JP2001312085A - Electrophotographic photoreceptor and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has good electric characteristics and in which peeling, scratches or wear are not caused even in long-term use. SOLUTION: In the electrophotographic photoreceptor having a photoconductive layer consisting of a non-single crystal material essentially comprising silicon atoms and a surface layer consisting of non-single crystal carbon containing at least hydrogen formed on a conductive substrate, the surface layer has >=500 Å and <=2,000 Å surface roughness Rz for 5 μm referential length and contains two or more kinds of atoms selected from oxygen, nitrogen, fluorine and boron. The surface layer is formed at a smaller deposition rate than the deposition rate of the layer in contact with the surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, it is resistant to scratches and abrasion in various electrophotographic processes, has excellent printing durability, has a long service life, has little fluctuation in potential characteristics, and has a high sensitivity. And an electrophotographic photoreceptor having less afterimage phenomenon.

[0002]

2. Description of the Related Art Selenium, cadmium sulfide, zinc oxide, phthalocyanine, amorphous silicon (hereinafter referred to as "a-S
Various types of materials have been proposed. Above all, a non-single crystalline deposited film containing a silicon atom typified by a-Si as a main component, for example, an amorphous deposited film such as a-Si compensated with hydrogen and / or halogen (for example, fluorine, chlorine or the like) has a high performance. , Highly durable and pollution-free photoreceptors, some of which have been put to practical use.

Conventionally, as a method of forming such a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), and a method of decomposing a source gas by light (optical CV)
Many methods are known, including a method D) and a method of decomposing a source gas by plasma (plasma CVD method). Among them, the plasma CVD method, that is, the raw material gas is DC or high frequency (R
F, VHF), a method of forming a thin-film deposited film on a conductive substrate such as glass, quartz, a heat-resistant synthetic resin film, stainless steel, and aluminum is decomposed by a glow discharge or the like such as a microwave. At present, practical application of a method for forming an a-Si deposited film and the like has been extremely advanced, and various apparatuses for this purpose have been proposed.

[0004] For example, Japanese Patent Application Laid-Open No. 57-115551 discloses that silicon atoms and silicon atoms are formed on a photoconductive layer composed of an amorphous material mainly composed of silicon atoms and containing at least one of hydrogen atoms and halogen atoms. There is disclosed an example of a photoconductive member having a carbon atom as a base and a surface barrier layer formed of a non-photoconductive amorphous material containing a hydrogen atom.

[0005] JP-A-61-219961 discloses that a
-As a surface protective layer formed on the Si-based photosensitive layer,
An example of an electrophotographic photosensitive member composed of amorphous carbon containing 10 to 40 atomic% of hydrogen atoms (hereinafter referred to as “aC: H”) is disclosed.

Japanese Patent Application Laid-Open No. Hei 6-317920 discloses that 20M
A photoconductive layer made of a non-single-crystal silicon-based material having a silicon atom as a base material and an aC: H surface protective layer having a hydrogen atom content of 8 to 45 atomic% using a high frequency of not less than Hz. A method for manufacturing an electrophotographic photosensitive member is disclosed.

Japanese Patent Application Laid-Open No. 60-186849 discloses that a microwave (for example, a frequency of 2.
A method and an apparatus for forming an electrophotographic device having a top blocking layer by a microwave plasma CVD method using 45 GHz) are disclosed.

[0008] These techniques have improved electrical, optical, photoconductive properties, use environment properties, and durability, and also improved image quality.

However, in recent years, the electrophotographic apparatus has been required to have higher speed and higher image quality. When trying to speed up electrophotographic equipment, charging, exposure,
It is necessary to increase the copy paper feed speed by accelerating the cycle of development, transfer, and static elimination. In this case, the number of times and time per unit time that the electrophotographic photosensitive member comes into contact with a copy sheet, a cleaning mechanism, and the like increase dramatically. Further, the higher the speed of the process, the more difficult it becomes to completely clean the cleaning blade, and there is a tendency to increase the rubbing force on the electrophotographic photosensitive member in order to prevent chattering of the cleaning blade and toner slip-through. Therefore, as the process speed increases, the force with which the drum itself is rubbed relatively increases. Therefore, physical damage such as abrasion or abrasion of the surface layer which has not been worn at all in the conventional processes is becoming remarkable.

Therefore, there has been a demand for an electrophotographic photoreceptor which enables complete cleaning in any high-speed process and is free from abrasion of the photoreceptor. Such abrasion is a serious problem in that it becomes more remarkable especially when the size of the electrophotographic photosensitive member is reduced in order to reduce the size of the electrophotographic apparatus.

As a countermeasure against such a problem, a method of making the outermost surface of the electrophotographic photosensitive member harder or more slippery to prevent scratches and abrasion has been taken, and has recently attracted attention. As an optimal material for this purpose, there is an amorphous carbon film aC: H film containing hydrogen. This aC: H film is considered to be the most suitable material for the above purpose because it has a very high hardness, also called diamond-like carbon (DLC), and has a unique lubricating property. . However, although it has a very high hardness, it also has the disadvantage that the internal stress in the film is large and the film is easily peeled off. For this reason, it was sometimes difficult to deposit a required film thickness without peeling. Further, when the film quality is viewed from the viewpoint of use in an electrophotographic photoreceptor, there is an insufficient point as a semiconductor film. However, there have been cases where defects such as deterioration of the afterimage phenomenon and further increase in the residual potential are observed.

On the other hand, when the process speed is increased to increase the speed, there is a problem that the charge time decreases because the time for charging is shortened. Further, since the time required for light exposure is similarly shortened, it is necessary to irradiate stronger image exposure. That is, in general, the higher the speed of the process, the lower the charge amount and the lower the sensitivity. Therefore, further improvement in charging performance and sensitivity is increasingly required more than ever.

In the past, high-speed electrophotographic apparatuses were mainly required to improve productivity, and in many cases, high image quality was not required to be so high. It is being sought. In particular, a
In an electrophotographic photoreceptor using -Si, the after-image phenomenon is apt to occur, that is, the previously copied image is thinly transferred to the intermediate density portion of the next image. However, in recent years in which high image quality is required as described above, the demand for the afterimage phenomenon is becoming more severe.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recent electrophotographic apparatus which is required to have a high speed and a long service life, to enable good cleaning, and to prevent scratches, abrasion and wear when used for a long time. An object of the present invention is to provide a highly durable and excellent electrophotographic photoreceptor having a surface layer free from problems such as film peeling.

It is another object of the present invention to provide an electrophotographic photoreceptor which can obtain a sufficient amount of charge, has a high sensitivity, has a sufficiently low residual potential, and is easy to use in an electrophotographic apparatus, even in a high-speed electrophotographic process. And

Further, an electrophotographic photoreceptor which can sufficiently cope with high image quality in a recent electrophotographic apparatus, that is, a halftone image having a low afterimage phenomenon and a uniform density can be obtained, and a high-resolution and clear image can be obtained for a long time. An object of the present invention is to provide an electrophotographic photoreceptor that can output stably over a period.

[0017]

The electrophotographic photoreceptor of the present invention has a photoconductive layer made of a non-single-crystal material having a silicon atom as a base on a conductive substrate, and comprises a non-monocrystalline material containing at least hydrogen. In an electrophotographic photoreceptor having a surface layer made of crystalline carbon, the surface layer has a surface roughness Rz of 500 Å or more when a reference length is set to 5 μm.
2,000 angstroms or less, and the surface layer contains two or more atoms selected from oxygen, nitrogen, fluorine and boron atoms, and the deposition rate is lower than the deposition rate of the layer adjacent to the surface layer. It is characterized by being formed by.

The surface layer further comprises oxygen, nitrogen, fluorine,
Containing at least two types of atoms selected from boron atoms,
It is preferred that their content be higher than the layer in contact with the surface layer. Further, a buffer may be provided between the photoconductive layer and the surface layer, and the buffer layer may be made of a non-single-crystal material containing silicon atoms as a base and containing carbon atoms. Further, it is preferable that the buffer layer is formed such that the deposition rate is lower than the deposition rate of the photoconductive layer in contact with the buffer layer. Further, the sum of the contents of at least two kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms contained in the surface layer is 0.001 atomic% to 5 atomic%.
Atomic% is good.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have paid attention to using an aC: H film as a surface protective layer as a method for solving the above various problems. The aC: H film has a very high hardness, which is also called DLC (diamond-like carbon). If the surface protection layer of the aC: H film is used for a conventional electrophotographic photoreceptor, the photoreceptor is scraped or scratched. It was found that a remarkable effect was obtained for However, the aC: H film, which is very resistant to abrasion, also has a property that it has a strong internal stress and is also very easily peeled off, so that it is difficult to deposit a desired thickness with good reproducibility. It could not be used effectively as a surface layer of an electrophotographic photosensitive member.

As a result of a detailed study of the ease of peeling, a-
It became clear that there was a correlation with the surface roughness of the C: H surface layer. That is, the surface roughness of the surface layer is set to a reference length of 5 μm.
When Rz was set to 500 Å or more, good results were obtained. The fact that the surface roughness of the aC: H surface layer is large means that the interface between the surface layer and the photoconductive layer is rough, and as a result, the adhesiveness is increased due to an increase in the contact area. It is thought that it has improved. However, on the other hand, the surface roughness is Rz: 2
It was also found that a sensitivity lower than 1000 Å was observed. The details of this are unknown at this time, but we believe that the light scattering effect due to the roughened surface may be involved. In any case, a sufficient effect can be obtained by setting the surface roughness of the aC: H surface layer itself to Rz = 500 Å to 2,000 Å, and a sufficient effect can be obtained. There was no need to specify the directness.

Further, the gist of the present invention is that the aC: H surface layer contains two or more kinds of atoms selected from N, O, F, and B atoms and deposits the photoconductive layer at a deposition rate. To make the deposition speed slower. N, O,
The structure on the surface on which the deposited film of the surface layer grows by simultaneously containing at least two types of atoms selected from F and B atoms and by lowering the deposition rate than the layer in contact with the aC: H surface layer. It was found that the relaxation was promoted, and the effect of improving the adhesion was obtained. As a result, even if the surface roughness is controlled within the above range, occurrence of defects due to occasional unexplained peeling can be reduced to zero. N, O,
At least two kinds of atoms selected from F and B atoms are a-
If the deposition rate of the aC: H surface layer is lower than that of the layer in contact with the C: H surface layer, the same effect can be obtained by any combination. Therefore, it is only necessary to supply a gas containing two kinds of elements that are most easily prepared from the types of production gas prepared in the production facility, and there is an advantage that investment in the production facility can be minimized. Also, by containing more N, O, F, and B atoms in the layer in contact with the aC: H surface layer, more remarkably,
The effects of the present invention can be obtained with good reproducibility.

Further, according to the present invention, N, O, F,
The effect of containing at least two kinds of atoms selected from B atoms and the effect of lowering the deposition rate of the surface layer than the layer in contact with the aC: H surface layer is not only an improvement in adhesion, but also an effect of charging the electrophotographic photosensitive member. And improved photosensitivity, resulting in a reduction in the afterimage phenomenon. This is because at least two types of atoms selected from N, O, F, and B are a- under the condition that the deposition rate of the aC: H surface layer is lower than that of the layer in contact with the aC: H surface layer. I imagine that this may be because the structural relaxation of the C: H film is promoted to remove structural defects, and that the film effectively functions as a terminator. The characteristics of the aC: H film as a semiconductor are still under research and are not necessarily completed, and there is room for improvement. However, this aC: H film and N, O, F,
The compatibility of two or more atoms selected from the B atoms is specifically good, and the aC: H surface layer has a lower deposition rate than the layer in contact with the aC: H surface layer. I imagine that it effectively reduces the localized level density generated from existing structural defects. For this reason, injection of charged carriers through structural defects in the surface layer is prevented, which contributes to improvement in charging performance. Further, since the optical carrier is prevented from being trapped in the localized level, it leads to an improvement in optical sensitivity and a reduction in an afterimage phenomenon. Further, at the outermost surface of the deposited film, N, O, F, B
Since at least two kinds of atoms selected from atoms and the active species have sufficient time to relax the structure, a film can be easily obtained by forming a denser three-dimensional network. It is supposed that this, the effect of promoting structural relaxation and the effect of termination interact with each other, leading to a remarkable improvement in characteristics.

The content of each of at least two kinds of atoms selected from N, O, F, and B atoms is desirably 0.001 to 5 atomic%. The term "atomic%" as used herein means a ratio to all elements. If the content is less than 0.001 atomic%, the above effects may not be obtained. If the content exceeds 5 atomic%, the band gap of the aC: H film may be reduced, which may lead to deterioration of photosensitivity. It is desirable that the content of each of the at least two types of atoms selected from N, O, F, and B atoms be at least 0.0001 atomic% or more.

The above effect is obtained by simultaneously containing two or more kinds of atoms selected from N, O, F and B atoms in the aC: H layer,
It was obtained only when the deposition rate of the aC: H surface layer was lower than that of the layer in contact with the aC: H surface layer. When only one of these atoms is contained, charging ability, sensitivity,
Since there is no improvement in the afterimage phenomenon, the combination of these specific atoms and the deposition rate are considered to be very important.

Hereinafter, the present invention will be specifically described with reference to the drawings.

FIG. 1 is a schematic diagram illustrating an electrophotographic photosensitive member according to the present invention. FIG. 1 shows a photoconductor in which a photoconductive layer is referred to as a single-layer type having no functional separation, and a conductive substrate 10 is provided.
A photoconductive layer 102 made of a-Si containing at least hydrogen and a surface layer 103 made of non-single-crystal carbon are stacked on the semiconductor device 1. The surface layer 103 contains at least two kinds of atoms selected from N, O, F, and B atoms,
The deposition rate during deposition is lower than that of the photoconductive layer 102, and the surface irregularities are controlled so that Rz at a reference length of 5 μm is 500 to 2000 Å. In the present invention, the effect of the present invention is more remarkably obtained by allowing the photoconductive layer 102 to contain at least two kinds of atoms selected from N, O, F, and B atoms contained in the surface layer 103 in a larger amount. This is also preferable for improving the reproducibility.

FIG. 2 is a schematic view of the electrophotographic photosensitive member of the present invention in which a buffer layer 204 is further provided between the surface layer 203 and the photoconductive layer 202. The surface layer 203 is made of N, O,
At least two kinds of atoms selected from the F and B atoms are contained in the buffer layer 204 more, and the deposition rate during deposition is lower than the deposition rate of the buffer layer. Further, the surface irregularities are such that Rz is 5 at a reference length of 5 μm.
It is controlled to be not less than 00 Å and not more than 2000 Å. In this case, at least two types of atoms selected from N, O, F, and B atoms are simultaneously contained in the buffer layer 204, and the content thereof is increased more than that of the photoconductive layer 202, and at the same time, the deposition rate of the buffer layer during deposition is increased. It is preferable that the deposition rate be lower than the deposition rate of the conductive layer because the effects of the present invention can be obtained.

FIG. 3 shows a photoconductive layer 302 and a conductive substrate 301.
FIG. 9 is a schematic diagram of the electrophotographic photoreceptor of the present invention in a case where a lower blocking layer 305 is further provided between the two.

FIG. 4 shows a photoreceptor called a function-separated type because the photoconductive layer is separated into two functions, that is, a charge generation layer and a charge transport layer. If necessary, a lower blocking layer 405 is provided on the conductive substrate 401, and a layer composed of at least hydrogen-containing a-Si, which is functionally separated from the charge transport layer 406 and the charge generation layer 402, is deposited thereon. A surface layer 403 made of non-single-crystal carbon is laminated thereon. Here, the order of the charge transport layer 406 and the charge generation layer 402 is not limited to the order shown in the schematic diagram, and may be arbitrary. Further, when the function separation is performed by changing the composition, the composition may be changed continuously.

FIG. 5 shows the conductive substrate 501 and the lower blocking layer 50.
5, photoconductive layer 502, buffer layer 504, surface layer 503
It is a schematic diagram in the case of having provided.

In the photoreceptors shown in FIGS. 1 to 5, each layer may have a continuous composition change and may not have a clear interface.

The conductive substrate 10 used in the present invention
1 to 201, 301, 401 and 501 (hereinafter, 10
Abbreviated as 1 to 501) have a material, a shape, or the like according to the purpose of use. For example, as to the shape, when it is used for an electrophotographic photoreceptor, a cylindrical shape is desirable, but it may be a flat shape, a plate-like endless belt shape, or another shape as needed. The thickness is appropriately determined so that a desired electrophotographic photoreceptor can be formed. However, when flexibility is required, the thickness is as far as possible within a range where the function as a support can be sufficiently exhibited. Can be thin. However, the thickness of the support is usually 10 μm or more in terms of production, handling, mechanical strength and the like. In the material, copper, aluminum, gold and silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and two or more of these materials, polyester, polyethylene, polycarbonate, Cellulose acetate, polypropylene, polyvinyl chloride,
An insulating material such as polyvinylidene chloride, polystyrene, glass, ceramics, paper or the like coated with a conductive material can be used.

The lower blocking layers 305, 405 and 505 in the electrophotographic photoreceptor of the present invention are respectively provided from the conductive supports 101 to 501 side when the electrophotographic photoreceptor is provided with a charging treatment having a fixed polarity on its free surface. Photoconductive layer 102,2
02, 302, 402 and 502 (hereinafter, 102 to 5)
02), and has a function of preventing charge injection, and does not exhibit such a function when subjected to charging treatment of the opposite polarity, that is, has a so-called polarity dependency. . In order to provide such a function, the lower blocking layer 30 is provided.
5,405 and 505 contain a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. Lower blocking layer 30
As an atom for controlling conductivity contained in 5,405 and 505, a Group 3b atom or a Group 5b atom can be used. In the present invention, the lower blocking layers 305, 4
The content of the atom controlling the conductivity contained in each of 05 and 505 is appropriately determined as desired so that the object of the present invention can be effectively achieved.
1 × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³
Atomic ppm, optimally 1 × 10 ² to 1 × 10 ³ atomic pp
m.

The lower blocking layers 305, 405, and 505 contain at least one of carbon atoms, nitrogen atoms, and oxygen atoms, so that the lower blocking layers 305, 405, and 505 contain at least one atom.
Adhesion with other layers provided in direct contact with 405 and 505, respectively, can be further improved. Carbon atoms and / or nitrogen atoms contained in all the layer regions of lower blocking layers 305, 405 and 505 and / or
Alternatively, the content of oxygen atoms is, in the case of one kind, as the amount, and in the case of two or more kinds, the sum thereof, preferably 1 ×
10 ^-3 to 50 atomic%, more preferably 5 × 10 ^-3 30 atomic%, optimally 1 × 10 ^-2 to 10 atomic%.

The lower blocking layers 305, 405, and 505 contain hydrogen atoms and / or halogen atoms to compensate for dangling bonds existing in the layers, thereby improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the lower blocking layers 305, 405 and 505 is preferably 1 to 50 atomic%, more preferably 5 to 40 atomic%, and most preferably Is 10 to 30 atomic%.

The thickness of the lower blocking layers 305, 405 and 505 is preferably 0.1 to 5 μm, and most preferably 1 to 4 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economic effects.

The photoconductive layers 102 to 502 in the electrophotographic photoreceptor of the present invention need to contain hydrogen atoms and / or halogen atoms in the film. This is because it is indispensable for compensating for dangling bonds of silicon atoms and improving the layer quality, particularly, the photoconductivity and the charge retention characteristics. The content of hydrogen or halogen atoms,
Alternatively, the amount of the sum of the hydrogen atom and the halogen atom is 1 to the sum of the silicon atom and the hydrogen atom and / or the halogen atom.
It is 0 to 30 atomic%, and more preferably 15 to 25 atomic%. In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layers 102 to 502, for example, the temperature of the support, the amount of the raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the amount introduced into the reaction vessel, the discharge power and the like.

It is preferable that the photoconductive layers 102 to 502 contain atoms for controlling conductivity as necessary. The atoms that control the conductivity include lower blocking layers 305 and 405.
And 505 can be used. The content of atoms for controlling the conductivity contained in the photoconductive layers 102 to 502 is preferably 1 ×
10 ^-2 to 1 × 10 ⁴ atomic ppm, more preferably 5 × 1
0 ^{-2 to} 5 × 10 ³ atomic ppm, optimally 1 × 10 ^-1 to 1
× 10 ³ atomic ppm.

Further, in the present invention, the photoconductive layer 102
It is also effective to include a carbon atom and / or an oxygen atom and / or a nitrogen atom in -502. The content of the carbon atom and / or the oxygen atom and / or the nitrogen atom is preferably 1 × 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁵ %, based on the sum of the silicon atom, the carbon atom, the oxygen atom and the nitrogen atom. ^-4 to 8 atomic%, optimally 1 × 10 ^-3
５5 at%. The carbon atoms and / or oxygen atoms and / or nitrogen atoms do not necessarily need to be contained in the entire layer, but may be distributed only partially or in the film thickness direction.

In the present invention, the photoconductive layers 102 to 502
Is determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 10 to 50 μm, more preferably 20 to 45 μm.
m, optimally 25 to 40 μm.

The buffer layers 204 and 504 are provided as necessary to achieve mechanical and electrical matching between the photoconductive layers 102 to 502 and the surface layers 103 to 503. In this case, the materials include the photoconductive layers 102 to 502 and the surface layer 10.
S having an intermediate composition from the viewpoint of consistency with 3-503
It is desirable to use an iC layer. The buffer layers 204 and 504 may be uniform layers having a constant composition, or the compositions may be continuously changed. The buffer layer contains at least two types of atoms selected from N, O, F, and B atoms as necessary.
It can be smaller than 02 to 502. in this case,
By making the content of at least two kinds of atoms selected from N, O, B, and F atoms larger than that of the photoconductive layers 102 to 502, the adhesion can be improved, and the adhesion and electrophotographic characteristics can be improved. preferable.

The buffer layers 204 and 504 may contain atoms for controlling the conductivity similarly to the lower blocking layers 305, 405 and 505. As the atoms that control the conductivity contained in the buffer layers 204 and 504, Group 3b atoms or Group 5b atoms can be used.
In the present invention, the content of the atoms controlling the conductivity contained in the buffer layers 204 and 504 is appropriately determined as desired so that the object of the present invention can be effectively achieved. 1 × 10 ⁴ atom pp
m, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

The thickness of each of the buffer layers 204 and 504 is appropriately set to an appropriate value according to the purpose, but is generally 0.01 μm to 10 μm, preferably 0.05 μm to 5 μm.
μm, optimally between 0.1 μm and 1 μm.

Surface layers 103-50 according to the invention
3 is composed of non-single crystalline carbon. The term "non-single-crystal carbon" as used herein mainly refers to amorphous carbon having properties intermediate between graphite (graphite) and diamond, but may partially include microcrystals or polycrystals. The surface layers 103 to 503 have a free surface and can be used mainly for preventing scratches and abrasion during long-term use, improving chargeability and improving sensitivity without increasing peeling, residual potential, and residual image development. Provided to achieve the purpose.

As a raw material gas for forming the surface layers 103 to 503 of the present invention, a gaseous hydrocarbon is used at normal temperature and normal pressure, and can be produced by a plasma CVD method, a sputtering method, an ion plating method, or the like. The film made by using the plasma CVD method has high transparency and hardness,
It is preferable to use as a surface layer of an electrophotographic photosensitive member. Plasma C for forming surface layers 103 to 503 of the present invention
Any frequency can be used as the discharge frequency used in the VD method. Industrially, a high frequency of 1 to 20 MHz, particularly 13.5 MHz, which is called an RF frequency band, can be suitably used. Especially 50-450MHz and VHF
In the case of using a high frequency in a frequency band referred to as the above, both transparency and hardness can be further increased, so that it is more preferable when used as a surface layer.

The surface layers 103 to 503 of the present invention need to have a surface roughness of not less than 500 angstroms and not more than 2000 angstroms per 5 μm of reference length. In order to control the surface layers 103 to 503 to this roughness range, fine irregularities may be created, for example, by optimizing the cutting conditions of the conductive substrate. Also, the photoconductive layers 102 to 50
Roughness can also be controlled by adjusting various manufacturing parameters. Generally, the surface roughness tends to increase as the discharge excitation power increases and the bias increases. Alternatively, after deposition up to the photoconductive layer or the buffer layer, plasma discharge may be performed with a fluorine-containing gas or a hydrogen gas, and the surface may be roughened by etching for adjustment.

In order to obtain the effect of the present invention, it is necessary that the surface layers 103 to 503 further contain at least two kinds of atoms selected from N, O, F and B atoms. Further, by making the deposition rate at the time of lamination lower than the deposition rate of the layer in contact with the surface layers 103 to 503, a specific synergistic effect between the selected atoms and the aC: H film is promoted. It is considered that the structural defects in the film are effectively compensated for on the outermost surface where the film grows, and the local level density is reduced. As a result, the transparency of the film is improved and the light sensitivity is dramatically improved by suppressing unwanted unwanted light absorption in the surface layer. In addition, since the surface layer is densified, injection of charged carriers is suppressed, and charging characteristics are improved.
At the same time, at least two types of atoms selected from N, O, F, and B exhibit an effect of improving the adhesion of the film. : It is possible to use a material such as H without peeling off the film.

The sum of the contents of at least two types of atoms selected from the N, O, F, and B atoms is 0.001 atomic% to 5 atomic%.
Atomic% is desirable. If the content is less than 0.001 atomic%, the above effects cannot be obtained. When the content exceeds 5 atomic%, the band gap of the aC: H film is reduced, and conversely, the photosensitivity is deteriorated. Also, N, O,
It is desirable that the content of each of the at least two types of atoms selected from the F and B atoms be at least 0.0001 atomic% or more.

According to the present invention, at least two kinds of atoms selected from N, O, F, and B atoms are selected and contained in the surface layer, and at the same time, the aC: H surface layer is in contact with the surface layer when the surface layer is formed. If the deposition rate is reduced, the effect of the present invention can be obtained by any combination of atoms. Therefore, it is only necessary to select two types of elements which are most easily prepared from the types of production gas prepared in the production facility, and there is an advantage that investment in the production facility can be minimized.

The deposition rate of the surface layer is as follows.
Is smaller than the deposition rate of the layer in contact with, the effect of the present invention can be obtained. In this case, it is desirable that the deposition rate be as small as possible because the effect of the present invention can be more remarkably obtained as the deposition rate is reduced. Specifically, it cannot be unconditionally determined by the manufacturing conditions, the composition of the contacting film, and the layer constitution of the photoreceptor, but for example, 0.01 Å / sec to 20 Å / sec, preferably 0.1 Å / sec to 10 Å. Angstrom / sec, more preferably 0.5 angstrom / sec to 5 angstrom / sec.

The aC film used for the surface layers 103 to 503 of the present invention needs to appropriately contain hydrogen atoms. The content of hydrogen atoms contained in the aC: H film is 10 at% to 60 at% in H / (C + H), and more preferably 20 to 40 at%. 1 hydrogen
If it is less than 0 atomic%, the optical band gap becomes narrow, and it is not suitable in terms of sensitivity. On the other hand, if the content exceeds 60 atomic%, the hardness is reduced, and shaving is likely to occur. Generally, the optical band gap can be suitably used as long as it has a value of about 1.2 eV to 2.2 eV, and 1.6 eV from the viewpoint of sensitivity.
It is more desirable to make the above. Refractive index is 1.8 ~
If it is about 2.8, it is preferably used. The film thickness is between 50 Angstroms and 10000 Angstroms, preferably between 100 Angstroms and 2000 Angstroms. If the thickness is less than 50 angstroms, a problem occurs in mechanical strength. If the thickness is more than 10,000 angstroms, a problem occurs in light sensitivity.

The substrate temperature is adjusted from room temperature to 350 ° C., but if the substrate temperature is too high, the band gap decreases and the transparency decreases, so a lower temperature setting is preferable.

The high-frequency power is preferably as high as possible because the decomposition of hydrocarbon proceeds sufficiently, and specifically, the power is preferably 5 W / cc or more with respect to the hydrocarbon raw material gas. However, if the temperature is too high, an abnormal discharge occurs and the characteristics of the electrophotographic photoreceptor deteriorate. Therefore, it is necessary to suppress the electric power to such an extent that the abnormal discharge does not occur.

Regarding the pressure in the discharge space, when a film is formed using a raw material gas such as hydrocarbon which is hardly decomposed, a polymer is liable to be generated if the decomposed species collide in the gas phase. High vacuum is desirable. 13.3 when using normal RF (typically 13.56 MHz) power
Pa to 1330 Pa, VHF band (typically 50 to 45
MHz) when using 13.3 mPa to 13.3 P
a is maintained.

The atom for controlling the conductivity used in the present invention, for example, the Group 3b atom is specifically B-atom.
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. As the group 5b atom, specifically, P (phosphorus), As (arsenic), Sb
(Achimon), Bi (bismuth), etc.
As is preferred.

In order to structurally introduce a Group 3b atom or a Group 5b atom, a source material for introducing a Group 3b atom or a source material for introducing a Group 5b atom in a gaseous state at the time of forming a layer. What is necessary is just to introduce into a reaction container with another gas. As a source material for introducing a Group 3b atom or a source material for introducing a Group 5b atom, a material that is gaseous at ordinary temperature and normal pressure or that can be easily gasified at least under layer forming conditions is desirable. As such a raw material for introducing a group 3b atom, specifically, as a boron atom introduction, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B _{6
H 10, B 6 H 12,} B 6 borohydride of H _14, etc., BF _3, B
Examples include boron halides such as Cl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ )
₃ , InCl ₃ , TlCl _{3 and the} like.
Effectively used as a raw material for introducing group 5b atoms are phosphorus hydrides such as PH ₃ and P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ and PCl ₃ for introducing phosphorus atoms. , PCl
₅ , PBr ₃ , PBr ₅ , PI _{3 and the} like. In addition, AsH ₃ , AsF ₃ , AsCl ₃ ,
AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF
₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ ,
BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group 5b atoms. These raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He as necessary.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃
Silicon hydrides (silanes) in a gas state such as H ₈ , Si ₄ H ₁₀ or the like, which can be gasified, are effectively used, and further, ease of handling at the time of forming a layer, good Si supply efficiency, etc. In view of the above, SiH ₄ and Si ₂ H ₆ are preferred.

In order to structurally introduce hydrogen atoms into each of the layers to be formed and to make it easier to control the rate of introduction of hydrogen atoms, and to obtain film characteristics which achieve the object of the present invention, these layers are used. A desired amount of a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom can be further mixed with the gas to form a layer. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

[0059] the flow rate of the use as diluent gas H ₂ and / or He may be appropriately selected within an optimum range in accordance with the layer design, the H ₂ and / or He with respect to Si-feeding gas, in the case of normal 3 to 20 times, preferably 4-1
It is desirable to control the range of 5 times, optimally 5 to 10 times.

Also, the halogen used in the present invention
As an effective source gas for atom supply, for example,
Halogen including halogen gas, halide, halogen
Intermediate compounds, gases such as silane derivatives substituted with halogens
Preferred are gaseous or gasifiable halogen compounds.
Can be Furthermore, it comprises silicon atoms and halogen atoms
Gaseous or gasifiable halogen atoms as elements
Silicon hydride compounds containing
Can be. Halogenation that can be suitably used in the present invention
As the compound, specifically, fluorine gas (F_Two ), BrF,
CIF, CIF _Three , BrF_Three , BrF_Five , IF_Three , IF
₇ And the like. Haloge
With a silicon compound containing a halogen atom, a so-called halogen atom
Specific examples of the silane derivative include, for example, S
iF_Four , Si_Two F₆ Etc. are preferred.
Can be mentioned.

Substances that can serve as a carbon supply gas include:
Examples include gaseous hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ , and hydrocarbons which can be gasified, and further, such as ease of handling at the time of forming a layer, and high Si supply efficiency. In C
H ₄ and C ₂ H ₆ are preferred.

Substances that can become nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ , C
Compounds in a gaseous state or gasifiable such as O, CO ₂ , and N ₂ are mentioned.

The atoms contained in each layer may be distributed evenly and uniformly in the layer, or may be contained evenly in the thickness direction of the layer but in a non-uniformly distributed state. There may be parts that are. However, in any case, it is necessary to be uniformly contained in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics uniform in the in-plane direction.

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

FIG. 6 shows a high frequency plasma CVD (hereinafter referred to as “R”).
FIG. 2 is a schematic configuration diagram illustrating an example of a method of manufacturing an electrophotographic photoreceptor by a method described as “F-PCVD”). This apparatus is roughly classified into a deposition apparatus 5100 and a source gas supply apparatus 52.
00, an exhaust device 5117 for reducing the pressure inside the reaction vessel 5111. In a reaction vessel 5111 in the deposition apparatus 5100, a conductive support 5112, a heater 5113 for heating a substrate, a raw material gas introduction pipe 5114 are provided, and a high frequency matching box 5115 is connected.

The raw material gas supply device 5200 includes SiH ₄ ,
Source gas cylinders 5221 to 5226 such as H ₂ , CH ₄ , NO, B ₂ H ₆ , GeH ₄ and valves 5231 to 523
6, 5241 to 5246, 5251 to 5256, and mass flow controllers 5211 to 5216, and the cylinders for each source gas are connected to a gas introduction pipe 5114 in a reaction vessel 5111 via a valve 5260.

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the conductive substrate 51
12 is set in the reaction vessel 511. Conductive substrate 5112
Is preferably a cylindrical shape in the case of an electrophotographic photosensitive member. After installation,
The inside of the reaction vessel 5111 is evacuated by the exhaust device 5117 (for example, a vacuum pump). Subsequently, the heater 5113 for heating the support is turned ON, and the temperature of the conductive support 5112 is set to 50.
The temperature is controlled to a predetermined temperature of from 500C to 500C.

A source gas for forming a deposited film is supplied to a reaction vessel 511.
In order to make the gas flow into the gas cylinder 1, the valves 5231 to 5231 of the gas cylinder
236, confirming that the leak valve 5123 of the reaction vessel is closed, and checking the inflow valves 5251 to 625
6. Outflow valves 5241 to 5246, auxiliary valves 526
0 is open and the main valve 51
18 to open the reaction vessel 5111 and the inside of the gas pipe 511
Exhaust 6

Next, the reading of the vacuum gauge 5124 is about 6.65 ×
When the pressure reaches 10 ⁻⁴ Pa, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed. Thereafter, each gas is supplied from the gas cylinders 5221 to 5226 to the valves 5231 to 5223.
36 is opened and introduced, and each gas pressure is adjusted by the pressure adjusters 5261 to 5266 (for example, 196 kPa). Next, the inflow valves 5241 to 5246 are gradually opened, and each gas is introduced into the mass flow controllers 5211 to 5216.

When the conductive support 5122 reaches a predetermined temperature, necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5221 to 5226 to the gas introduction pipe 5.
It is introduced into the reaction vessel 5111 via 114. Next, each source gas is adjusted by the mass flow controllers 5211 to 5216 so as to have a predetermined flow rate. that time,
The opening of the main valve 5118 is adjusted while watching the vacuum gauge 5124 so that the pressure in the reaction vessel 5111 becomes a predetermined pressure of 133 Pa or less. When the internal pressure is stable,
An RF power source (not shown) is set to a desired power, and the reaction vessel 5111 is passed through a high-frequency matching box 5115.
RF power is introduced into the device to generate an RF glow discharge.
The source gas introduced into the reaction vessel is decomposed by the discharge energy, and a predetermined deposited film is formed on the conductive support 5112. After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed, the flow of gas into the reaction vessel is stopped, and the formation of the undercoat layer is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a multilayer structure such as a lower blocking layer, a photoconductive layer, and a surface protective layer is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed.
, Outflow valves 5251-5256 to reaction vessel 511
In order to avoid remaining in the piping leading to 1, the operation of closing the outflow valves 5251 to 5256, opening the auxiliary valve 5260, and further fully opening the main valve 5118 to once evacuate the system to a high vacuum as necessary. Do it. Also,
To achieve uniform film formation, the conductive support 5112 is rotated at a predetermined speed by a driving device (not shown) during the film formation.

It goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

Next, a method of manufacturing an electrophotographic photosensitive member formed by a high-frequency plasma CVD (hereinafter abbreviated as “VHF-PCVD”) method using a VHF band frequency will be described.

RF-PC in the manufacturing apparatus shown in FIG.
By replacing the deposition apparatus 5110 by the VD method with the deposition apparatus 6100 shown in FIG. 7 and connecting it to the raw material gas supply apparatus 5200, an electrophotographic photosensitive member manufacturing apparatus for electrophotography by the VHF-PCVD method can be obtained.

This apparatus is roughly composed of a reaction vessel 6111 having a vacuum-tight structure and capable of reducing pressure, a supply device 5200 for raw material gas, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. ing. Reaction vessel 611
1, a conductive support 6112, a heater 6113 for heating the support, a raw material gas introduction pipe (not shown), and an electrode 6115 are provided.
116 is connected. Further, the inside of the reaction vessel 6111 is connected to a diffusion pump (not shown) through an exhaust pipe 6121.

The source gas supply device 5200 is composed of SiH ₄ , G
Cylinders 5221 to 5226 for source gases such as eH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ and valves 5231 to 523
6, 5241 to 5246, 5251 to 5256, and mass flow controllers 5211 to 5216. Each raw material gas cylinder is connected to a gas introduction pipe (not shown) in the reaction vessel 6111 via a valve 5260. A space 6130 surrounded by the conductive support 6112 forms a discharge space.

The formation of a deposited film in this apparatus by the VHF-PCVD method can be performed as follows. First,
A conductive support 6112 is provided in a reaction vessel 6111,
The support 6112 is rotated by the driving device 6120, and the reaction vessel 6 is rotated by an exhaust device (not shown) (for example, a diffusion pump).
111 is evacuated through an exhaust pipe 6121 and the reaction vessel 6 is exhausted.
The pressure in 111 is adjusted to 1.33 × 10 ⁻⁵ Pa or less. Subsequently, the temperature of the conductive support 6112 is heated and held at a predetermined temperature of 50 ° C. to 500 ° C. by the support heating heater 6113.

A source gas for forming a deposited film is supplied to a reaction vessel 611.
In order to make the gas flow into 1, the gas cylinder valve 54231-
5236, confirm that the leak valve (not shown) of the reaction vessel is closed,
After confirming that the 5246, the outflow valves 5251 to 5256, and the auxiliary valve 5260 are open, first, the main valve (not shown) is opened to evacuate the reaction vessel 6111 and the gas pipe.

Next, the reading of a vacuum gauge (not shown) is about 6.65.
When the pressure becomes × 10 ⁻⁴ Pa, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed.

Thereafter, gases are introduced from gas cylinders 5221 to 5226 by opening valves 5231 to 5236, respectively.
Each gas pressure is set to 2 × 1 by the pressure regulators 5261 to 5266.
Adjust to 0 ⁵ Pa. Next, the inflow valves 5241 to 52
46 is gradually opened, and each gas is introduced into the mass flow controllers 5211-5216.

After the preparation for film formation is completed as described above, a deposited film is formed on the conductive support 6112 as follows.

When the conductive support 6112 reaches a predetermined temperature, necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5211 to 5226 to the gas inlet pipe (not shown). Through the discharge space 61 in the reaction vessel 6111
30. Next, the mass flow controller 521
Adjustment is made so that each source gas has a predetermined flow rate according to 1-5216. At this time, the pressure in the discharge space 3130 becomes 1
The opening of the main valve (not shown) is adjusted while watching the vacuum gauge (not shown) so that the pressure becomes a predetermined pressure of 33 Pa or less.

When the pressure is stabilized, for example, the frequency 1
A VHF power supply (not shown) of 05 MHz is set to a desired power, and a discharge space 6 is supplied through a matching box 6116.
VHF power is introduced into 130 to cause glow discharge. Thus, in the discharge space 6130 surrounded by the support 6112, the introduced source gas is excited by the discharge energy and dissociated, and a predetermined deposited film is formed on the support 6112. At this time, simultaneously with the introduction of the VHF power, the output of the heater 6113 for heating the support is adjusted to change the temperature of the conductive support at a predetermined value. At this time, a motor 6120 for rotating the support is used to make the layer formation uniform.
To rotate at a desired rotation speed.

After the desired film thickness is formed, the supply of VHF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the layer is completed.

By repeating the same operation a plurality of times, an electrophotographic photosensitive member having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed.
, Outflow valves 5251-5256 to reaction vessel 611
In order to avoid remaining in the piping leading to 1, the operation of closing the outflow valves 5251 to 5256, opening the auxiliary valve 5260, and further fully opening the main valve (not shown) to once evacuate the system to a high vacuum is performed. Perform as needed.

It goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

The method of heating the conductive supports 5112 and 6112 may be a heating element that uses vacuum, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, or a ceramic heater. , Halogen lamps, infrared lamps and other heat radiation lamps,
A heating element using a gas or the like as a heat medium and a heat exchange unit may be used. As the surface material of the heating means, metals such as stainless steel, nickel, aluminium, and copper, ceramics, heat-resistant polymer resins, and the like can be used. Also, the reaction vessel 51
In addition to providing a container dedicated to heating in addition to 11 and 6111 and heating the conductive supports 5112 and 6112, the reaction container 511 is heated.
1,6111, conductive supports 5112, 61 in vacuum
For example, a method of transporting No. 12 is used.

The size and shape of the electrode 6115 provided in the discharge space in the VHF-PCVD method may be any as long as they do not disturb the discharge.
A cylindrical shape with a length of m to 10 cm is preferred. At this time, the length of the electrode 6115 can be arbitrarily set as long as the electric field is uniformly applied to the conductive support 6112.

The material of the electrode 6115 may be any material as long as its surface becomes conductive. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, T
Metals such as e, V, Ti, Pt, Pb, and Fe, alloys thereof, and glass and ceramics whose surfaces are subjected to conductive treatment are usually used.

The electrophotographic photosensitive member manufactured by the method of the present invention is used not only for electrophotographic machines but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making machines. Can also be widely used.

[0093]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 Using a plasma CVD apparatus shown in FIG. 6, a lower blocking layer and a photoconductive layer were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1. Next, the surface was etched under the conditions shown in Table 2 to change the surface irregularities. Thereafter, the surface layers shown in Table 3 were laminated to complete an electrophotographic photosensitive member. As shown in the table, each deposition rate was 4 Å / sec.
c, 10 angstroms / sec, and 0.5 angstroms / sec. In this embodiment, seven photoconductors were prepared by changing the etching conditions.

N, in the surface layer of the produced electrophotographic photosensitive member,
The content of O was measured by SIMS analysis to be 0.5 atomic% and 0.8 atomic%, respectively, and the content in the photoconductive layer in contact with the surface layer was 0.0005 atomic%, respectively.
It was 0.0010 atomic%. Regarding F and B, there was no significant difference between the two. The surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope).

The thus prepared electrophotographic photosensitive member was evaluated as follows.

Adhesion test: Cross-hatched streaks were made on the surface of the produced electrophotographic photosensitive member at intervals of 1 cm using a sharp needle. This was immersed in water for one week, taken out, and visually inspected for any peeling of the film from the damaged part.

◎ No peeling occurred, very good Δ Peeling spread to a very small portion from the muscle wound.

C: Peeling occurred over a wide area.

Endurance test: The electrophotographic photosensitive member was mounted on a modified copy machine NP-5060 manufactured by Canon Inc., and 100,000 sheets were subjected to durability while passing A4 copy paper. The image during the durability test and the surface of the photoreceptor after the durability test were visually inspected to determine whether or not the surface layer had peeled off.

◎ No peeling occurred, very good △ Very small peeling occurred × Wide peeling occurred and there was a problem in practice Forced jam test: Installed in electrophotographic apparatus and passed paper A paper jam condition was forced. This work 1
It was repeated 0 times, and it was checked on the image whether or not the photoconductor was peeled off.

◎ Very good without scratching △ The photoreceptor was slightly scratched but did not appear on the image,
No problem in practical use × There is a problem in practical use with scratches appearing on the image Charging ability: Install the electrophotographic photosensitive member in the electrophotographic device, apply a high voltage of +6 kV to the charger, perform corona charging, and use a surface potentiometer. The dark surface potential of the electrophotographic photosensitive member was measured at the developing position.

Sensitivity: The electrophotographic photosensitive member is charged to a constant dark area surface potential. And immediately use a filter 5
Irradiation with halogen lamp light excluding light in a wavelength range of 50 nm or more is performed, and the amount of light is adjusted such that the surface potential of the bright portion of the electrophotographic photosensitive member becomes a predetermined value. At this time, the necessary light amount is converted from the lighting voltage of the halogen lamp light source. The sensitivity was evaluated from this light amount.

Residual potential: The electrophotographic light-receiving member is charged to a constant dark-area surface potential. Then, a relatively strong light (for example, 2 L.s) having a constant light amount is immediately irradiated. The light image is 550 using a halogen lamp light source and a filter.
Irradiation was performed with light excluding light in the wavelength range of nm or more. At this time, the surface potential of the light portion of the electrophotographic light-receiving member was measured with a surface electrometer.

Ghost: A ghost test chart made by Canon (part number: FY9-9040) has a reflection density of 1.
1. A black circle having a diameter of 5 mm is attached to the front end of the image on the platen, and a Canon halftone chart (part number: FY9-9042) is placed on top of the image. The difference between the reflection density of φ5 mm of the ghost chart and the reflection density of the halftone portion observed in the above was measured and evaluated.

The above-mentioned charging ability, sensitivity, residual potential, and ghost were ranked as follows.

非常 Very good 良好 Good △ Conventional level, no practical problem × No practical problem The results of Example 1 are shown in Table 4. From the first embodiment, the effect of the present invention is that the surface roughness is controlled to 500 Å to 2000 Å and N and O are 0.001 atomic%.
It has been found that a particularly remarkable effect is obtained when the content is 5 to 5 atomic%.

[0108]

Table 1 Photoconductor production conditions Lower blocking layer: SiH ₄ 200 sccm H ₂ 500 sccm NO 5 sccm B ₂ H ₆ 2000 ppm Power 150 W Internal pressure 80 Pa Base temperature 200 ° C. Film thickness 1.5 μm Deposition rate 4 Å / sec Photoconductive layer ... SiH ₄ 510 sccm H ₂ 450 sccm Power 450 W Internal pressure 73 Pa Base temperature 200 ° C. Film thickness 20 μm Deposition rate 10 Å / sec

[0109]

Table 2 Etching conditions: CF ₄ 400 sccm Power 50 W to 2000 W Base temperature 200 ° C. Pressure 50 Pa

[0110]

Table 3 Surface layer according to the present invention Surface layer: CH ₄ 200 sccm NO 1 sccm Power 1000 W Internal pressure 67 Pa Base temperature 200 ° C. Film thickness 0.3 μm Deposition rate 0.5 Å / sec

[0111]

[Table 4] Example 2 Using a plasma CVD apparatus shown in FIG. 6, a lower blocking layer and a photoconductive layer were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1. Next, the surface was etched under the conditions shown in Table 2 to control the surface irregularities to about 800 Å. Thereafter, the surface layers shown in Table 5 were laminated to complete an electrophotographic photosensitive member. As shown in the table, each deposition rate
4 angstroms / sec, 10 angstroms /
sec, 2.5 angstroms / sec. In the present embodiment, six electrophotographic photoreceptors in which the contents of F and B contained in the surface layer were changed were prepared. The contents of F and B in the surface layer of the produced electrophotographic photosensitive member were measured by SIMS analysis. The contents in the photoconductive layer in contact with the surface layer were 0.0005 atomic% and 0.0005 atomic%, respectively.
Regarding N and O, no significant difference was found between the two.

The thus prepared electrophotographic photosensitive member was evaluated in the same manner as in Example 1.

Table 6 shows the results. From Example 2, it was found that the effect of the present invention was particularly remarkable when the surface roughness was controlled to 500 Å to 2,000 Å and F and B were contained at 0.001 to 5 atomic%. did.

[0114]

Table 5 Surface layer according to the present invention Surface layer: CH ₄ 500 sccm B ₂ H ₆ (change) CF ₄ (change) Power 1000 W Internal pressure 67 Pa Base temperature 200 ° C. Film thickness 0.3 μm Deposition rate 2.5 Å / sec

[0115]

[Table 6] Comparative Example 1 A lower blocking layer and a photoconductive layer were sequentially laminated on a cylindrical Al substrate under the conditions shown in Table 1 using the plasma CVD apparatus shown in FIG. Next, the surface was etched under the conditions shown in Table 2 to control the surface irregularities. Thereafter, the surface layers shown in Table 7 were laminated to complete an electrophotographic photosensitive member. As shown in the table, each deposition rate was 4 Å / sec.
c, 10 angstroms / sec, and 0.5 angstroms / sec.

When the contents of N, O, F, and B in the surface layer of the electrophotographic photosensitive member and the photoconductive layer in contact with the surface layer were measured by SIMS analysis, a large difference was found between the two. Did not. When the surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope), Rz was about 1500 angstroms.

The electrophotographic photosensitive member thus prepared was evaluated in the same manner as in Example 1. Table 8 shows the results. From the results of Comparative Example 1, the surface roughness was 500 Å to 2000
Even if the thickness is controlled to Angstroms, the effect of the present invention may not be obtained if at least two or more atoms selected from N, O, F, and B are not contained in a larger amount than the layer in contact with the surface layer. Understand.

[0118]

Table 7 Surface layer according to the present invention Surface layer: CH ₄ 200 sccm Power 1000 W Internal pressure 67 Pa Base temperature 200 ° C. Film thickness 0.3 μm Deposition rate 0.5 Å / sec

[0119]

[Table 8] Example 3 Using a plasma CVD apparatus shown in FIG. 6, a lower blocking layer and a photoconductive layer were formed on a cylindrical Al substrate under the conditions shown in Table 1, and subsequently, a-SiC shown in Table 9 was formed. An electrophotographic photosensitive member was formed by laminating buffer layers. Next, the surface was etched under the conditions shown in Table 2 to control the surface irregularities. Thereafter, the surface layers shown in Table 10 were laminated to complete the electrophotographic photosensitive member. As shown in the table, each deposition rate was 4 angstroms / sec, 10 angstroms / sec, 3.0 angstroms / sec,
0.5 angstrom / sec.

O, in the surface layer of the produced electrophotographic photosensitive member,
When the content of B was measured by SIMS analysis, it was 0.8 atomic% and 0.025 atomic%, respectively, and the content in the a-SiC buffer layer in contact with the surface was 0.1 atomic%, respectively.
0090 atomic% and 0.0017 atomic%. Regarding N and F, no large difference was found between the two. When the surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope), Rz was about 1000 angstroms.

Table 11 shows the results of evaluating the electrophotographic photosensitive member thus produced in the same manner as in Example 1. From Example 3, it was found that the effect of the present invention can be similarly obtained even if there is a buffer layer such as a-SiC between the photoconductive layer and the surface layer.

[0122]

Table 9 Buffer layer manufacturing conditions a-SiC buffer layer: SiH ₄ 50 sccm CH ₄ 450 sccm Power 450 W Internal pressure 40 Pa Base temperature 200 ° C. Film thickness 0.5 μm Deposition rate 3.0 Å / sec

[0123]

Table 10 Surface layer according to the present invention Surface layer: CH ₄ 200 sccm B ₂ H ₆ (H ₂ dilution 10,000 ppm) 50 sccm O ₂ (He dilution) 20 sccm Power 1000 W Internal pressure 67 Pa Base temperature 200 ° C. Film thickness 0.3 m Deposition rate 2.5 angstroms / sec

[0124]

[Table 11] Example 4 A lower blocking layer and a photoconductive layer were formed on a cylindrical Al substrate using the plasma CVD apparatus shown in FIG. 6 under the conditions shown in Table 1, and subsequently the a-SiC shown in Table 9 was formed. An electrophotographic photosensitive member having a buffer layer laminated thereon was prepared. In this example, the surface layers shown in Table 12 were laminated without any control of the surface irregularities to complete the electrophotographic photosensitive member. As shown in the table, each deposition rate was 4 Å / sec.
c, 10 angstroms / sec, and 0.5 angstroms / sec.

O, in the surface layer of the produced electrophotographic photosensitive member,
The F content was measured by SIMS analysis to be 0.4 atomic% and 0.12 atomic%, respectively, and the content in the a-SiC buffer layer in contact with the surface was 0.00 atomic%, respectively.
80 atomic% and 0.0041 atomic%. Regarding N and B, no significant difference was found between the two. When the surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope), Rz was about 2000 angstroms.

The electrophotographic photosensitive member thus produced was evaluated in the same manner as in Example 3, and as a result, very good results similar to those in Example 3 were obtained. From this, it was found that if the unevenness of the surface was within the range of the present invention, it was not necessary to intentionally control by etching or the like, and the effect of the present invention could be obtained.

[0127]

Table 12 Surface layer according to the present invention Surface layer: CH ₄ 200 sccm CF ₄ 5 sccm O ₂ (He dilution 10%) 10 sccm Power 1000 W Internal pressure 67 Pa Substrate temperature 200 ° C. Film thickness 0.3 m Deposition rate 0.5 Å / sec Example 5 Using a plasma CVD apparatus shown in FIG. 6, a lower blocking layer and a photoconductive layer were formed on a cylindrical Al substrate under the conditions shown in Table 1, and subsequently, a-SiC shown in Table 13 was formed.
An electrophotographic photosensitive member having a buffer layer laminated thereon was prepared. The a-SiC buffer layer of this example was of an all-layer variable type, and was formed so that the composition would change smoothly from the photoconductive layer toward the surface layer. Therefore, the surface layer shown in Table 13 was further laminated without any control of the surface irregularities to complete the electrophotographic photosensitive member. As shown in the table, each deposition rate
4 angstroms / sec, 10 angstroms /
sec, 3.0 → 1.0 angstroms / sec,
0.5 angstrom / sec.

N, in the surface layer of the produced electrophotographic photosensitive member,
When the content of F was measured by SIMS analysis, it was 0.50 atomic% and 0.04 atomic%, respectively. The content at the central position in the film thickness direction in the a-SiC buffer layer in contact with the surface was: They were 0.0010 atomic% and 0.0014 atomic%, respectively. Regarding O and F, no large difference was found between the two. When the surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope), R
z was about 1800 angstroms.

The electrophotographic photoreceptor thus produced was evaluated in the same manner as in Example 3. As a result, very good results similar to those in Example 3 were obtained. From this, it was found that the effect of the present invention can be similarly obtained even when the composition of the buffer layer changes in the film thickness direction.

[0130]

Table 13 a-SiC buffer layer: SiH ₄ 50 sccm CH ₄ 450 → 50 sccm Power 450 W Internal pressure 50 Pa Substrate temperature 200 ° C. Film thickness 0.5 μm Deposition rate 3.0 → 1.0 Å / sec Surface layer: CH ₄ 50 sccm N ₂ 1 sccm B ₂ H ₆ (H ₂ dilution 1000 ppm) 15 sccm power 1000 W internal pressure 67 Pa substrate temperature 200 ° C. film thickness 0.3 m deposition rate 0.5 angstrom / sec Example 6 Instead of the plasma CVD apparatus shown in FIG. A lower blocking layer, a photoconductive layer, an a-SiC buffer layer, and a surface layer are laminated on a cylindrical Al substrate under the conditions shown in Table 14 using a mass-production type apparatus using the VHF plasma CVD method shown in FIG. An electrophotographic photosensitive member was prepared. The electrophotographic photoreceptor was completed without any control of surface irregularities.

N, in the surface layer of the produced electrophotographic photosensitive member,
When the content of F was measured by SIMS analysis, it was 0.5 atomic% and 0.12 atomic%, respectively, and the content in the a-SiC buffer layer in contact with the surface was 0.001% each.
5% by atom and 0.0050% by atom. For O and B, no significant difference was found between the two. a-SiC
The contents of N and F in the photoconductive layer in contact with the buffer layer were 0.0005 atomic% and 0.0035 atomic%, respectively. When the surface roughness of the obtained electrophotographic photosensitive member was measured by AFM (atomic force microscope), Rz was about 180.
It was 0 angstroms.

The electrophotographic photoreceptor thus produced was evaluated in the same manner as in Example 4. As a result, very good results similar to those in Example 4 were obtained. From this, it has been found that the effects of the present invention can be obtained regardless of the film formation method.

[0133]

Table 14 Manufacturing conditions of photoreceptor Lower blocking layer: SiH ₄ 150 sccm H ₂ 350 sccm NO ₃ sccm B ₂ H ₆ 2000 ppm Power 200 W Internal pressure 7 Pa Base temperature 200 ° C. Film thickness 1.5 μm Deposition rate 6 Å / sec Photoconductive layer ... SiH ₄ 200sccm H ₂ 350sccm power 450W pressure 5Pa substrate temperature 200 ° C. The film thickness 20μm deposition rate 9.0 Å / sec a-SiC layer buffer layer ... SiH ₄ 10sccm CH ₄ 400sccm power 450W pressure 5Pa substrate temperature 200 ° C. The film thickness 0 0.5 μm Deposition rate 2.0 Å / sec Surface layer: CH ₄ 200 sccm N ₂ 1 sccm CF ₄ 5 sccm Power 1000 W Internal pressure 7 Pa Substrate temperature 200 ° C. Film thickness 0.2 μm Deposition rate 0. Example 8 A lower blocking layer and a photoconductive layer were sequentially laminated on a cylindrical Al substrate under the conditions described in Table 1 using the plasma CVD apparatus shown in FIG. 6 under the conditions shown in Table 1, and subsequently shown in Table 15. A-S
An electrophotographic photoreceptor having an iC buffer layer laminated thereon was prepared.
Next, the surface was etched under the conditions shown in Table 2 to control the surface irregularities to about 1500 angstroms. Next, Table 1
As shown in FIG. 5, the CH ₄ flow rate was changed to 10 to 500 sccm, and surface layers with different deposition rates were laminated to complete seven electrophotographic photosensitive members. Each deposition rate was 4 Å / sec, 10 Å / sec,
3.0 angstrom / sec, and 0.1 to 4.0 angstrom / sec. Further, the content of N, O, F, and B contained in the surface layer of the present example was changed, and eight electrophotographic photosensitive members were prepared.

N, in the surface layer of the produced electrophotographic photosensitive member,
The results of measuring the contents of O, F, and B by SIMS analysis are shown in Table 16. The contents in the a-SiC buffer layer in contact with the surface were 0.0010 atomic% and 0.0085 atomic%.
It was confirmed that at least two or more atoms contained much more than atomic%, 0.0040 atomic%, and 0.0015 atomic%. The contents of the photoconductive layer in contact with the a-SiC buffer layer are 0.0005 atomic%, 0.0009 atomic%, 0.0035 atomic%, and 0.005 atomic%, respectively.
00010 atomic%.

The thus prepared electrophotographic photosensitive member was evaluated in the same manner as in Example 1.

The results are shown in Table 16, and it was found that the surface layer of the present invention had a remarkable effect when the deposition rate was lower than that of the buffer layer in contact with the surface layer.

[0137]

Table 15 Buffer layer manufacturing conditions a-SiC layer buffer layer: SiH ₄ 20 sccm CH ₄ 300 sccm power 400 W internal pressure 30 Pa base temperature 200 ° C. Film thickness 0.5 μm Deposition rate 3.0 angstrom / sec Surface layer: CH ₄ (Change) N ₂ (Change) O ₂ (He dilution 10%) (Change) B ₂ H ₆ (H ₂ dilution 1000 ppm) (Change) CF ₄ (Change) Power 1000 W Internal pressure 67 Pa Base temperature 200 ° C. Film thickness 0.3 μm Deposition rate 0.1-5.0 angstroms / sec

[0138]

[Table 16]

[0139]

According to the present invention, a photoconductive layer composed of a non-single-crystal material mainly composed of silicon atoms is provided on a conductive substrate, and at least a surface layer made of non-single-crystal carbon containing hydrogen. Is formed on the electrophotographic photosensitive member, the surface layer has a surface roughness Rz of 50 μm when the reference length is 5 μm.
0 Å or more and 2000 Å or less, and the surface layer contains at least two types of atoms selected from oxygen, nitrogen, fluorine and boron atoms, and has a deposition rate smaller than that of the layer in contact with the surface layer. By doing so, it is possible to provide a high-quality electrophotographic photoreceptor with good electrical characteristics, which does not cause peeling, scratching, or abrasion during long-term use.

[Brief description of the drawings]

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

FIG. 2 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member according to the present invention.

FIG. 3 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member according to the present invention.

FIG. 4 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member according to the present invention.

FIG. 5 is a schematic configuration diagram for explaining a configuration of a preferred embodiment of an electrophotographic photosensitive member according to the present invention.

FIG. 6 is a schematic explanatory view of an example of an apparatus used for forming an electrophotographic photosensitive member according to the present invention, which is a manufacturing apparatus using an RF glow discharge method.

FIG. 7 is a schematic explanatory view of an example of an apparatus used for forming an electrophotographic photosensitive member according to the present invention, which is a mass-production type manufacturing apparatus using a VHF glow discharge method.

[Explanation of symbols]

101, 201, 301, 401, 501 Conductive substrate 102, 202, 302, 402, 502 Photoconductive layer 103, 203, 303, 403, 503 Surface layer 204, 504 Buffer layer 305, 405, 505 Lower blocking layer 402 Charge Generation layer 406 Charge transport layer 5100, 6100 Deposition device 5111, 6100 Reaction vessel 5112, 6112 Conductive support 5113, 6113 Support heating heater 5114 Source gas introduction pipe 5115, 6115 Matching box 5116 Source gas pipe 5117 Reaction vessel leak valve 5118 Main exhaust valve 5119 Vacuum gauge 5200 Source gas supply device 5211-5216 Mass flow controller 5221-5226 Source gas cylinder 5231-5236 Source gas cylinder valve 5241-5 46 gas inlet valve 5251 to 5,256 gas outflow valves 5261 to 5266 pressure regulators 6115 electrodes 6120 support rotating motor 6121 exhaust pipe 6130 discharge space

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) in Canon Inc. 2H068 CA03 DA12 DA15 DA17 DA23 DA41 EA34

Claims (14)

[Claims] 1. An electrophotography having a photoconductive layer made of a non-single-crystal material mainly composed of silicon atoms on a conductive substrate, and having a surface layer made of non-single-crystal carbon containing at least hydrogen. In the photoreceptor, the surface layer has a reference length of 5
a surface roughness Rz of 500 μm or more and 2000 Å or less in the case of μm, and the surface layer contains two or more kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms. An electrophotographic photoreceptor, wherein the deposition rate of the surface layer is lower than the deposition rate of the layer in contact with the surface layer. 2. The method according to claim 1, wherein the surface layer contains at least two kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms, and the content of these atoms is larger than that of the layer in contact with the surface layer. 2. The electrophotographic photosensitive member according to 1. 3. The electrophotographic photosensitive member according to claim 1, further comprising a buffer layer provided between the photoconductive layer and the surface layer. 4. The electrophotographic photosensitive member according to claim 3, wherein the buffer layer is made of a non-single-crystal material containing silicon atoms as a base and further containing carbon atoms. 5. The buffer layer further contains at least two kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms, and the content of these atoms is higher than that of the layer on the conductive substrate side in contact with the buffer layer. 4. The method according to claim 3, wherein the number is large.
Or the electrophotographic photosensitive member according to 4. 6. The electrophotographic photosensitive member according to claim 3, wherein the buffer layer is formed so that the deposition rate of the buffer layer is lower than that of the layer on the side of the conductive substrate in contact with the buffer layer. 7. The method according to claim 1, wherein the content of at least two kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms contained in the surface layer is 0.001 at% to 5 at%. 7. The electrophotographic photosensitive member according to 1 to 6. 8. A photoconductive layer composed of a non-single-crystal material having silicon atoms as a base on a conductive substrate, and a surface layer composed of non-single-crystal carbon containing at least hydrogen, wherein the surface layer is , Surface roughness Rz when reference length is 5 μm
In a method for producing an electrophotographic photoreceptor in which the surface layer contains at least two atoms selected from oxygen, nitrogen, fluorine, and boron atoms, wherein the deposition of the surface layer is not less than 500 angstroms and less than 20,000 angstroms. A method for producing an electrophotographic photoreceptor, wherein the lamination is performed so that the speed is lower than that of the layer in contact with the surface layer. 9. The surface layer according to claim 8, wherein the content of at least two kinds of atoms selected from oxygen, nitrogen, fluorine and boron atoms is larger than that of the layer in contact with the surface layer.
3. The method for producing an electrophotographic photoreceptor according to item 1. 10. The method according to claim 8, further comprising providing a buffer layer between the photoconductive layer and the surface layer. 11. The method according to claim 10, wherein the buffer layer is made of a non-single crystal material containing silicon atoms as a base material and further containing carbon atoms. 12. The method according to claim 12, wherein the buffer layer further comprises oxygen, nitrogen,
12. The semiconductor device according to claim 10, comprising at least two kinds of atoms selected from fluorine and boron atoms, wherein the content of these atoms is larger than that of the layer on the conductive substrate side in contact with the buffer layer. A method for producing an electrophotographic photoreceptor. 13. The method according to claim 10, wherein the deposition rate of the buffer layer is smaller than the deposition rate of the layer on the conductive substrate side in contact with the buffer layer. A method for producing an electrophotographic photoreceptor. 14. Oxygen, fluorine contained in the surface layer,
14. The method according to claim 8, wherein the content of at least two kinds of atoms selected from boron atoms is 0.001 to 5 atomic%. Method.