing an electrophotographic photosensitive member, comprising: (i) forming a part of the light-receiving layer; and (ii) forming a surface of the formed layer,
A plurality of nuclei serving as a starting point for forming a region having a columnar structure are stably attached, and (iii) the step (i) is performed on the surface of the layer to which the plurality of nuclei are attached to form a plurality of the nuclei. A method for producing an electrophotographic photosensitive member, characterized in that a region having a columnar structure which is substantially parallel to a growth direction of the layer as a starting point is formed at a density of 5 pieces / cm ^{2 to} 500 pieces / cm ² . 8. The method for manufacturing an electrophotographic photosensitive member according to claim 7, wherein the material forming the core is a crystalline material. 9. The method for manufacturing an electrophotographic photosensitive member according to claim 7, wherein the diameter of the region of the columnar structure is in the range of 1 μm to 300 μm. 10. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the nucleus is arranged at a position of 1 μm or more from an interface position of the light receiving layer on the substrate side. 11. The electrophotographic photosensitive material according to claim 7, wherein the non-single-crystal material forming the light receiving layer contains carbon atoms in the range of 2.0 atom% to 25 atom% with respect to silicon atoms. Body manufacturing method. 12. The non-single crystal constituting the light receiving layer contains fluorine atoms of 2.0 ppm to 90 relative to silicon atoms.
The method for producing an electrophotographic photosensitive member according to claim 7, wherein the electrophotographic photosensitive member is contained in the range of ppm. 13. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the material forming the nucleus is charged and introduced into the reaction container. 14. The charging according to claim 1, wherein the charging is corona charging.
4. The method for producing an electrophotographic photosensitive member according to item 3. 15. The adhesion of the nucleus to the surface of the layer is 1V.
The method for producing an electrophotographic photosensitive member according to claim 13, wherein the method is performed under an electric field of / cm to 100 V / cm.