JP2001330981A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor in which image defects such as leak spots caused by an abnormal discharge or the like of an electrifying device and pressure flaws caused by external impact force added on the photoreceptor are prevented and with which images of high quality and high picture quality can be supplied for a long period. SOLUTION: The electrophotogrphic photoreceptor is obtained by laminating a nonsingle crystal hydrogenated carbon film as a base coating layer on a conductive substrate and further successively laminating light-accepting layers including a photoconductive layer which consists of a non-single crystal material essentially comprising at least silicon atoms on the base coating layer. The distribution of the hydrogen amount in the base coating layer shows a region with a high hydrogen content and a region with a low hydrogen content in the film thickness direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron which is susceptible to electromagnetic waves such as light (here, light in a broad sense, which means ultraviolet light, visible light, infrared light, X-rays, .gamma.-rays, etc.). It relates to a photoreceptor.

[0002]

2. Description of the Related Art As a material for forming a photoconductive layer in a solid-state image pickup device, an electrophotographic photosensitive member in the field of image formation, or a document reading device, the SN ratio [photocurrent (Ip) / (Id)] is high. High, having an absorption spectrum characteristic matched to the spectral characteristic of the irradiating electromagnetic wave, fast light response, having a desired dark resistance value,
It is required that the device be harmless to the human body when used, and that the solid-state imaging device be capable of easily processing an afterimage within a predetermined time. Particularly in the case of an electrophotographic photosensitive member used in an office as an office machine, the above harmlessness during use is an important point.

[0003] A material that has attracted attention from such a viewpoint is amorphous silicon (hereinafter, referred to as dangling bond) modified with a monovalent element such as hydrogen or a halogen atom.
"A-Si").
No. 86341 describes an application to an electrophotographic photosensitive member.

Conventionally, as a method of forming an electrophotographic photosensitive member having a light-receiving layer made of a-Si on a conductive substrate, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), There are many known methods such as a method of decomposing a source gas (optical CVD method) and a method of decomposing a source gas by plasma (plasma CVD method). Above all, the plasma CVD method, that is, a method of decomposing a raw material gas by direct current or high frequency, microwave glow discharge and the like to form a deposited film on a conductive substrate, is currently in practical use, such as a method of forming an electrophotographic photosensitive member. It is going to.

As a layer structure of such a deposited film, an attempt has been made to use a material other than a-Si in addition to an electrophotographic photoreceptor having conventionally used a-Si as a base and appropriately modifying elements added thereto. Has also been made.

Japanese Patent Application Laid-Open No. 60-63541 discloses a photoconductor in which an intermediate layer of a diamond-like carbon film is laminated on a conductive substrate, and a photoconductive layer is laminated thereon.

Japanese Patent Application Laid-Open No. Sho 62-196371 discloses a technique using an amorphous carbon intermediate layer on a substrate.

[0008] For example, Japanese Patent Application Laid-Open No. 63-61261 discloses that an a-Si photosensitive layer is provided between a conductive substrate and an a-Si photosensitive layer.
A photosensitive member having a C: H film is disclosed.

[0009] However, any of these techniques is a technique for improving the adhesion and the stopping power, and no technique for simultaneously improving the adhesion, the hardness, and the electric breakdown voltage is disclosed.

[0010]

According to such a conventional method for forming an electrophotographic photosensitive member, it has become possible to obtain an electrophotographic photosensitive member having some practical characteristics and uniformity. However, these conventional methods for forming an electrophotographic photosensitive member have the following problems to be solved in an electrophotographic process in which charging, exposure, development, and cleaning steps are sequentially performed.

As a means for efficiently recovering the developer without impairing the cleaning property in the cleaning step, a spike of the developer is formed by a magnet roller, and the surface of the electrophotographic photosensitive member is rubbed with a developer brush. Thus, means for collecting the developer has been proposed.

However, an a-Si type electrophotographic photosensitive member,
Particularly, in an electrophotographic apparatus using a so-called blocking type electrophotographic photosensitive member having a charge injection blocking layer, a photoconductive layer, and a surface protective layer formed on the surface of a conductive substrate, the developer has an insulating property. When the above-described rubbing with the developer brush is performed using the magnetic toner, the material forming the brush and the toner may be charged by friction with each other or with the surface of the electrophotographic photosensitive member, and may be charged up. is there.

Although the average potential of the charged toner is about 700 V on the magnet roller, there is a difference in the charge amount of each toner particle, and it is considered that some of the high potential toners reach 1500 V.

For this reason, a minute dielectric breakdown occurs in the electrophotographic photosensitive member, and white spots occur in a solid black image portion in the case of normal development, and black spots occur in a solid white image portion in the case of reverse development. In some cases, image quality was impaired.

In the blocking type photoreceptor, the charge injection blocking layer, the photoconductive layer and the surface protective layer have a thickness of 1 to 5 respectively.
μm, 20 to 30 μm, 0.1 to 1 μm, relative dielectric constants of 7.5, 11, and 4 respectively, and a shared electric field ratio of 6: 4: 11.
Is well known.

On the other hand, the electric field resistance (dielectric breakdown voltage per unit layer thickness) of each of the layers is substantially equal between the charge injection blocking layer and the photoconductive layer, and the surface protective layer is about one digit larger.

That is, the surface protection layer having a withstand voltage of about 10 times that of the photoconductive layer is applied with only about three times the shared voltage, and the charge injection blocking layer has the same withstand voltage as the photoconductive layer. , A shared electric field of about 1.5 times is applied.

Although the dielectric breakdown voltage of the a-Si photosensitive member is 2 kV or more, it is considered that the potential rise due to frictional charging of the toner rarely reaches this value as described above. Further, as can be seen immediately from the above values, it is considered that the charge injection blocking layer having the largest ratio of the shared electric field to the withstand electric field among the layers of the blocking type photoconductor is destroyed first.

Such damage to the electrophotographic photosensitive member cannot be easily confirmed from the outside, unlike dielectric breakdown due to abnormal discharge, etc. However, this is formed on the entire surface of the electrophotographic photosensitive member, and an image as described above is formed. Spots are generated and image quality is impaired.

The image forming process for the electrophotographic photoreceptor includes a plurality of steps for charging or discharging the surface of the photoreceptor (band discharging step). A corona discharge charger is generally used as a device for removing static electricity.

The corona charger basically includes a shield member made of a conductive material called a corona house having a discharge opening, a discharge wire provided in the corona house, and a grid electrode provided in the discharge opening. Having (scorotron)
In general, the corona charger is arranged such that a discharge opening is close to and opposed to a photoconductor surface, and a corona generated by applying a voltage to a charging wire is applied to the photoconductor surface, so that a photoconductor surface is formed. Is subjected to a charging process or a static elimination process.

The grid electrode is charged due to environmental fluctuations such as contamination of a charged line, contamination of a corona house, humidity, etc., particularly in charging including a negative component and uniform charging of the photosensitive member surface prior to formation of a latent image. It is provided to prevent unevenness and a decrease in charging ability. Specifically, a metal wire of φ60 μm to 100 μm stretched in parallel with the discharge opening at an equal interval, a mesh-shaped metal thin plate manufactured by etching, and the like are kept at an interval of about 1 to 3 mm with respect to the photoconductor surface. opposite. The grid effect of the electrodes prevents image density unevenness, separation retransfer, and the like, and ensures stable supply of high image quality.

The provision of the grid electrode in the corona charger has the significance as described above. On the other hand, the corona charger having the grid electrode has a problem in that the charging wire, the toner of the grid electrode, paper powder, and other dusts are used. In some cases, abnormal discharge may occur between the charged wire and the grid electrode due to adhesion of chemical products or the like.

This abnormal discharge can be broadly classified into two types, spot-like abnormal discharge and spark discharge in corona discharge. In the latter case, a part of the spark discharge has a distance of 1 to 3 mm between the grid electrode and the photosensitive member surface. In some cases, the light may jump over the space and reach the photoconductor surface.

When the photoreceptor is an a-Si photoreceptor, it is liable to be damaged (discharge destruction mark) by the spark discharge acting on the photoreceptor surface. Specifically, an image was formed in an electrophotographic apparatus in which the corona charger generates the above-described spark discharge, and the damage to the a-Si photoconductor was examined. In some cases, white spots of 6 mm (image defects that appear white on the image) were continuously formed in a perforated manner at intervals of 2 mm.

The following experiment was also conducted. A separation corona charger for electrostatically separating transfer paper from the surface of the photoreceptor is provided with a mixture of aluminum chips and paper powder artificially adhered to grid electrodes provided on a plurality of grid electrodes. When the applied voltage was raised to a level higher than usual and discharge was performed, charges were accumulated in a mixture of aluminum chips and paper powder on the grid electrode, and a spark discharge was generated therefrom.

It has been found that the spark discharge causes damage in the same manner as described above.

Further, while the a-Si based photoreceptor has high hardness, when a high load is applied to a very small area, the above-mentioned type of flaw is different from other types of photoreceptors. For example, a load is applied to a diamond needle having a tip diameter of 0.8 mm to
-When the surface of the Si-based photoreceptor is scratched, the appearance potential flaw is not observed at all on the surface of the a-Si-based photoreceptor, but the dark portion potential holding ability of the portion is significantly reduced, and the abrasion on the image is caused. In some cases, an image defect was generated as a black streak called a black streak depending on the developing conditions.

This puncture phenomenon is particularly conspicuous in halftone images.
It disappears by heating at 0 ° C. for about one hour, but if a blemish occurs in the market, it is impossible to take such a measure and it is also difficult to predict the occurrence of the bum in advance.

Conventionally, a photoreceptor protector has been used as a countermeasure against the above-mentioned problems, and a sufficient effect has been obtained to solve the above problems. Fundamental improvement was desired.

The present invention is directed to the generation of pinholes due to abnormal discharge in the charging step in the electrophotographic apparatus using the conventional amorphous silicon photoreceptor as described above, particularly, the occurrence of pinholes due to leak discharge at the time of clogging of the transfer material at the transfer and separation sites. An object of the present invention is to provide an electrophotographic photoreceptor which overcomes the problem of image defects caused by scratches, extends the life of an amorphous silicon photoreceptor, and is free from image defects and can provide excellent images over a long period of time.

[0032]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to eliminate the above-mentioned leak spots and pressure marks, and as a result, have found that between the conductive substrate and the light receiving layer including the a-Si based photoconductive layer. It has been found that the above problem can be solved by providing an undercoat layer made of a non-single-crystal hydrogenated carbon film.

Further, as a result of studying the most suitable undercoat layer for the a-Si based photoreceptor, the hydrogen content of the non-single-crystal hydrogenated carbon film was reduced to 50 atomic% or less, whereby the film hardness and It was found that the electrical withstand voltage was improved, and the effect of preventing leak spots and nicks was extremely high. However, a non-single-crystal hydrogenated carbon film having a hydrogen content of 50 atomic% or less has an extremely high effect of preventing leak spots and injuries, but on the contrary, the adhesion to the conductive substrate tends to deteriorate. found.

The relationship between the properties of the non-single-crystal hydrogenated carbon film and the hydrogen content was examined in order to achieve the opposite properties of hardness, electrical breakdown voltage, and adhesion. As a result, it was found that the direction of the stress (compression and expansion) of the film was reversed when the hydrogen content was between 40 atomic% and 50 atomic%. Utilizing this property, a plurality of layers having different hydrogen contents are laminated, or when the hydrogen content is distributed in a single-layer type undercoating layer, excellent adhesion is obtained without impairing the film hardness and electric breakdown voltage. It turned out that a pull layer was obtained.

Based on the above findings, the present invention provides a method for forming a non-single-crystal hydrogenated carbon film as an undercoat layer on a cylindrical conductive substrate made of aluminum, and further forming a base material containing at least silicon atoms. A light receiving layer comprising a photoconductive layer made of a non-single-crystal material is sequentially laminated, and the amount of hydrogen contained in the undercoat layer has a distribution of a high hydrogen content region and a low hydrogen content region. An electrophotographic photoreceptor characterized by the following:

The amount of hydrogen contained in the undercoat layer may be not less than 10 atomic% and not more than 70 atomic% based on all elements, and may not have photoconductivity.

Further, the thickness of the region having a large hydrogen content in the undercoat layer is preferably 0.1 μm to 2 μm, and the thickness of the region having a low hydrogen content in the undercoat layer is preferably 0.3 μm to 8 μm.

The thickness of the undercoat layer is preferably 0.4 μm or more from the viewpoint of the electric breakdown voltage and the film hardness of the undercoat layer.
It is desirable that the thickness be 0 μm or less.

Further, the undercoat layer further comprises a second layer of the periodic table.
It may contain an element selected from Group I or Group V, and may also function as a lower blocking layer for preventing charge injection from the conductive substrate.

[0040]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for forming an electrophotographic photosensitive member according to the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic sectional view of an electrophotographic photosensitive member according to the present invention, and 101 is a conductive substrate made of aluminum. Reference numeral 102 denotes an undercoat layer made of aC: H according to the present invention.
And the upper layer 106. The present invention is characterized in that one of the lower layer 105 and the upper layer 106 has a high hydrogen content and the other has a low hydrogen content.
Reference numeral 103 denotes a photoconductive layer made of a-Si, which is constituted by a single layer whose functions are not separated.
In addition to 03, a surface protection layer 104 may be provided for the purpose of protecting the surface, improving environmental resistance, and improving electrical characteristics.

FIG. 2 shows a charge transport layer 207 composed of a non-single-crystal material containing at least silicon atoms and carbon atoms, and a charge generation layer composed of a non-single-crystal material containing at least silicon atoms. This is a specific example when the layer 208 is removed. When the electrophotographic photosensitive member is irradiated with light, carriers mainly generated in the charge generation layer 208 reach the conductive support 201 through the charge transport layer 207.
The effect of the present invention can be sufficiently obtained even if the electrophotographic photoreceptor of the present invention is a so-called function-separated type as a structure of the photoconductive layer.

FIG. 3 shows a specific example in which a lower blocking layer 309 for blocking carrier injection from the conductive substrate 301 is provided in addition to the photoconductive layer 303. The lower blocking layer is configured to be laminated on the undercoat layer 302.

FIG. 4 further shows a charge transport layer 407 in which the photoconductive layer 403 is made of a non-single-crystal material containing at least silicon atoms and carbon atoms, and a charge generation layer made of a non-single-crystal material containing at least silicon atoms. This is a specific example in the case where a configuration of a function separation type consisting of 408 is adopted.

FIG. 5 shows an electrophotographic photosensitive member in which the undercoat layer 502 is composed of a single layer and has a first region 505 and a second region 506 having different hydrogen content distributions.

The distribution form of the hydrogen content in the first region 505 and the second region 506 is, for example, as follows.

FIG. 9 is an example showing a distribution form in which the hydrogen content in the undercoat layer is higher on the substrate side and lower on the photoconductive layer side. On the other hand, FIG. 10 is an example showing a distribution mode in which the hydrogen content in the undercoat layer is lower on the substrate side and higher on the photoconductive layer side.

Note that the distribution of the hydrogen content shown in FIGS. 9 and 10 is merely an example. The effects of the invention can be obtained.

FIG. 6 shows a specific example of the electrophotographic photosensitive member in which the undercoat layer 602 is further composed of a first region 605, a second region 606 and a third region 607 having different hydrogen contents.

The distribution form of the hydrogen content in the first region 605, the second region 606, and the third region 607 is as follows, for example.

FIG. 11 is an example showing a distribution form in which the hydrogen content in the undercoat layer is small on the substrate side and on the photoconductive layer side and large in the center. On the other hand, FIG. 12 shows an example in which the hydrogen content in the undercoat layer is large on the substrate side and the photoconductive layer side, and is small in the central part.

Note that the distribution of the hydrogen content shown in FIGS. 11 and 12 is merely an example, and the distribution of the hydrogen content is not limited even if the distribution of the hydrogen content is high or low. The effects of the invention can be obtained.

The conductive substrate 10 used in the present invention
1 to 601 may be any as long as they have a material and a shape according to the purpose of use. For example, the shape is preferably a cylindrical shape, but may be a flat plate shape or another shape as necessary. The materials are aluminum, gold,
Silver, copper, platinum, lead, nickel, cobalt, iron, chromium,
Molybdenum, titanium, stainless steel, and composite materials of two or more of these materials, as well as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass, quartz, ceramic, paper, etc. An insulating material coated with a conductive material can be used.

Undercoat layers 102 to 6 according to the present invention
02 is composed of non-single-crystalline carbon (hereinafter referred to as an aC film). As a raw material gas, a gaseous hydrocarbon is used at normal temperature and normal pressure, and is produced by glow discharge decomposition with high frequency, and does not need to have photoconductivity. However, the photoconductive layers 103 to 6
03 to the conductive supports 101 to 60
1 is required to have smooth charge transport capability. In order to have charge transport ability, it is necessary that the aC film appropriately contains hydrogen atoms. A preferred hydrogen atom content range is from 10 atomic% to 70 atomic% based on all atoms.

In the present invention, in order to change the hydrogen content in the undercoat layer, for example, the source gas is diluted with hydrogen, the discharge power or the pressure of the discharge space is changed, or the substrate temperature is changed. It can be controlled by changing various film forming parameters such as.

Further, when the undercoat layer also serves as a lower blocking layer, or in order to improve the charge transporting ability of the undercoat layer, atoms for controlling conductivity may be contained according to the purpose. Examples of the atoms that control the conductivity contained in the undercoat layers 102 to 602 include so-called impurities in the semiconductor field, and include atoms belonging to Group III of the periodic table that provide p-type conductivity characteristics (hereinafter, “atoms”). Group III atom) or an atom belonging to Group V of the periodic table that provides n-type conduction characteristics (hereinafter abbreviated as “Group V atom”). In the present invention, the content of the atoms controlling the conductivity contained in the undercoat layers 102 to 602 is appropriately determined as desired so that excellent charge transporting ability can be exhibited, but is preferably 10 to 1 ×. 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm, optimally 1 × 1
Desirably, the concentration is from 0 ² to 1 × 10 ³ atomic ppm.

The thickness of the undercoat layers 102 to 602 of the present invention is preferably 0.4 μm or more from the viewpoint of mechanical strength, and is preferably 10 μm or less in order to reduce the residual potential.

The high-frequency power is preferably as high as possible because the decomposition of hydrocarbons proceeds sufficiently. Specifically, the high-frequency power is preferably 10 W or more per 1 ml / min (normal) of a hydrocarbon raw material gas. When this happens, abnormal discharge occurs, and the undercoat layers 102 to 602 are deteriorated. Therefore, it is necessary to suppress the electric power to such an extent that abnormal discharge does not occur.

Regarding the pressure in the discharge space, when a film is formed with a raw material gas which is hardly decomposed like a hydrocarbon, a polymer is likely to be generated if there is collision between decomposed species in a gas phase. High vacuum is desirable. Specifically, 133P
a or less, more preferably 80 Pa or less, and still more preferably 5 Pa or less.
It is 3 Pa or less.

The lower blocking layers 309 to 609 in the electrophotographic photoreceptor of the present invention are provided with a conductive support 101 to 101 when the free surface of the electrophotographic photoreceptor is subjected to a charging treatment of a fixed polarity.
It has a function of preventing charges from being injected from the side 601 to the photoconductive layers 103 to 603, and does not exhibit such a function when subjected to a charging treatment of the opposite polarity. Have. In order to provide such a function, the lower blocking layers 309 to 609 contain relatively more atoms for controlling conductivity than the photoconductive layer. As the atoms for controlling the conductivity contained in the lower blocking layers 309 to 609, Group III atoms or Group V atoms can be used. In the present invention, the content of the atoms for controlling the conductivity contained in the lower blocking layers 309 to 609 is appropriately determined as desired so that the object of the present invention can be effectively achieved. ~ 1 × 10 ⁴ atom p
pm, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

Further, the lower blocking layers 309 to 609 include
By containing at least one of a carbon atom, a nitrogen atom and an oxygen atom, the adhesion to another layer provided in direct contact with the lower blocking layers 309 to 609 can be further improved. In the present invention, the content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in all the layer regions of the lower blocking layers 309 to 609 is the amount in the case of one kind, and the total amount in the case of two or more kinds. Is preferably 1 × 10 ⁻³ to 50 atomic%, more preferably 5 × 10 ⁻³ to 30 atomic%, and most preferably 1 × 10 ^−2.
Desirably, it is set to 10 to 10 atomic%.

In the present invention, the lower blocking layers 309 to
The hydrogen atoms and / or halogen atoms contained in 609 compensate for dangling bonds existing in the layer, and are effective in 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 309 to 609 is preferably 1 to 50 atomic%, more preferably 5 to 50 atomic%.
It is desirable to set it to 40 atomic%, optimally 10 to 30 atomic%.

In the present invention, the lower blocking layers 309 to 60
The layer thickness of 9 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 103 to 603 in the electrophotographic photosensitive member of the present invention need to contain hydrogen atoms and / or halogen atoms in the films. 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. Therefore, the content of the hydrogen atom or the halogen atom, or the sum of the hydrogen atom and the halogen atom is preferably 10 to 30 atom%, more preferably 15 to 25 atom%, based on the sum of the silicon atom and the hydrogen atom and / or the halogen atom. It is desirable to be. In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layers 103 to 603, for example, the temperature of the support, the amount of a 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.

In the present invention, the photoconductive layers 103 to 60
Preferably, 3 contains an atom for controlling conductivity as necessary. As the atoms for controlling the conductivity, the same atoms as those for the lower blocking layers 309 to 609 can be used. The content of the atoms controlling the conductivity contained in the photoconductive layers 103 to 603 is preferably 1 × 10 ⁻² to 1
× 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 ×
It is desirable that the concentration be 10 ³ atomic ppm, optimally 1 × 10 ⁻¹ to 1 × 10 ³ atomic ppm.

Further, in the present invention, the photoconductive layer 103
It is also effective to include carbon atoms and / or oxygen atoms and / or nitrogen atoms in 〜603. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 10 atomic%, more preferably 1 × 10 ⁵ atomic%, based on the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. ^-4 to 8 atomic%, optimally 1 × 10 ^{-3 to} 5 atomic%
Is desirable.

The carbon atoms and / or oxygen atoms / and / or nitrogen atoms do not necessarily need to be contained in all layers, but may be distributed only partially or in the film thickness direction.

In the present invention, the photoconductive layers 103 to 603
The layer thickness is determined as desired from the viewpoint that desired electrophotographic characteristics can be obtained, and economic effects,
Preferably 10 to 50 μm, more preferably 20 to 45
μm, optimally 25 to 40 μm.

In the present invention, the photoconductive layers 103 to 60
3 and a-Si based surface protective layers 104 to 604
Is preferably formed. This surface protective layer 104-6
Reference numeral 04 has a free surface and is provided in order to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability. Further, in the present invention, the photoconductive layers 103 to 603 constituting the light receiving layer are used.
Since each of the non-single-crystal materials forming the surface protective layers 104 to 604 has a common component of silicon atoms, sufficient chemical stability is ensured at the lamination interface.

The surface protective layers 104 to 604 can be made of any material as long as they are a-Si-based materials. For example, the surface protective layers 104 to 604 contain a hydrogen atom (H) and / or a halogen atom (X), and further contain a carbon atom. A-Si containing atoms (a-Si
C: H-X, a-Si containing a hydrogen atom (H) and / or a halogen atom (X) and further containing an oxygen atom
A-Si (a-SiN: H, X) containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a nitrogen atom (a-SiO: H, X); ) And / or a halogen atom (X), further comprising a carbon atom,
A-S containing at least one of an oxygen atom and a nitrogen atom
Materials such as i (a-SiCON: H, X) are preferably used.

The content of an element selected from carbon, nitrogen and oxygen is preferably in the range of 30 to 90 atomic% based on the sum of silicon atoms, carbon atoms, nitrogen atoms and oxygen atoms. In the present invention, when hydrogen atoms and / or halogen atoms are contained in the surface protective layers 104 to 604, the hydrogen content is usually 30 to 70 atomic%, preferably 30 to 70 atomic%, based on the total amount of the constituent atoms. Is desirably 35 to 65 at%, optimally 40 to 60 at%. The content of fluorine atoms is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%.
It is desirable to set it as atomic%.

Further, in the present invention, the surface protective layer 10
The atoms 4 to 604 may contain an atom for controlling conductivity as necessary.

The surface protective layers 104 to 604 in the present invention
Is usually 0.01 to 3 μm, preferably 0.1 to 0.3 μm.
Desirably, the thickness is 1 to 2 μm, most preferably 0.5 to 1 μm. When the layer thickness is less than 0.01 μm, the surface protective layer is lost due to abrasion or the like during use of the electrophotographic photoreceptor, and when it exceeds 3 μm, the electrophotographic characteristics such as an increase in residual potential are reduced. There are cases.

The atoms for controlling the conductivity used in the present invention, for example, the Group III atoms include B (boron), Al (aluminum), Ga (gallium),
There are n (indium), Tl (thallium) and the like, and B, Al and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and P and As are particularly preferable.

A group III atom or a group V atom is structurally
In order to introduce a group III atom,
Raw material or raw material for group V atom introduction
Can be introduced into the reaction vessel together with other gases
No. Raw material for introducing Group III atoms or Group V atoms
Materials that can be used for introduction
Gaseous or easily gaseous at least under layering conditions
It is desirable that a material that can be used is adopted. Such first
As a raw material for introducing a group III atom, specifically, boron
For atom introduction, B_TwoH₆, B_FourH_Ten, B_FiveH₉, B_FiveH
₁₁, B₆H_Ten, B₆H ₁₂, B₆H₁₄Such as boron hydride, B
F_Three, BCl_Three, BBr_ThreeSuch as boron halide
Can be In addition, AlCl_Three, GaCl_Three, Ga (C
H_Three)_Three, InCl_Three, TlCl_ThreeAnd so on.
You. Effectively used as a raw material for introducing Group V atoms
The reason for this is that PH_Three, P_TwoH_FourEtc.
Phosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three, PC
l_Five, PBr_Three, PBr_Five, PI_ThreeAnd the like.
Can be In addition, AsH_Three, AsF_Three, AsCl_Three, As
Br_Three, AsF_Five, SbH_Three, SbF_Three, SbF_Five, SbC
l_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_ThreeEtc.
Listed as effective starting materials for introducing group V atoms
be able to. For introducing atoms to control these conductivity
If necessary, add H_TwoAnd / or by He
It may be used after dilution.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H
_8. Silicon hydrides (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified are effectively used, and furthermore, such as ease of handling at the time of forming a layer, high Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferred.

Then, hydrogen atoms are structurally introduced into each layer to be formed, and the control of the introduction ratio of hydrogen atoms is made easier to obtain a film characteristic which achieves the object of the present invention. In addition to these gases, H ₂ and / or H
A desired amount of a gas of silicon compound containing e or a hydrogen atom may be mixed 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.

The raw material gas for supplying halogen atoms used in the present invention is, for example, a gaseous or gaseous gas such as a halogen gas, a halide, an interhalogen compound containing a halogen, or a silane derivative substituted with a halogen. The obtained halogen compounds are preferred. Further, a gaseous compound containing a silicon atom and a halogen atom or a silicon hydride compound containing a halogen atom that can be gasified can also be mentioned as an effective compound.

Halogen which can be suitably used in the present invention
As the compound, specifically, fluorine gas (F_Two), Br
F, ClF, ClF_Three, BrF_Three, BrF_Five, IF_Three, IF
₇And the like. Haloge
With a silicon compound containing a halogen atom, a so-called halogen atom
Specific examples of the silane derivative obtained include, for example, Si
F _Four, Si_TwoF₆And the like are preferred.
Can be

Substances that can serve as a carbon supply gas include:
CH_Four, C_TwoH₆, C_ThreeH₈, C_FourH_TenEtc. in the gas state, also
Means that gasifiable hydrocarbons are used effectively
In addition, ease of handling when forming layers, Si supply efficiency
CH in terms of goodness etc._Four, C_TwoH ₆Are preferred
I can do it.

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

The atoms contained in each layer may be uniformly distributed throughout the layer, or may be uniformly distributed in the layer thickness direction, but may be distributed unevenly. There may be a part containing. However, in any case, it is important from the viewpoint of uniformity of the characteristics in the in-plane direction that the content is uniformly distributed in the in-plane direction parallel to the surface of the conductive substrate.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design.
× 10 ^-2 Pa to 1.3 × 10 ³ Pa, preferably 6.6.
× 10 ^-2 Pa to 665 Pa, optimally 0.13 Pa to 1
It is preferably set to 33 Pa.

Further, the temperature of the support is appropriately selected in an optimum range according to the layer design, but is usually preferably 50 to 500 ° C., more preferably 200 to 350 ° C.
It is desirable that

In the present invention, the preferable ranges of the mixing ratio of the source gases, the gas pressure, the temperature of the support, and the discharge power for forming each layer include the above-mentioned ranges. However, it is desirable to determine an optimum value based on mutual and organic relevance in order to form a deposited film having desired characteristics.

The electrophotographic photoreceptor of the present invention is produced by a vacuum deposition film forming method.

More specifically, for example, a glow discharge method (an AC discharge CVD method such as a low frequency CVD method, a high frequency CVD method or a microwave CVD method, or a DC discharge CVD method),
It can be formed by various thin film deposition methods such as a sputtering method, a vacuum evaporation method, an ion plating method, an optical CVD method, and a thermal CVD method. These thin film deposition methods
It is appropriately selected and adopted depending on factors such as the manufacturing conditions, the load under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic photoconductor to be manufactured. The glow discharge method, particularly the high frequency glow discharge method using a power supply frequency of 1 MHz to 450 MHz in the RF band or the VHF band, is preferable because the control of the conditions is relatively easy.

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

FIG. 7 is a schematic diagram showing an example of a general apparatus for manufacturing an electrophotographic photosensitive member by a high-frequency plasma CVD method.

This apparatus can be roughly classified into a deposition apparatus 710
0, a source gas supply device 7200, and the reaction vessel 7110 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Reaction vessel 71 in deposition apparatus 7100
10, a conductive substrate 7112, a substrate heating heater 7113, a raw material gas introduction pipe 7114, and a cathode electrode 71.
And a high-frequency power supply 712 via a high-frequency matching box 7115 to the cathode electrode 7111.
0 is connected.

The raw material gas supply device 7200 includes SiH ₄ ,
_{H 2, CH 4, N 2} , B 2 H 6, a cylinder of the raw material gas GeH ₄ such from 7221 to 7226 and the valve 7231～7236,7
241-7246, 7251-7256 and mass flow controllers 7211-7216.
16 and a gas introduction pipe 7114 in the reaction vessel 7110
It is connected to the.

The formation of a deposited film using this apparatus can be performed, for example, as follows.

First, the conductive substrate 7112 is placed in the reaction vessel 71.
Set at 10. The conductive substrate 7112 preferably has a cylindrical shape when an electrophotographic photoreceptor is manufactured.

After installation, the inside of the reaction vessel 7110 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). continue,
When the substrate heating heater 7113 is turned on, the conductive substrate 71 is turned on.
The temperature of No. 12 is controlled to a predetermined temperature of 250 ° C to 500 ° C.

A source gas for forming a deposited film is supplied to a reaction vessel 711.
0, the gas cylinder valves 7231-7
236, confirming that the leak valve 7117 of the reaction vessel is closed, and checking the inflow valves 7251 to 725
6. Outflow valves 7241 to 7246, auxiliary valves 721
0 is open, and the main valve 7
Open 118 to open reaction vessel 7110 and gas pipe 71
Exhaust 16.

Next, the vacuum gauge 7119 reads about 0.7 Pa.
At the time when the auxiliary valve 7210 and the outflow valve 725
Close 1-7256.

After that, the valves 7231 to 7236 of the gas cylinders 7221 to 7226 are opened to introduce each gas, and each gas pressure is adjusted by the pressure regulators 7261 to 7266 (for example, 1.96 × 10 ⁵ Pa). Next, the inflow valve 7
By gradually opening 241 to 7246, each gas is introduced into the mass flow controllers 7211 to 7216.

After the preparation for the film formation is completed as described above, an undercoat layer made of an aC film is first formed on the conductive substrate 7112.

When the conductive substrate 7112 reaches a predetermined temperature, necessary ones of the outflow valves 7251 to 7256 and the auxiliary valve 7210 are gradually opened, and a predetermined gas is supplied from the gas cylinders 7221 to 7226 to the gas introduction pipe 71.
Introduced into the reaction vessel 7110 via.

Next, the mass flow controllers 7211 to 7211
In accordance with 7216, each source gas is adjusted so as to have a predetermined flow rate. At that time, the pressure in the reaction vessel 7110 was 133
The opening of the main valve 7118 is adjusted while watching the vacuum gauge 7119 so that the pressure becomes equal to or lower than the predetermined pressure Pa. When the internal pressure is stabilized, the high-frequency power source 7120 is set to a desired power, and high-frequency power is introduced to the cathode electrode 7111 through the high-frequency matching box 7115 to cause glow discharge. The source gas introduced into the reaction vessel is decomposed by the discharge energy, and the conductive substrate 711 is decomposed.
2, a deposited film mainly containing predetermined carbon is formed.
After the formation of the desired film thickness, the supply of the high-frequency 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 7251-7256 to reaction vessel 711
In order to avoid remaining in the piping to reach zero, the outflow valves 7251 to 7256 are closed, the auxiliary valve 7210 is opened, and the main valve 7118 is fully opened to temporarily exhaust the system to a high vacuum as necessary. Do it. Also,
In order to achieve uniform film formation, the conductive base 7112 may be 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.

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

FIG. 8 is a diagram schematically showing a measuring method for measuring the electric breakdown voltage of the electrophotographic photosensitive member of the present invention. Electrophotographic photosensitive member 8 with conductive substrate 801 grounded
02, a small amount of glycerin 803 was placed on the surface, and an electrode needle 804 having a tip diameter of φ0.1 mm was brought into contact with the dc power source 805.
, A voltage until the electrophotographic photosensitive member was electrically destroyed and leaked was measured, and the value before the leak was defined as an electric breakdown voltage.

[0106]

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

[Example 1] As a sample for evaluating an undercoat layer, a lower layer 305 and an upper layer 306 of an undercoat layer were respectively deposited on a Si wafer substrate under the conditions shown in Table 1 to form an aC: H film. Was prepared, and the hydrogen content was measured.

Next, the undercoat layer was deposited on the cylindrical conductive substrate using the plasma CVD apparatus shown in FIG. 7 under the conditions shown in Table 1, and then the blocking layer 309, the photoconductive layer 303, and the surface were prepared under the conditions shown in Table 2. The layers 304 were laminated to produce electrophotographic photoconductors A to F having the configuration shown in FIG.

In this embodiment, the frequency is 13.56 MHz.
An electrophotographic photoreceptor was manufactured using the high-frequency power source of the above.

[0110]

[Table 1]

[0111]

[Table 2]

Samples Made and Electrophotographic Sensitivity A to F
Was evaluated according to the following procedure.

(Hydrogen Content in Film) The hydrogen content H / (C + H) of the undercoat layer samples A to F deposited on the Si wafer substrate was measured by the infrared absorption method.

(Electrical Withstand Voltage) The electrical withstand voltages of the photoreceptor samples A to F were measured by the withstand voltage measuring method shown in FIG. Therefore, the larger the value, the higher the electrical withstand voltage and the better.

(Pressure test) A constant load is applied to a diamond needle having a curvature of 0.8 mm in tip diameter using a surface property tester manufactured by HEIDON to bring the diamond needle into contact with the surface of the electrophotographic photosensitive member sample. In this state, the diamond needle is moved at a speed of 50 mm / min in the longitudinal direction of the electrophotographic photosensitive member. This operation is repeated while moving the measurement position while changing the load.

Next, after confirming that no scratch is generated on the surface of the electrophotographic photosensitive member, a halftone image having a reflection density of 0.5 is formed by an electrophotographic apparatus. The load at which the scratch starts to be generated from this image is defined as the pressure at which the scratch is generated.
And a relative comparison. Therefore, the larger the numerical value, the better the pressure scar is less likely to occur and the better.

Comparative Example 1 A blocking layer and a photoconductive layer were formed on a cylindrical conductive substrate using the plasma CVD apparatus shown in FIG. 7 under the conditions shown in Table 2, except that the undercoat layer of the present invention was not formed. A surface layer was laminated to produce an electrophotographic photoreceptor.
An electrical withstand voltage test and a bruise test were conducted in the same manner as in the above.

The evaluation results of Example 1 and Comparative Example 1 are summarized in Tables 3 and 4. In Table 4, the evaluation results of Comparative Example 1 are shown as relative values with 100 being set.

[0119]

[Table 3]

[0120]

[Table 4]

As a result, it was confirmed that the electrophotographic photosensitive member provided with the undercoat layer having a thickness within the range of the present invention has improved electric breakdown voltage and pressure scar.

Example 2 As a sample for evaluating an undercoat layer, a lower layer 105 and an upper layer 106 of an undercoat layer were respectively deposited on a Si wafer substrate under the conditions shown in Table 5 to form an aC: H layer. Sublayer samples GI were prepared and the hydrogen content was measured. Next, the undercoat layer was deposited on the cylindrical conductive substrate under the conditions of Table 5 using the plasma CVD apparatus shown in FIG.
The surface layer 104 was laminated, and electrophotographic photosensitive member samples GI having the configuration shown in FIG. 1 were manufactured. In this example, an electrophotographic photosensitive member was manufactured using a high-frequency power source having a frequency of 13.56 MHz.

[0123]

[Table 5]

[0124]

[Table 6]

The prepared samples and electrophotographic photosensitive members G to
I was evaluated in the same manner as in Example 1.

Tables 7 and 8 summarize the evaluation results of Example 2.
Shown in As a result, it was confirmed that the electrophotographic photosensitive member provided with the undercoat layer having a hydrogen content within the range of the present invention had improved electric breakdown voltage and pressure scar.

[0127]

[Table 7]

[0128]

[Table 8]

[Comparative Example 2] As a sample for evaluating the undercoat layer, single-layer undercoat layers A 'and B' were deposited on a Si wafer substrate under the conditions shown in Table 9, and the hydrogen content was measured. .

Next, using the plasma CVD apparatus shown in FIG. 7, a single layer of undercoat layer was deposited on the cylindrical conductive substrate under the conditions shown in Table 9, and then the blocking layer, photoconductive layer, The surface layers were laminated to produce electrophotographic photosensitive members A 'and B'.

In this comparative example, the frequency is 13.56 MHz.
An electrophotographic photoreceptor was manufactured using the high-frequency power source of the above.

[0132]

[Table 9]

The prepared sample and electrophotographic photosensitive member A '
And B ′ were evaluated in the same manner as in Example 1.

Table 10 shows the evaluation results of Comparative Example 2. As a result, the electrophotographic photosensitive member A ′ provided with the undercoat layer outside the range of the present invention improved the electric breakdown voltage, and the electrophotographic photosensitive member B ′ improved the pressure scar, but did not improve other characteristics. .
In the case of the photoconductor A ′ in which the thickness of the undercoat layer exceeds 10 μm, the residual charge increases, and the hydrogen content of the undercoat layer is further reduced to 10 atomic%.
In the case of the photoreceptor B ′ having a thickness lower than the above, film peeling may occur.

[0135]

[Table 10]

Example 3 As a sample for evaluating an undercoat layer, a lower layer 205 and an upper layer 206 of an undercoat layer were deposited on a Si wafer substrate under the conditions shown in Table 11 to obtain aC: H. Undercoat layer samples J to O were prepared, and the hydrogen content was measured.

Next, the undercoat layer was deposited on the cylindrical conductive substrate under the conditions shown in Table 11 using the plasma CVD apparatus shown in FIG.
7. Electrophotographic photoreceptors J to J having the configuration shown in FIG.
O was produced.

[0138]

[Table 11]

[0139]

[Table 12]

In this example, an undercoat layer sample and an electrophotographic photosensitive member were manufactured using a high-frequency power source having a frequency of 105 MHz.

The prepared samples and electrophotographic photosensitive members J to
O was evaluated in the same manner as in Example 1.

Tables 13 and 14 show the evaluation results of Example 3. As a result, it was confirmed that the electrophotographic photosensitive member provided with the undercoat layer according to the present invention using a high-frequency power source having a frequency of 105 MHz also improved the electric withstand voltage and the scratch resistance.

[0143]

[Table 13]

[0144]

[Table 14]

[Embodiment 4] Plasma CVD shown in FIG.
An undercoating layer made of an aC: H film is formed on a cylindrical conductive substrate using the apparatus under the conditions shown in Table 15, and then the blocking layer 509, the photoconductive layer 503, and the surface layer 504 are formed under the conditions shown in Table 2.
Were laminated to produce an electrophotographic photosensitive member having the configuration shown in FIG. However, in the present embodiment, the first area 505 and the second area 5
06, the hydrogen content was changed to the distribution shown in FIG.
An electrophotographic photosensitive member provided with a single-layer type undercoat layer 502 made of a C: H film was manufactured.

[0146]

[Table 15]

The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Table 16 shows the evaluation results of Example 4. As a result, even in an electrophotographic photoreceptor provided with a single-layer type undercoat layer in which the hydrogen content in the first and second regions of the undercoat layer was changed according to the distribution shown in FIG. It was confirmed that the withstand pressure and the dent were improved, and no defects such as film peeling occurred.

[0148]

[Table 16]

[Embodiment 5] Plasma CVD shown in FIG.
Using an apparatus, an undercoat layer made of an aC: H film is formed on a cylindrical conductive substrate under the conditions shown in Table 17, and then the blocking layer 509, the photoconductive layer 503, and the surface layer 504 are formed under the conditions shown in Table 2.
Were laminated to produce an electrophotographic photosensitive member. However, the distribution of hydrogen in the first region 505 and the second region 506 in the undercoat layer was the distribution shown in FIG.

[0150]

[Table 17]

The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Table 18 shows the evaluation results of Example 5. As a result, even in an electrophotographic photosensitive member provided with a single-layer type undercoat layer in which the hydrogen content in the first region and the second region of the undercoat layer was changed according to the distribution shown in FIG. It was confirmed that the withstand pressure and the dent were improved, and no defects such as film peeling occurred.

[0152]

[Table 18]

[Embodiment 6] Plasma CVD shown in FIG.
Using an apparatus, an undercoat layer made of an aC: H film is formed on a cylindrical conductive substrate under the conditions shown in Table 19, and then the blocking layer 609, the photoconductive layer 603, and the surface layer 604 are obtained under the conditions shown in Table 2.
Were laminated to produce an electrophotographic photosensitive member having the configuration shown in FIG. However, regarding the hydrogen content of the first region 605, the second region 606, and the third region 607 in the undercoat layer 602, FIG.
The distribution was as shown in the figure.

[0154]

[Table 19]

The produced electrophotographic photosensitive member was evaluated in the same manner as in Example 1. Table 20 shows the evaluation results of Example 6. As a result, the electrophotographic photoreceptor provided with a single-layer type undercoat layer in which the hydrogen content in the first region, the second region, and the third region of the undercoat layer was changed according to the distribution shown in FIG. In this case, it was also found that the electric withstand voltage and the scratch were improved, and no defects such as film peeling occurred.

[0156]

[Table 20]

[Embodiment 7] The plasma CVD shown in FIG.
After forming an undercoat layer made of an aC: H film on the cylindrical conductive substrate under the conditions shown in Table 21 using the apparatus, the blocking layer 609, the photoconductive layer 603, and the surface layer 604 are formed under the conditions shown in Table 2.
Were sequentially laminated to produce an electrophotographic photosensitive member. However, the distribution of hydrogen in the first region 605, the second region 606, and the third region 607 in the undercoat layer 602 has the distribution shown in FIG. The prepared electrophotographic photoreceptor was evaluated in the same manner as in Example 1.

[0158]

[Table 21]

Table 22 shows the evaluation results of Example 7. As a result, the electrophotographic photoreceptor provided with the single-layer type undercoat layer in which the hydrogen content was changed in the distribution shown in FIG. 12 in the first region, the second region, and the third region of the undercoat layer. In this case, it was also found that the electric breakdown voltage and the scratch were improved, and no defects such as film peeling occurred.

[0160]

[Table 22]

[0161]

As described above, the electrophotographic photoreceptor according to the present invention comprises a non-single-crystal hydrogenated carbon having a hydrogen content distribution in the thickness direction as a subbing layer on a conductive substrate. By depositing a film and further laminating thereon a photoconductive layer made of a non-single-crystal material having at least silicon atoms as a base material, the electric breakdown voltage and the mechanical strength are improved, and as a result, corona charging is achieved. It is possible to prevent image defects such as leak spots due to abnormal discharge of the vessel and bruises due to external pressure, and to provide high-quality and high-quality images for a long period of time.

[Brief description of the drawings]

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

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

FIG. 7 is a schematic explanatory view showing an example of an apparatus for forming an electrophotographic photosensitive member according to the present invention.

FIG. 8 is a schematic explanatory view showing an example of an apparatus for measuring the electric breakdown voltage of the electrophotographic photosensitive member according to the present invention.

FIG. 9 is a schematic explanatory view for explaining a hydrogen content distribution of a single-layered undercoat layer in the present invention.

FIG. 10 is a schematic explanatory view for explaining a hydrogen content distribution of a single-layered undercoat layer in the present invention.

FIG. 11 is a schematic explanatory view for explaining a hydrogen content distribution of a single-layered undercoat layer in the present invention.

FIG. 12 is a schematic explanatory view for explaining a hydrogen content distribution of a single-layer undercoat layer according to the present invention.

[Explanation of symbols]

 101, 201, 301, 401, 501, 601, 801 conductive substrate 102, 202, 302, 402, 502, 602 undercoat layer 103, 203, 303, 403, 503, 603 photoconductive layer 104, 204, 304, 404, 504, 604 Surface protective layer 105, 205, 305, 405 Lower layer 106, 206, 306, 406 Upper layer 505, 605 Undercoat layer first region 506, 606 Undercoat layer second region 607 Undercoat layer third Region 207, 407 Charge transport layer 208, 408 Charge generation layer 309, 409, 509, 609 Lower blocking layer 7100 Deposition device 7110 Reaction vessel 7111 Cathode electrode 7112 Conductive substrate 7113 Heater for substrate heating 7114 Source gas inlet tube 7115 Matching box 7116 Source gas piping 7117 Reactor vessel leak valve 7118 Main exhaust valve 7119 Vacuum gauge 7120 High frequency power supply 7121 Insulation material 7122 Exhaust pipe 7123 Receiving stand 7200 Source gas supply device 7210 Auxiliary valve 7211-7216 Mass flow controller 7221-7226 Source gas cylinder 7231-7236 Source gas cylinder Valve 7241 ~ 7246 Gas flow Valve 7251-7256 gas outflow valves 7261 to 7266 pressure regulators 802 electrophotographic photoreceptor 803 Glycerin 804 electrode needles 805 DC power supply

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Ryuji Okamura 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 CA03 DA03 DA42 DA62 DA64 DA68 DA69

Claims (16)

[Claims] 1. A non-single-crystal hydrogenated carbon film is deposited as a subbing layer on a conductive substrate, and further includes a photoconductive layer made of a non-single-crystal material containing at least silicon atoms as a base material. An electrophotographic photoreceptor characterized in that a light-receiving layer made of the following is sequentially laminated, and the amount of hydrogen contained in the undercoat layer has a distribution of a region with a high hydrogen content and a distribution of a region with a low hydrogen content. 2. The electrophotographic photoreceptor according to claim 1, wherein the amount of hydrogen contained in the undercoat layer is at least 10 at% and at most 70 at% based on all elements. 3. In the undercoat layer, the thickness of a region having a low hydrogen content is 0.3 μm or more and 8 μm or less, and the thickness of a region having a high hydrogen content is 0.1 μm or more and 2 μm or less. The electrophotographic photoreceptor according to claim 1, wherein: 4. The undercoat layer has a thickness of 0.4 μm or more,
4. The electrophotographic photosensitive member according to claim 1, wherein the thickness is 10 μm or less. 5. The hydrogen content of the undercoat layer in the high hydrogen content region is at least 40 at% and at most 70 at% with respect to all elements, and The electrophotographic photoreceptor according to any one of claims 1 to 4, wherein the amount of hydrogen contained in the region having a small amount is 10 atom% or more and 50 atom% or less based on all elements. 6. The method according to claim 1, wherein the undercoat layer comprises two layers, a lower layer and an upper layer, one of which has a high hydrogen content and the other has a low hydrogen content. An electrophotographic photoreceptor according to any one of the preceding claims. 7. The method according to claim 1, wherein the undercoat layer is formed as a single layer and includes a first region and a second region having different hydrogen contents. Electrophotographic photoreceptor. 8. The method according to claim 1, wherein the undercoat layer is formed of a single layer and includes a first region, a second region, and a third region having different hydrogen contents. 2. The electrophotographic photoreceptor of claim 1. 9. The electrophotographic photoreceptor according to claim 1, wherein the undercoat layer further contains a group III-V element of the periodic table. 10. The electrophotographic photoreceptor according to claim 1, wherein the undercoat layer has no photoconductivity. 11. The electrophotographic photosensitive member according to claim 1, wherein the undercoat layer also functions as a lower blocking layer. 12. The electrophotographic photoreceptor according to claim 1, wherein the light receiving layer comprises a photoconductive layer and a surface protective layer. 13. The electrophotographic photosensitive member according to claim 1, wherein the light receiving layer comprises a lower blocking layer and a photoconductive layer. 14. The light receiving layer according to claim 1, wherein the light receiving layer comprises a lower blocking layer, a photoconductive layer, and a surface protection layer.
0. The electrophotographic photosensitive member according to any one of 0. 15. The electrophotographic photosensitive member according to claim 12, wherein said photoconductive layer comprises a charge transport layer and a charge generation layer. 16. The method according to claim 1, wherein each of the layers provided on the substrate of the electrophotographic photoreceptor is manufactured by a plasma CVD method in which a discharge is excited at a discharge frequency of 1 MHz to 450 MHz. 13. The electrophotographic photoreceptor according to item 6.