JP2003015335A - Electrophotographic photoreceptor for negative electrification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance electrification capability and sensitivity, to reduce optical memory, to suppress image running and to enhance image quality in an a- Si(amorphous silicon) electrophotographic photoreceptor for negative electrification. SOLUTION: A coating film 102 and a light receiving layer 103 are stacked on an aluminum-base substrate 101. The thickness of the coating film 102 is adjusted to 0.5 to 15 nm and the film 102 is formed from 0.1 to 1 part by atom of silicon and 1 to 5 parts by atom of oxygen on the basis of 1 part by atom of aluminum. The light receiving layer 102 is formed by stacking a lower charge-injection blocking layer 104 consisting of a non-single-crystalline silicon film containing nitrogen and oxygen, using silicon as a matrix and not doped with an impurity, a photoconductive layer 105 consisting of a non-single- crystalline silicon film, an upper charge-injection blocking layer 106 consisting of a non-single-crystalline silicon film containing carbon and a group 13 atom and using silicon as a matrix and a surface protective layer 107 consisting of a non-single-crystalline silicon film containing carbon and using silicon as a matrix.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negatively charging electrophotographic photosensitive member having a functional film formed on an aluminum or aluminum alloy substrate.

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity,
High SN ratio [photocurrent (Ip) / dark current (Id)], having an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be irradiated, fast photoresponsiveness, having a desired dark resistance value, during use It is required to have characteristics such as being harmless to the human body. Particularly, in the case of an electrophotographic photosensitive member incorporated in an electrophotographic apparatus used as an office machine in an office, the pollution-free property at the time of use is an important point.

Amorphous silicon (also referred to as a-Si) is known as a photoconductive material exhibiting excellent properties in this respect, and is attracting attention as a light receiving member for an electrophotographic photoreceptor.

In such a light receiving member, a conductive support is generally heated to 50 ° C. to 350 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, A photoconductive layer made of a-Si is formed by a film forming method such as a photo CVD method or a plasma CVD method. Among them, the plasma CVD method, that is, the method of decomposing a raw material gas by high frequency or microwave glow discharge to form an a-Si deposited film on a support is put to practical use as a suitable one.

For example, in Japanese Patent Laid-Open No. 57-115556, a photoconductive member having a photoconductive layer composed of an a-Si deposited film is electrically connected to a photoconductive member such as dark resistance, photosensitivity and photoresponsiveness.
In order to improve the use environment characteristics such as optical and photoconductive characteristics and humidity resistance, and further the temporal stability, silicon atoms and carbon atoms are formed on the photoconductive layer composed of an amorphous material with silicon atoms as a base material. A technique for providing a surface barrier layer composed of a non-photoconductive amorphous material containing is described.

Further, Japanese Patent Laid-Open No. 6-83090 discloses that
An electrophotographic photosensitive member for negative charging is described, in which a charge trap layer and a charge injection blocking layer made of doped a-Si are provided on a photoconductive layer so as to perform sufficient charging even in high humidity, and contact charging is performed. .

Further, JP-A-6-242623 discloses that amorphous silicon is mainly contained between the photoconductive layer and the surface layer of the electrophotographic photoreceptor for negative charging and contains less than 50 ppm of boron. Alternatively, a technique is described in which a hole-trapping layer containing no element that controls conductivity is provided to obtain excellent electrophotographic characteristics.

In addition, Japanese Patent Laid-Open No. 11-194515 discloses an electronic device which forms a silicate film between a conductive substrate and a functional film to provide an image having excellent chargeability and a uniform and high-quality image. Techniques for obtaining photographic photoreceptors are described.

The above-mentioned techniques have improved the electrical, optical and photoconductive characteristics of the electrophotographic photosensitive member and the use environment characteristics, and the image quality has been improved accordingly.

[0010]

Recently, due to the spread of computers and the networking of offices,
Electrophotographic devices are required not only to function as conventional analog copiers, but also to be digitized to play the role of facsimiles and printers. Furthermore, digital full-color copying for full-color output of digitized information. Machine is required.

In response to these requirements, when a conventional positive charging electrophotographic photosensitive member is installed in a digital color copying machine,
The following problems are a concern.

First, as a toner for a color copying machine used in a digital full color copying machine, a negative polarity toner is generally used, and a latent image is formed by combining a negative polarity toner and a positive charging electrophotographic photoreceptor. Since the background exposure method exposes the non-image area (background area), it may be difficult to achieve high image quality.

Further, in the digital full-color copying machine, unlike a black-and-white copying machine which mainly forms an image of only characters, the main purpose is to form an image such as a full-scale photograph. Therefore, minute electric potential unevenness of the photoconductor sensitively affects the image quality, which may be difficult to control.

For example, an optical memory typified by a ghost is one of the causes. However, in a conventional electrophotographic photoreceptor for positive charging, the optical memory cannot be reduced to a level required for a full color copying machine. It can be difficult.
Therefore, there has been a strong demand for an electrophotographic photosensitive member that can achieve a ghostless image. However, in the conventional electrophotographic photoreceptor for positive charging, great effort is required to achieve further reduction of the optical memory. Further, even in the conventional electrophotographic photoreceptor for negative charging, there is still room for improvement for further reduction of optical memory.

Further, in the digital full-color copying machine, as one of the process conditions, when a plurality of developing devices are provided around the electrophotographic photosensitive member or a large developing means is used, the distance from the charging device to the developing device is increased. May be easily separated. Therefore, in order to compensate for the potential drop from the charging device to the developing device, it is necessary to increase the charging potential not only for the positive charging electrophotographic photosensitive member but also for the negative charging electrophotographic photosensitive member, Furthermore, the photosensitivity must be high.

It should be noted that in order to realize a high chargeability compatible with the digital full-color copying process, it is possible to deal with it to some extent by increasing the thickness of the photoconductive layer, but on the other hand, defects occur during the formation of the deposited film. There are problems in terms of technology and cost, such as increased probability and image defects.
I am in a difficult situation.

The latent image formation of the digital copying machine is so-called "dot" latent image formation. For this reason, halftone images, etc., may appear as jagged even if the level of image flow is not a problem in the conventional analog copying machine. Reduction is essential.

That is, in the conventional photoconductor, when the exposure amount is increased to obtain an image with a high contrast from the original of the color background, a large amount of photocarriers are generated by the irradiation of the strong exposure, and the photocarriers are likely to move. A phenomenon occurs in which the flow concentrates on. Due to this phenomenon, it is necessary to take measures against the image flow at the time of strong exposure in which the character portion is blurred, that is, the so-called EV flow, more than ever before.

In view of the above situation, the main object of the present invention is to improve the charging ability and sensitivity of the a-Si photoreceptor having excellent stability and durability, and to reduce the optical memory.
An electrophotographic photoconductor for negative charging to be mounted on a digital copying machine composed of a non-single-crystal material with a silicon atom as a base material, which can realize reduction of image deletion at a high level and dramatically improve image quality. To provide.

[0020]

According to the present invention for achieving the above object, at least a coating and a light receiving layer are laminated in this order on an aluminum or aluminum alloy substrate, and an electrophotographic photosensitive material for negative charging is formed. The body has a film thickness of 0.5 nm or more and 15 nm or less, and is mainly composed of aluminum, silicon, and oxygen, and 0.1 atomic part or more and 1 atomic part or less of silicon with respect to 1 atomic part of aluminum. And 1 atomic part or more and 5 atomic parts or less of oxygen, and the photoreceptive layer is a lower charge injection layer made of a non-single-crystal silicon film containing at least nitrogen and oxygen and having silicon as a base and not doped with impurities. A blocking layer and a photoconductive layer formed of a non-single crystal silicon film having silicon as a base,
An upper charge injection blocking layer formed of a non-single-crystal silicon film containing carbon and a Group 13 atom as a base and silicon, and a surface protection layer formed of a non-single-crystal silicon film containing carbon as a base of silicon are laminated in this order. An electrophotographic photoconductor for negative charging is provided.

The film can be formed by using water containing an inhibitor. When a silicate is used as the inhibitor, the film is also referred to as a silicate film. Further, non-single-crystal silicon means polycrystalline silicon and amorphous silicon (a-
Si), etc., and the light receiving layer of the electrophotographic photosensitive member is generally made of amorphous silicon.

The present inventors have made aluminum or aluminum alloys (these are also referred to as aluminum-based materials).
A lower charge injection blocking layer on the silicate film formed on the substrate,
The characteristics of the electrophotographic photoreceptor for negative charging in which the configurations of the photoconductive layer, the upper charge injection blocking layer and the surface protective layer were optimized were examined under various conditions. As a result, they have found that the mobility can be improved by changing the charge polarity of the electrophotographic photosensitive member to a negative charge and changing the photocarriers from holes to electrons, and the optical memory, especially the ghost, can be significantly reduced.

Further, the upper charge injection blocking layer made of a non-single-crystal silicon carbide film having silicon containing carbon and a Group 13 atom as a matrix improves the charging ability and sensitivity, and at the same time, a large amount of light is irradiated by irradiation of strong exposure. It has been found that the so-called EV flow, which is an image flow at the time of strong exposure, in which a character part is blurred due to a phenomenon in which carriers are generated and the optical carriers concentrate and flow into a part where it easily moves, is found.

Further, not only in the digital full-color copying machine but also in the conventional digital copying machine, when the negative charging is performed by the corona charging method which is the mainstream of the charging method, a large amount of ozone products are generated as compared with the positive charging. Since there is a problem of image deletion because it is generated, it is necessary to further improve the charging ability and suppress the amount of ozone generated.

Therefore, as a result of intensive investigations by the present inventors regarding the charging ability of the negatively charged electrophotographic photosensitive member,
By combining a silicate film formed on an aluminum-based material substrate and a lower charge injection blocking layer containing nitrogen and oxygen, a good interface can be formed when forming a deposited film, and holes are effectively formed. In addition, since the electrons are allowed to pass smoothly and the electrons pass smoothly, a significant improvement in the charging ability can be obtained because of the dramatic improvement in the blocking ability. It was found that reduction of optical memory and improvement of charging ability can be achieved at a high level.

In addition, due to the interfacial modification effect formed by the silicate film and the lower charge injection blocking layer, the impurities of Groups 13 and 15 in the conventional photoconductor are blocked without being added to the lower charge injection blocking layer. By maintaining sufficient performance, optical memory, especially ghost, can be dramatically reduced.

Due to the synergistic effect of the negatively charged layer structure and the silicate film as described above, in the negatively charged electrophotographic photoreceptor, the charging ability and sensitivity are improved, and the optical memory is reduced.
Image reduction can be realized at a high level, and image quality can be dramatically improved.

The electrophotographic photosensitive member for negative charging according to the present invention has a particularly remarkable effect when mounted on a digital full-color copying machine, but the same effect can be obtained when mounted on a digital monochrome copying machine. Needless to say.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

FIG. 1 shows an example of a suitable layer structure of the electrophotographic photosensitive member of the present invention. In this case, the light receiving layer 103 is provided on the cylindrical aluminum-based material base 101, and the silicate film 102 is formed between the cylindrical aluminum-based material base 101 and the light receiving layer 103.
The light receiving layer 103 includes a lower charge injection blocking layer 104, a photoconductive layer 105, and an upper charge injection blocking layer 10 in this order from the substrate side.
6 and the surface protection layer 107.

<Substrate> The substrate is generally cylindrical and
l, Cr, Mo, Au, In, Nb, Te, V, T
It is made of an aluminum-based material such as an alloy of at least one metal selected from i, Pt, Pb and Fe and Al.

The surface of the cylindrical substrate is treated by a lathe or the like, and the surface of the substrate is degreased and washed before the film forming step of forming a deposited film on the substrate. In the process, a silicate film described below is formed.

The surface of the cylindrical substrate is mirror-finished by the following procedure, for example. That is, a lathe with an air damper for precision cutting (PNEUMO PRECLSION
A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in (made by the company) so as to obtain a rake angle of 5 ° with respect to the cylinder center angle. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / mi.
Mirror cutting is performed under the conditions of n and feed rate of 0.01 mm / R so as to obtain a desired outer diameter.

<Silicate film> The silicate film contains aluminum, silicon, and oxygen as main constituent elements formed by using an aqueous detergent in which silicate is dissolved as a corrosion inhibitor (inhibitor) (Al-Si- It is also a film). By forming a silicate film on the surface of the substrate, defects on the surface of the substrate are reduced, and by forming a photoreceptive layer on it, there are no image defects and the electrophotographic characteristics such as charging property and photosensitivity are improved. It becomes possible to form an electrophotographic photoreceptor for negative charging.

The aluminum-based material substrate is, for example, a degreasing and cleaning step for degreasing and cleaning the surface of the substrate, and a silicate for forming a silicate film before forming a deposited film on the aluminum-based material substrate whose surface has been cut by a lathe or the like. The film forming step, the rinse step of rinsing the substrate surface, and the drying step of drying the substrate surface are performed in this order. In the silicate film forming step, residues such as oils and fats and halides on the substrate are removed by incorporating a water-based detergent having a surfactant, and further silicate is added to form on the surface of the aluminum substrate. . Further, pure water can be used in the rinsing step and the drying step after the film is once formed on the substrate.

The silicate film is formed by a method of incorporating silicate into an aqueous cleaning agent containing a surfactant in a degreasing / cleaning tank in a degreasing / cleaning step after cutting the surface of the substrate, or by using the silicate in the degreasing / cleaning step. First, there is a method of using silicate in the rinsing step, or a method of using silicate in the rinsing step and drying step without using the degreasing and washing step, or a method of using silicate in all steps. preferable.

Examples of the silicate include potassium silicate and sodium silicate, and any of them may be used, but potassium silicate is particularly preferable.

Further, the silicate concentration is preferably 0.1% by mass or more and 2% by mass or less in the range where stains are not generated on the substrate.

The film thickness of the film formed on the aluminum-based material substrate is 0.5 nm or more, preferably 1 nm or more, more preferably 1.5 nm or more, from the viewpoint of ensuring a sufficient effect of the film. . On the other hand, from the viewpoint of ensuring sufficient conductivity of the substrate, it is set to 15 nm or less, 1
It is more preferably 3 nm or less, further preferably 12 nm or less.

Formed on an aluminum-based material substrate,
Mainly consists of aluminum, silicon and oxygen (Al-
With regard to the composition ratio of the (Si—O) film, by setting the contents of Si and O within an appropriate range, sufficient performance as a film and appropriate conductivity can be realized. It is also considered to contribute to the configuration of the interface with the deposited film, and is believed to contribute to the improvement of charging characteristics and the like.

From such a viewpoint, when Al is 1 atomic part, Si is 0.1 atomic part or more, 0.15 atomic part or more is more preferable, and 0.2 atomic part or more is further preferable. Further, it is 1 atom part or less, more preferably 0.8 atom part or less, and further preferably 0.6 atom part or less. on the other hand,
When Al is 1 atomic part, O is 1 atomic part or more,
It is more preferably 1.5 atom parts or more, still more preferably 2 atom parts or more. Further, it is 5 atomic parts or less, more preferably 4 atomic parts or less, still more preferably 3.5 atomic parts or less.

Further, the silicate film may contain nitrogen. Nitrogen is considered to contribute to the adhesion to the deposited film and the relaxation of stress, and the adhesion of the deposited film is improved. Also, S
Like i and O, it is considered to contribute to the interface structure with the deposited film, and it is considered to contribute to the improvement of charging characteristics. From this point of view, the content of nitrogen is preferably 1 atom ppm or more with respect to aluminum, and 100 atom pp
m or more is more preferable, while 10 atom% or less is preferable, and 1 atom% or less is more preferable.

The procedure for forming a silicate film on a cylindrical substrate after cutting will be described below. FIG. 3 shows a cleaning device for forming a silicate film layer on the surface of the substrate and for cleaning the surface of the substrate.

The cleaning device comprises a processing section 302 and a substrate transfer mechanism 303. The processing unit 302 includes the substrate loading table 3
11, a degreasing cleaning tank 321, a silicate film forming tank 331, a rinse tank 341, a drying tank 351, and a substrate unloading table 361. Each tank is equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transport mechanism 303 is
The transfer mechanism includes a transfer rail 375 and a transfer arm 371, and the transfer arm 371 moves on the rail 375.
2. A chucking mechanism 373 for holding the substrate 301 and an air cylinder 374 for moving the chucking mechanism 373 up and down.

The substrate 301 placed on the loading table 311 is
It is transported to the degreasing cleaning tank 321 by the transport mechanism 303.
An aqueous cleaning agent containing a surfactant is contained in the degreasing cleaning tank 321, and the substrate 301 is ultrasonically cleaned therein to clean dust, oil and fat adhering to the surface.

After the degreasing and washing process is completed, the substrate 301 goes to the silicate film forming process. The transport mechanism 303 carries the silicate film to the silicate film forming tank 331 to form a silicate film. The silicate film forming tank 331 contains a water-based cleaning agent containing a silicate-added surfactant, and further ultrasonically cleans the substrate 301 to clean dust, oil and fat adhering to the surface. At the same time, a silicate film is formed on the surface of the substrate 301.

Furthermore, it is also effective to introduce a nitrogen atom by introducing, for example, amino alcohol, benzotriazole or the like in the silicate coating step.

Substrate 301 that has completed the silicate film formation process
Then reaches the rinse step. It is carried to the rinse tank 341 by the transport mechanism 303 and further rinsed with pure water or the like kept at a temperature of 25 ° C. The purity of pure water and the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba Ltd.). The substrate 301 that has completed the rinsing step is then subjected to the drying step. The substrate 301 is moved to the drying tank 351 by hot pure water or the like by the transport mechanism 303, and pulled up and dried by a lifting device (not shown) with hot pure water or the like kept at a temperature of 60 ° C. The accuracy of hot pure water and the like is constantly controlled by an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba Ltd.).

The substrate 301 having undergone the drying process is carried to the carry-out table 361 by the carrying mechanism 303 and carried out from the cleaning device shown in FIG.

<Lower Charge Injection Blocking Layer> A lower charge injection blocking layer having a function of blocking the injection of charges from the substrate side is provided below the photoconductive layer. The lower charge injection blocking layer is, when the photoreceptive layer undergoes a constant polarity charging treatment on its free surface,
It has a function of preventing charges from being injected from the substrate side to the photoconductive layer side, and does not exhibit such a function when subjected to a charging treatment of opposite polarity.

Here, the lower charge injection blocking layer is not doped with impurities such as group 13 atoms and group 15 atoms,
An intrinsic non-single-crystal silicon film, more preferably an intrinsic amorphous silicon film, is used as a base material. In this case, the adhesiveness and interface structure between the aluminum-based substrate on which the film is formed and the lower charge injection blocking layer are further improved, and the electrophotographic characteristics are improved.

The lower charge injection blocking layer is made of a non-single-crystal silicon film containing at least nitrogen and oxygen, and is made of a-Si containing hydrogen and / or halogen, nitrogen and oxygen. It is preferable. By adopting such a configuration, the adhesion between the lower charge injection blocking layer and the cylindrical substrate can be improved, and excellent blocking ability can be realized.

The nitrogen and oxygen contained in the lower charge injection blocking layer may be evenly distributed in the layer.
Alternatively, it may be contained evenly in the layer thickness direction, but may be contained in a non-uniformly distributed state. When the distribution concentration is non-uniform, it is preferable that the distribution concentration is large so that it is distributed on the substrate side.

However, in any case, it is necessary to make the content evenly distributed in the in-plane direction parallel to the surface of the substrate in order to achieve uniform properties in the in-plane direction.

Nitrogen and oxygen are contained in the entire region of the lower charge injection blocking layer, and carbon may be contained in the entire region as necessary. The total amount of those atoms added is determined by the characteristics of the electrophotographic photosensitive member to be obtained, but is preferably 0.1 atom% or more, more preferably 1 atom% or more, and more preferably 5 atom% with respect to the silicon atom. The above is more preferable.
Further, it is preferably 40 atomic% or less, more preferably 30 atomic% or less, still more preferably 20 atomic% or less.

When the sum of nitrogen and oxygen is 0.1 atomic% or more with respect to silicon, the chargeability can be improved and the adhesion between the lower charge injection blocking layer and the substrate can be improved, so that film peeling can be suppressed. . In addition, if 40 atomic% or less,
Excessive electric resistance of the lower charge injection blocking layer can be realized and residual charge can be reduced.

Further, hydrogen and halogen compensate for dangling bonds existing in the lower charge injection blocking layer and improve the film quality. The total amount of these atoms added is preferably 1 atom% or more, more preferably 5 atom% or more, still more preferably 10 atom% or more, with respect to silicon. Also,
It is preferably 50 atomic% or less, more preferably 40 atomic% or less, still more preferably 30 atomic% or less.

The thickness of the lower charge injection blocking layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, and 0.5 from the viewpoint of desired electrophotographic characteristics and economic effects.
More preferably, it is at least μm. Further, it is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less. If the layer thickness is 0.1 μm or more, the injection of charges from the substrate can be sufficiently blocked, and if it is 5 μm or less, the production time can be shortened without lowering the electrophotographic characteristics and the production cost can be reduced.

The lower charge injection blocking layer can be formed by a vacuum deposition method. In order to form the lower charge injection blocking layer having desired characteristics, the mixing ratio of the gas for supplying Si and the diluting gas and the reaction vessel inside the reaction vessel are set. It is necessary to properly set the gas pressure, the discharge power and the temperature of the substrate.

The flow rate of H ₂ and / or He, which is a diluent gas, is appropriately selected according to the layer design.
It is desirable to control H ₂ and / or He in the range of 0.3 to 20 times, preferably 0.5 to 15 times, and most preferably 1 to 10 times with respect to the Si supply gas.

Similarly, the gas pressure in the reaction vessel is also appropriately selected according to the layer design, but in the usual case 1.0 × 10 ^{-2 to} 1.0 × 10 ³ Pa, preferably 5.
0 × 10 ^{-2 to} 5.0 × 10 ² Pa, optimally 1.0 × 1
It is preferably from 0 ^{−1 to} 1.0 × 10 ² Pa.

Further, the discharge power is also appropriately selected in the optimum range according to the layer design, and the ratio of the discharge power to the flow rate of the gas for supplying Si is usually 0.5 to
8, preferably 0.8 to 7, and optimally 1 to 6 is desirable.

In addition, the temperature of the substrate is appropriately selected according to the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 330.
It is desirable that the temperature is set to 0 ° C, optimally 250 to 310 ° C.

The above-mentioned ranges are mentioned as desirable numerical ranges of the mixing ratio of the diluent gas for forming the lower charge injection blocking layer, the gas pressure, the discharge power, and the temperature of the support, but these layer forming factors are usually independent. It is desirable to determine the optimum value of each layer preparation factor on the basis of mutual and organic relationships so as to form a surface layer having desired characteristics, rather than being determined separately.

By combining the silicate film formed on the aluminum-based substrate with the lower charge injection blocking layer containing nitrogen and oxygen, the charge blocking ability of holes is dramatically improved, so that negative charge is particularly required. In the electrophotographic photoconductor for use, the charging property is remarkably improved.

<Photoconductive Layer> The photoconductive layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, a glow discharge method (low frequency CVD method, high frequency CV
AC discharge CVD method such as D method or microwave CVD method,
Or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method, thermal C
It can be formed by various thin film deposition methods such as the VD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the light receiving member to be produced, but they have desired characteristics. The glow discharge method, particularly the high-frequency glow discharge method using a power supply frequency in the RF band, is preferable because it is relatively easy to control the conditions for manufacturing the light receiving member.

In order to form a photoconductive layer by the glow discharge method, it is basically possible to supply silicon atoms (Si) to S.
i source gas for supplying and H capable of supplying hydrogen atom (H)
A raw material gas for supply and / or a raw material gas for X supply capable of supplying a halogen atom (X) are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and glow discharge is performed in the reaction vessel. Amorphous silicon (a-Si: H, containing hydrogen and / or halogen atoms) is generated on a predetermined substrate that is previously installed at a predetermined position.
X) may be formed.

The photoconductive layer preferably contains hydrogen and / or halogen atoms, but these atoms compensate for dangling bonds of silicon atoms to improve the layer quality, particularly photoconductivity and charge retention. Improve the characteristics. The total amount of these atoms to be added is preferably 10 to 40 atom% with respect to the total amount of silicon atoms and added atoms.

As the substance which can be used as the Si supply gas,
SiH _4, the _{Si 2 H 6, Si 3 H} 8, Si 4 gas state of H _10, etc., or the like as silicon hydride can be gasified (silanes) is effectively used, when further layers produced SiH ₄ and Si ₂ are easy to handle and have good Si supply efficiency.
H ₆ is mentioned as a preferred one.

Then, in order to structurally introduce hydrogen atoms into the photoconductive layer to be formed, to make it easier to control the introduction ratio of hydrogen atoms, and to realize desired film characteristics, these gases are further added. A predetermined amount of at least one gas of a silicon compound containing H ₂ , He and hydrogen atoms is mixed to form a layer. Also,
Each gas may be mixed not only with a single kind but also with a plurality of kinds at a predetermined mixing ratio.

As a raw material gas for supplying halogen atoms, a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen is preferably used. . Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be cited as an effective one. Examples of halogen compounds that can be used particularly preferably include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , and Br.
Interhalogen compounds such as F ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, silicon fluoride such as SiF ₄ and Si ₂ F ₆ can be mentioned as a preferable example.

The amount of hydrogen and / or halogen atoms contained in the photoconductive layer can be controlled, for example, by the temperature of the substrate, in the reaction vessel of the raw material used to contain hydrogen and / or halogen atoms. It is sufficient to control the amount to be introduced into, the discharge power, etc.

Atoms for controlling the conductivity can be introduced into the photoconductive layer. Examples of atoms that control conductivity include so-called impurities in the field of semiconductors, and atoms that belong to Group 13 of the periodic table (abbreviated as Group 13 atoms) that give p-type conductivity can be used. .

Specific examples of the group 13 atom include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and the like, with B, Al, and Ga being particularly preferable. It is suitable.

Atoms that control conductivity, such as the thirteenth
In order to structurally introduce a group atom, the thirteenth
The raw material for introducing the group atom may be introduced in a gas state into the reaction vessel together with another gas for forming the photoconductive layer. As a raw material for introducing a Group 13 atom, it is desirable to employ a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions.

As such a raw material for introducing a Group 13 atom, specifically, for introducing a boron atom, B ₂ H ₆ ,
_{B 4 H 10, B 5 H} 9, B 5 H 11, B 6 H 10, B 6 H 12, B 6 H
Examples thereof include boron hydride such as ₁₄ and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ and Ga
Other examples include Cl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , and TlCl ₃ .

Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with H ₂ and / or He as necessary and used.

Further, it is also effective that the photoconductive layer contains at least one atom of carbon, oxygen and nitrogen. The total amount of these atoms to be added is preferably 1 × 10 ^{−5 with} respect to the total amount of silicon atoms and added atoms.
^-10 atom%, more preferably 1 × 10 ^-4 to 8 atom%,
Optimally, 1 × 10 ^{−3 to} 5 atom% is desirable.

The layer thickness of the photoconductive layer is determined from the viewpoint of desired electrophotographic characteristics and economic effects, and is preferably 20.
˜50 μm, more preferably 23 to 45 μm, most preferably 25 to 40 μm. Layer thickness is 20 μm
If it is at least 50 μm, sufficient charging ability and sensitivity can be secured.
When it is m or less, the production time can be shortened and the production cost can be reduced without deteriorating the electrophotographic characteristics.

In order to form a photoconductive layer having desired film characteristics, it is necessary to appropriately set the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the substrate temperature. Is.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but the optimum range is 1.0.
X10 ^{-2 to} 1.0 x 10 ³ Pa, preferably 5.0 x 1
0 ^{-2 to} 5.0 x 10 ² Pa, optimally 1.0 x 10 ^-1 to
It is preferably 1.0 × 10 ² Pa.

Similarly, the discharge power is also appropriately selected in accordance with the layer design, and the optimum range is selected. The optimum ratio of the discharge power to the flow rate of the gas for supplying Si is 0.3 to 8,
It is desirable to set it in the range of preferably 0.8 to 7, and most preferably 1 to 6.

Further, the temperature of the substrate is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 200 to 350 ° C, more preferably 230 to 330 ° C.
Optimally, the temperature is preferably 250 to 310 ° C.

The above-mentioned ranges are mentioned as desirable numerical ranges of the support temperature and the gas pressure for forming the photoconductive layer, but the conditions are not usually independently determined separately, but the desired characteristics are desired. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having.

<Upper Charge Injection Blocking Layer> Between the photoconductive layer and the surface protective layer, numerical conditions of film forming parameters are appropriately set so that the upper charge injection blocking layer can obtain desired characteristics by a vacuum deposition film forming method or the like. Is set and produced.

The upper charge injection blocking layer blocks injection of charges from the upper part to improve charging ability, and a large amount of photocarriers are generated by irradiation of strong exposure, and the photocarriers are concentrated on a portion where it easily moves. As a result, the image flow during strong exposure in which the character portion is blurred due to the phenomenon that flows in
It also plays the role of blocking the V flow.

In the case where a high resistance surface layer is provided with an upper blocking function like a conventional photoreceptor, carriers having a polarity opposite to the charging polarity generated by light irradiation may be accumulated in the surface layer, and the carriers flow laterally. Sometimes caused an EV flow.

On the other hand, the non-single-crystal silicon film containing carbon and silicon as a base material is used as the thirteenth film for the upper charge injection blocking layer.
By containing a desired amount of the group atom, it is possible to adjust the optimum resistance value which allows carriers having a polarity opposite to the charging polarity to pass while preventing lateral flow. Therefore, there is a marked improvement in EV flow.

The base of the upper charge injection blocking layer is a-
Any material can be used as long as it is a Si-based material,
For example, a-Si (a-SiC: containing hydrogen (H) and / or halogen (X) and further containing a carbon atom:
H and X are also described).

The amount of carbon contained in the upper charge injection blocking layer is 10 atomic% or more with respect to the sum of silicon and carbon.
It is preferably in the range of atomic% or less and less than the content of carbon in the surface protective layer.

When the carbon content is 10 atomic% or more with respect to the sum of silicon and carbon, a good interface with the photoconductive layer is formed and the ability to prevent charge injection is improved. Also,
If it is 70 atomic% or less with respect to the sum of silicon and carbon, proper electrical resistance can be realized without impairing the charge injection blocking ability, and the lateral flow of charges can be suppressed and the EV flow can be suppressed.

Further, by making the content of carbon in the upper charge injection blocking layer smaller than that of the surface protection layer, the retention of charges at the interface between the upper charge injection blocking layer and the surface protection layer is suppressed. The cause of the residual potential can be reduced. As a result, the lateral flow of accumulated charges is suppressed, and the adverse effects such as image deletion are suppressed.

Further, it is preferable that the upper charge injection blocking layer contains an atom for controlling conductivity, and contains a Group 13 atom.

The content of the Group 13 atom in the upper charge injection blocking layer is determined by comprehensively judging from the EV flow prevention capability, the charge injection blocking capability and the image quality. Usually, it is preferably 10 atomic ppm or more, more preferably 50 atomic ppm or more, still more preferably 100 atomic ppm or more with respect to silicon. Further, it is preferably 10000 atomic ppm or less, more preferably 5000 atomic ppm, still more preferably 3000 atomic ppm or less.

When the content of the group 13 atom is 10 atomic ppm or more with respect to silicon, charge injection from the surface can be sufficiently prevented, and EV flow can be suppressed.
If it is 10,000 atomic ppm or less, the EV flow can be suppressed without impairing the charge injection blocking ability.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors. Of these, the Group 13 atom is an impurity that imparts p-type conductivity. Specifically, group 13 atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and the like. B, Al, and Ga are particularly preferable.

In order to structurally introduce the group 13 atom, a raw material for introducing the group 13 atom is formed in a gas state in the reaction vessel during formation of the layer to form the upper charge injection blocking layer. It may be introduced together with other gas. As a material that can be a raw material for introducing a Group 13 atom, a material that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions is desirable. Specific examples of the raw material for introducing a Group 13 atom include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ and B ₆ H ₁₀ for introducing a boron atom. , B ₆
Boron hydride such as H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ , BB
Examples thereof include boron halides such as r ₃ . Besides this, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , Tl
Other examples include Cl _{3 and the} like.

Further, a raw material for introducing a Group 13 atom is
If necessary, it may be diluted with a gas such as H ₂ , He, Ar, or Ne before use.

The top charge injection blocking layer is carefully formed to provide the desired properties as desired.
That is, a substance containing Si and C and optionally added with H and / or X is structurally a crystalline form such as polycrystal or microcrystal to an amorphous form (generic term). And non-single crystal), and shows the properties from electrical conductivity to semiconductivity and insulation, and the properties from photoconductive properties to non-photoconductive properties. In the present invention, the formation conditions are strictly selected as desired so that a compound having desired properties depending on the purpose is formed.

In order to form the upper charge injection blocking layer having predetermined characteristics, it is necessary to appropriately set the temperature of the substrate, the gas pressure in the reaction vessel, and the discharge power according to the characteristics.

The temperature of the substrate is appropriately selected in accordance with the layer design, but usually it is preferably 200.
˜350 ° C., more preferably 230˜330 ° C., optimally 250˜310 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is preferably 1 × 10 ⁻² to 2 × 10 ³ Pa, more preferably 5 × 10 ⁻² Pa.
X10 ^{-2 to} 5 x 10 ² Pa, optimally 1 x 10 ^-1 to 2 x
The pressure is 10 ² Pa.

Similarly, the discharge power is also selected in an optimum range according to the layer design, but the ratio of the discharge power to the flow rate of the gas for supplying Si is usually 0.5-1.
It is set to 0, preferably 0.8 to 8, and optimally 1 to 6.

The above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature, gas pressure and discharge power for forming the upper charge injection blocking layer, but these conditions are not usually independently determined separately. It is desirable to determine the optimum value based on the mutual and organic relationships to form a light receiving member having the desired properties.

The layer thickness of the upper charge injection blocking layer is determined comprehensively by the layer thicknesses of the photoconductive layer and the surface protective layer, the required electrophotographic characteristics and the like. From the viewpoint of sufficiently exhibiting the ability to prevent charge injection from the surface and not affecting the image quality, it is usually 0.01 μm to 0.5 μm.
Design with m.

<Surface Protective Layer> An amorphous silicon (a-SiC) based surface protective layer containing carbon is formed on the upper charge injection blocking layer. The surface protective layer has a free surface, and is provided mainly for improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

The surface protective layer may be made of any material as long as it is an a-SiC type material. For example, hydrogen (H) is used.
And / or halogen-containing a-SiC (a-
SiC: H, X) is also preferable.

The surface protective layer is produced by the vacuum deposition film forming method, by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, alternating-current discharge CVD method such as microwave CVD method, or direct-current discharge CVD method), sputtering method, vacuum deposition method, ion plating method, It can be formed by various thin film deposition methods such as a photo CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be manufactured. From the viewpoint of productivity of the member, it is preferable to use the same deposition method as that for the photoconductive layer.

For example, a-Si is formed by the glow discharge method.
In order to form a surface protective layer composed of C: H, X, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a source gas for supplying C, which can supply carbon atoms (C), are used. A raw material gas, a raw material gas for supplying H that can supply hydrogen atoms (H), and a raw material gas for supplying X that can supply halogen atoms (X) are placed in a desired reaction vessel in a reaction vessel. Introduced in a gas state, causing glow discharge in the reaction vessel,
A layer made of a-SiC: H, X may be formed on the substrate on which the photoconductive layer has been formed, which is placed at a predetermined position in advance.

The carbon content in a-SiC as the material of the surface protective layer is preferably 40 atom% or more and 90 atom% or less with respect to the sum of silicon and carbon.

Further, hydrogen and halogen in the surface protective layer compensate for dangling bonds of constituent atoms such as silicon and improve the layer quality, especially the photoconductive property and the charge retention property. From such a viewpoint, the hydrogen content is preferably 30 to 70 atom%, more preferably 35 to 65 atom%, and further preferably 40 to 60 atom% with respect to the total amount of the constituent atoms. The content of fluorine, for example, as halogen is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%.
Atomic%, optimally 0.6 to 4 atomic%.

The thickness of the surface protective layer is preferably 0.01 to 3 μm, more preferably 0.05 to 2 μm.
It is particularly preferably 0.1 to 1 μm. Layer thickness 0.01
When it is at least μm, sufficient durability of the surface protective layer can be secured, and when it is at most 3 μm, an increase in residual potential is suppressed and sufficient electrophotographic characteristics can be realized.

FIG. 2 shows an example of the layer structure in which the non-single crystal carbon film 208 is formed as the outermost surface layer on the surface protective layer 207. Specifically, on the a-SiC: H, X surface protection layer 207, amorphous carbon (a containing mainly hydrogen (H) and / or halogen (X) as carbon atoms is used.
-C: H, X) layer 208 is laminated on the outermost surface.

In this case, the light receiving layer 203 is provided on the cylindrical aluminum substrate 201, and the cylindrical aluminum substrate 2
01 and the light receiving layer 203, a silicate film 202 is formed. In the light receiving layer 203, a lower charge injection blocking layer 204, a photoconductive layer 205, and an upper charge injection blocking layer 206 are formed in this order from the base side, and a-SiC: H, X surface protective layer 207 has a- The C: H, X outermost surface layer 208 is laminated.

Here, the outermost surface layer is formed in the same manner as the surface protective layer.

For example, by the glow discharge method, aC:
To form the outermost layer of H and X, basically,
A raw material gas for supplying C, which can supply carbon atoms (C), a raw material gas for supplying H, which can supply hydrogen atoms (H), and a raw material gas for X, which can supply halogen atoms (X). To
It is introduced in a desired gas state into a reaction vessel whose inside can be depressurized to cause glow discharge in the reaction vessel, and a is formed on a substrate on which a photoconductive layer and a surface protective layer are previously formed at predetermined positions. -A layer of C: H, X may be formed.

The electrophotographic photosensitive member using aC: H, X as the outermost surface layer has excellent surface hardness and durability, and maintains high image quality even when used for a long time. Further, ozone generated by corona discharge is less likely to adhere to the surface, and it is possible to provide a good image in which image deletion does not occur without heating the photoconductor in the electrophotographic apparatus. In particular,
It has been confirmed by our experiments that in the negatively charged development process, the amount of ozone products produced during corona charging is about 10 times that in the positively charged development process.
Therefore, it is particularly effective to use aC: H, X as the outermost surface layer.

Further, peeling of the deposited film caused by distortion of the deposited film due to long-term use, and generation of minute cracks generated in the deposited film due to corona exposure can be suppressed. The present inventors have found that suppression of such defects is a secondary effect obtained by combining with a silicate film provided between the substrate and the light receiving layer.

Siri used in the formation of the surface protective layer
As a substance that can be a gas for supplying Si (Si),
H_Four, Si₂H₆, Si₃H₈, Si_FourH_TenGas state,
Or silicon hydride (silanes) that can be gasified is effectively used.
It is used as an example. Especially when taking layers
SiH is easy to handle and has good Si supply efficiency._Four, S
i₂H₆Is preferred. In addition, the raw material gas for supplying these Si
H as needed ₂For gases such as He, Ar, Ne, etc.
You may use it after diluting it more.

As the substances which can be used as the carbon supply gas for the surface protective layer and the outermost surface layer, CH ₄ , C ₂ H ₂ , C ₂ H ₆ ,
Hydrocarbons in a gas state or gasifiable such as C ₃ H ₈ and C ₄ H ₁₀ are mentioned as being effectively used. In particular, CH ₄ , C ₂ H ₂ , and C ₂ H ₆ are preferable from the viewpoints of easy handling at the time of layer formation and good supply efficiency. In addition, these raw material gases for supplying C may be supplied with H ₂ , He and A as needed.
It may be diluted with a gas such as r or Ne before use.

In order to more easily control the introduction ratio of hydrogen introduced into the formed surface protective layer, hydrogen gas or a silicon compound gas containing a hydrogen atom may be added to these gases. It is preferable to form a layer by mixing a desired amount. Each gas may be mixed not only with a single kind but also with a plurality of kinds at a predetermined mixing ratio.

As a material gas effective for supplying halogen, for example, a halogen gas, a halide, an interhalogen compound containing halogen, a silane derivative substituted with halogen, or a gaseous or gasifiable halogen compound is preferable. It is mentioned as a thing. For forming the surface protective layer, a gaseous or gasifiable silicon hydride compound containing a halogen atom containing silicon atoms and a halogen atom as a mixed element is also effective.

As a halogen compound which can be preferably used
Is, specifically, fluorine gas (F₂), BrF, ClF,
ClF₃, BrF₃, BrF_Five, IF₃, IF₇Etc.
Intermetallic compounds. Contains a halogen atom
Silicon compounds, so-called silanes substituted with halogen atoms
Specific examples of the derivative include SiF._Four, Si₂F
₆And the like can be mentioned as preferred ones.
It

To control the amount of hydrogen and / or halogen atoms contained in the surface protective layer and the outermost surface layer,
For example, the temperature of the substrate, the amount of the raw material used to contain hydrogen and / or halogen atoms introduced into the reaction vessel, the discharge power, etc. may be controlled.

Next, the apparatus and film forming method for forming the light receiving layer will be described in detail.

FIG. 4 is a schematic block diagram showing an example of an apparatus for manufacturing a light receiving member by a high frequency plasma CVD method (hereinafter abbreviated as "RF-PCVD") using an RF band as a power supply frequency. The structure of the manufacturing apparatus shown in FIG. 4 is as follows.

This apparatus is roughly classified into a deposition apparatus (410
0), source gas supply device (4200), reaction vessel (4)
111) is composed of an exhaust device (not shown) for reducing the pressure inside. A cylindrical substrate (4112), a heater for heating a support (4113), a source gas introduction pipe (411) are provided in a reaction vessel (4111) in a deposition apparatus (4100).
4) is installed, and a high frequency matching box (41
15) is connected.

The source gas supply device (4200) is made of SiH.
₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other raw material gas cylinders (4221-4226) and valves (4231)
4236, 4241 to 4246, 4251 to 4256)
And a pressure regulator (4261 to 4266),
The cylinder of each source gas is connected to the gas introduction pipe (4114) in the reaction container (4111) via the valve (4260).

The deposited film can be formed using this apparatus, for example, as follows. First, the reaction vessel (41
11) A cylindrical support (4112) is installed in the reaction vessel (41) by an unillustrated exhaust device (eg, vacuum pump).
11) Exhaust the inside. Subsequently, the temperature of the cylindrical substrate (4112) is adjusted to 2 by the heater for heating the support (4113).
The temperature is controlled to a predetermined temperature of 00 ° C to 350 ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel (41
11), the gas cylinder valve (423
1-44236), leak valve (4117) of reaction vessel
Make sure that the inlet valve (42) is closed.
41-4246), outflow valves (4251-425)
6) After confirming that the auxiliary valve (4260) is open, first, the main valve (4118) is opened to exhaust the reaction vessel (4111) and the gas pipe (4116).

Next, the reading of the vacuum gauge (4119) is about 1 ×.
When the pressure reaches 10 ^-2 Pa, the auxiliary valve (4260) and the outflow valve (4251 to 4256) are closed.

After that, a gas cylinder (4221 to 422)
From (6), each gas is introduced by opening the valves (4231 to 4236), and the pressure of each gas is adjusted to 19.6 N / cm ² by the pressure adjuster (4261 to 4266). Next, the inflow valves (4241 to 4246) are gradually opened to introduce each gas into the mass flow controllers (4211 to 4216).

After the preparation for film formation is completed as described above, each layer is formed by the following procedure.

When the cylindrical support (4112) reaches a predetermined temperature, the necessary ones of the outflow valves (4251 to 4256) and the auxiliary valve (4260) are gradually opened, and the gas cylinders (4221 to 4226) are brought to a predetermined position. Of the gas of the reaction vessel (411) through the gas introduction pipe (4114).
1) Introduce. Next, mass flow controller (4
211-4216) so that each raw material gas is adjusted to have a predetermined flow rate. At that time, while watching the vacuum gauge (4119), the main valve (41) so that the pressure in the reaction vessel (4111) becomes a predetermined pressure of 1.5 × 10 ² Pa or less.
18) Adjust the opening. When the internal pressure is stable, set the RF power supply (not shown) having a frequency of 13.56 MHz to the desired power, and set the high frequency matching box (4115).
RF power is introduced into the reaction vessel (4111) through
Cause a glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support (4112). After the desired film thickness is formed, the supply of RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

In this case, between each layer, once the formation of one layer is completed, the discharge is completely stopped, the flow rate and pressure of the gas of the next layer are set, and then the discharge is generated again. Then, the next layer may be formed, or
After the formation of one layer, the gas flow rate over a certain period of time,
A plurality of layers may be continuously formed by gradually changing the pressure and the high frequency power to the set values of the next layer.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel (411).
1) In order to avoid remaining in the pipe from the outflow valve (4251 to 4256) to the reaction vessel (4111), the outflow valve (4251 to 4256) is closed, the auxiliary valve (4260) is opened, and the main valve is further opened. Valve (41
If necessary, the operation of 18) is fully opened and the system is once evacuated to a high vacuum.

Further, in order to make the film formation uniform, it is effective to rotate the substrate (4112) at a predetermined speed by a driving device (not shown) during the layer formation.

Further, it goes without saying that the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

In the above method, the temperature of the support during the formation of the deposited film is particularly 200 ° C. or higher and 350 ° C. or lower, preferably 2 ° C.
The temperature is preferably 30 ° C or higher and 330 ° C or lower, more preferably 250 ° C or higher and 310 ° C or lower.

[0141]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, commercially available high purity reagents were used.

Example 1 Using the apparatus for manufacturing a photoreceptive layer by the RF-PCVD method shown in FIG. 4, a lower charge injection blocking layer and a photoconductive layer were formed on a cylindrical aluminum substrate having a diameter of 80 mm and mirror-finished. , The upper charge injection blocking layer and the surface protective layer were formed in this order under the conditions shown in Table 1 to prepare an electrophotographic photoreceptor for negative charging.

In this example, the surface of the cylindrical aluminum substrate was cut before the formation of the lower charge injection blocking layer described above, and 15 minutes after the completion of the cutting, degreasing and silicate film formation on the surface of the substrate were performed under the conditions shown in Table 2. Then, rinsing and drying were performed to form a silicate film layer made of Al-Si-O.
The produced electrophotographic photosensitive member was subjected to secondary ion mass spectrometry (SI
The atomic composition ratio of the formed Al-Si-O film was 1: 0.25: 3 as measured by MS). In the present example, in addition to the conditions shown in Table 2, amino alcohol and benzotriazole were further introduced in the film forming step to contain a nitrogen atom. The formed silicate film had a film thickness of 8 nm and contained nitrogen atoms of 800 atom ppm with respect to aluminum atoms.

[0144]

[Table 1]

[0145]

[Table 2] Comparative Example 1 In this comparative example, as in Example 1, a silicate film layer was formed on a mirror-finished cylindrical aluminum substrate. Thereafter, each layer was formed in the order of the lower charge injection blocking layer, the photoconductive layer, and the surface protective layer under the conditions of Table 3 without forming the upper charge injection blocking layer, to prepare a positive charging electrophotographic photoreceptor.

[0146]

[Table 3] Comparative Example 2 In this comparative example, as in Example 1, a silicate film layer was formed on a mirror-finished cylindrical aluminum substrate. Then, each layer was formed in the order of the lower charge injection blocking layer, the photoconductive layer, and the surface protective layer under the conditions of Table 4 without forming the upper charge injection blocking layer, to prepare an electrophotographic photoreceptor for negative charging.

[0147]

[Table 4] As described above, the negative charging electrophotographic photosensitive member and the positive charging electrophotographic photosensitive member manufactured in Example 1, Comparative Example 1, and Comparative Example 2 were electrophotographic apparatus (manufactured by Canon, trade name: iR6000).
Was modified for evaluation) and the characteristics were evaluated. The negative charging electrophotographic photosensitive member was evaluated using the same device as the negative charging system modified.

As the evaluation items, three items of "charging ability", "sensitivity" and "ghost" were evaluated by the following concrete evaluation methods.

(Chargeability) Process speed of the electrophotographic apparatus is 265 mm / sec, pre-exposure (L of wavelength 660 nm).
ED) 7 Lux · sec, and a semiconductor laser having a wavelength of 655 nm was set for image exposure. After that, the current value of the charging device was set to 800 μA, and the surface potential meter (manufactured by TREK, trade name: M) set at the developing device position of the electrophotographic apparatus for evaluation.
The surface potential of the light receiving member was measured by the potential sensor of ode 344), and it was defined as the charging ability.

(Sensitivity) The charging conditions were set so that the dark portion potential was 450 V, and the image exposure light amount when the bright portion potential was 50 V was measured, which was taken as the sensitivity.

(Ghost) A ghost test chart made by Canon Inc. (part number: FY9-9040) had a reflection density of 1.
1. Place a black circle with a diameter of 5 mm on the image edge of the platen, and place a Canon halftone chart (part number: FY9-9042) on top of it. The difference between the reflection density of a black circle having a diameter of 5 mm and the reflection density of a halftone portion of the ghost chart observed on the copy was measured. Therefore, the smaller the value, the better.

For the above evaluation, relative comparison was performed with the value obtained in Comparative Example 1 as 100. The evaluation results are shown in Table 5.

[0153]

[Table 5] The larger the "chargeability" is, the better the charging characteristics are. The smaller the numerical values of “sensitivity” and “ghost”, the better.

As is clear from the results of Table 5, Example 1
In Comparative Example 1, it was found that the chargeability was improved, ghosts could be reduced, and good image characteristics were obtained as compared with Comparative Example 1.

Example 2 In this example, as in Example 1, after forming a silicate film on the surface of a cylindrical aluminum substrate having a mirror finish under the conditions shown in Table 2, the lower charge injection blocking layer was formed. , A photoconductive layer, an upper charge injection blocking layer, and a surface protective layer were formed in this order under the conditions of Table 6 to prepare an electrophotographic photosensitive member for negative charging.

[0156]

[Table 6] In Example 2, a photosensitive member was produced in which the amount of boron charged in the upper charge injection blocking layer was changed to change the boron atom content (atomic ppm) relative to silicon in the upper charge injection blocking layer.

The photoconductors prepared with the respective charged amounts were evaluated for charging ability and EV flow.

(Chargeability) Evaluation was carried out in the same manner as in Example 1. In this embodiment, the content of boron is 1000 atom pp.
Relative comparison was carried out with the photoconductor being 100 when m. The larger the value, the better the result.

(EV flow) A test chart (part number: FY9-9058) manufactured by Canon Inc. was used to form an exposure with an intensity 1.2 times and 1.5 times the exposure amount at an appropriate image density. Regarding the image deletion at the time of strong exposure, the image was visually compared and judged with the limit sample; 1: very good, 2: good, 3: practically no problem, 4: practically difficult, and ranked in four stages did. In addition, when it is difficult to determine the rank, it is described as rank 1.5 when the rank is between 1 and 2.

[0160]

[Table 7] The evaluation results are shown in Table 7. As shown in Table 7, the content of boron with respect to silicon is preferably 10 to 1000.
In the range of 0 ppm, more preferably 50 to 5000 ppm, and most preferably 100 to 3000 ppm,
Very good results were obtained for both items.

Example 3 In this example, as in Example 1, a silicate film was formed on the surface of a cylindrical aluminum substrate that had been mirror-finished under the conditions of Table 2, and then the lower charge injection blocking layer was formed. , A photoconductive layer, an upper charge injection blocking layer, and a surface protective layer were formed in this order under the conditions shown in Table 8 to prepare an electrophotographic photoreceptor for negative charging.

[0162]

[Table 8] In Example 3, CH when forming the upper charge injection blocking layer
_{4 The} photoconductor was prepared by changing the flow rate and changing the carbon content (atomic%) with respect to the sum of silicon and carbon in the upper charge injection blocking layer.

The photoconductors produced under the respective conditions were evaluated for charging ability and EV flow in the same manner as in Example 2.

[0164]

[Table 9] The evaluation results are shown in Table 9. As shown in Table 9, when the carbon content was within the predetermined range, good results were obtained for both items.

Example 4 An electrophotographic photosensitive member for negative charging was prepared in the same manner as in Example 1. However, in this embodiment,
By changing the flow rate of the nitric oxide (NO) gas that forms the lower charge injection blocking layer, the sum of the content of nitrogen atoms and oxygen atoms with respect to silicon atoms is 0.05 atom%, 0.1 atom%,
Photoconductors were prepared which were changed to 1.2 atom%, 10 atom%, 20 atom%, 40 atom% and 45 atom%.

<Comparative Example 3> In the same manner as in Example 1, an electrophotographic photosensitive member for negative charging was prepared.

In this comparative example, when the lower charge injection blocking layer was formed, oxygen (O ₂ ) diluted with helium gas was used as the raw material gas without using nitric oxide, and And 6 atomic% of oxygen atoms with respect to silicon atoms.

<Comparative Example 4> In the same manner as in Example 1, an electrophotographic photosensitive member for negative charging was prepared.

In this comparative example, at the time of forming the lower charge injection blocking layer, ammonia (NH ₃ ) was used as a source gas without using nitric oxide, and nitrogen atoms were added to the charge injection blocking layer. It was contained at 4 atom% with respect to the atom.

<Comparative Example 5> In the same manner as in Example 1, an electrophotographic photosensitive member for negative charging was prepared.

In this comparative example, the lower charge injection blocking layer was not formed.

As described above, Example 4, Comparative Example 3, Comparative Example 4
And the electrophotographic photosensitive member for negative charging produced in Comparative Example 5,
In the same manner as in Example 1, the three items of "charging ability", "sensitivity" and "ghost" were evaluated.

Table 10 shows the evaluation results. In Table 10, relative comparison was performed by setting the value of the sample prepared in Comparative Example 5 to 100.

[0174]

[Table 10] As is clear from Table 10, in Example 4, a silicate film was formed on a cylindrical aluminum substrate, and the sum of the content of oxygen atoms and nitrogen atoms with respect to silicon atoms was 0.1 atom% in the lower charge injection blocking layer. When the content is 40 atomic% or less, the charging ability is remarkably improved as compared with Comparative Examples 3 to 5, and good sensitivity and ghost are obtained. Further, it was found that good image characteristics can be obtained.

Example 5 In this example, an electrophotographic photosensitive member for negative charging was prepared in the same manner as in Example 1.

In this example, the treatment time in the silicate film forming step was changed to form silicate films having different film thicknesses as shown in Table 12, and then the negative charging electron was charged under the conditions of Table 1. A photographic photoreceptor was produced.

Comparative Example 6 In this comparative example, potassium silicate was not used as an inhibitor under the conditions shown in Table 11 on the surface of a cylindrical aluminum substrate mirror-finished in the same manner as in Example 1, and a silicate film of After degreasing and cleaning, rinsing and drying of the surface of the substrate without forming the film, an electrophotographic photosensitive member for negative charging was prepared under the conditions shown in Table 1.

[0178]

[Table 11] The photoreceptors produced under the respective conditions as described above were evaluated for "charging ability", "sensitivity" and "ghost" in the same manner as in Example 1.

The evaluation results are shown in Table 12. In Table 12, relative comparison was performed with the characteristics obtained in Comparative Example 6 as 100. The larger the "chargeability" is, the better the charging characteristics are. "Sensitivity" and "Ghost"
Indicates that the smaller the value, the better.

[0180]

[Table 12] As is clear from the results in Table 12, by forming a silicate film layer having a predetermined film thickness on the surface of the cylindrical substrate, the charging ability is improved and the ghost can be reduced as compared with Comparative Example 6. It was also found that good image characteristics were obtained.

<Embodiment 6> A digital full-color copying machine (manufactured by Canon Inc., trade name: C) was used as the photoconductor prepared in Embodiment 1.
It was mounted on a modified LC500) to form a full-color image, and a very good image was obtained.

Example 7 In this example, a silicate film was formed on the surface of a cylindrical aluminum substrate mirror-finished in the same manner as in Example 1 under the conditions of Table 2 in the same manner as in Example 1, and then The lower charge injection blocking layer, the photoconductive layer, the upper charge injection blocking layer, and the surface protective layer are formed in this order under the conditions shown in Table 1, and further, carbon is mainly contained in the hydrogen (H) under the conditions shown in Table 13. An outermost surface layer of amorphous carbon (aC: H) was laminated to prepare an electrophotographic photosensitive member for negative charging.

[0183]

[Table 13] <Comparative Example 7> In this Comparative Example, a negative charging photoreceptor was formed without using a silicate film under the same conditions as in Comparative Example 6, and the aC: H outermost surface was further prepared under the conditions shown in Table 13. Stacking layers,
An electrophotographic photosensitive member for negative charging was produced.

The photoreceptor prepared in Example 7, the photoreceptor prepared in Comparative Example 7, and the photoreceptor prepared under the same conditions as in Example 1 were evaluated for adhesion by the following evaluation method.
The results are shown in Table 14.

(Heat Shock Test) The produced electrophotographic photosensitive member was left for 12 hours in a container adjusted to a temperature of −50 ° C., and immediately thereafter, it was placed in a container adjusted to a temperature of 80 ° C. and a humidity of 80%. Left for hours. 10 this cycle
After repeating the cycle, observe the surface of the electrophotographic photosensitive member,
Evaluation was made according to the following criteria: ⊚: Very good, ◯: Good, Δ: Fine film peeling is partially observed, ×: Relatively large film peeling is partially observed.

(Observation of Edge Peeling) The area of the edges (50 mm from the upper and lower ends) of the produced electrophotographic photosensitive member was observed with a magnifying glass and evaluated according to the following criteria: ⊚: Very good, ◯: Good, Δ: A part of minute film peeling is recognized, ×: A part of relatively large edge peeling is recognized.

[0187]

[Table 14] With the photoconductor manufactured in this example, good results were obtained in both the heat shock test and the observation of edge peeling.

[0188]

EFFECTS OF THE INVENTION According to the present invention, both improvement of charging ability and sensitivity and reduction of optical memory are achieved at a high level, the image quality is dramatically improved, and it is used for a long time or in a severe environment. In this case, a negative charging electrophotographic photosensitive member composed of a non-single-crystal material having a silicon atom as a base and capable of maintaining image quality can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining a structural example of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a schematic cross-sectional view for explaining a structural example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic diagram for explaining a procedure for forming a silicate film.

FIG. 4 is a schematic cross-sectional view for explaining a light-receiving layer forming device.

[Explanation of symbols]

101 base 102 Silicate film 103 Photoreceptive layer 104 Lower charge injection blocking layer 105 Photoconductive layer 106 upper charge injection blocking layer 107 surface protection layer 201 base 202 Silicate film 203 Photoreceptive layer 204 Lower charge injection blocking layer 205 Photoconductive layer 206 Upper charge injection blocking layer 207 Surface protection layer 208 Non-single crystal carbon film 301 base 302 processing unit 303 Substrate transport mechanism 311 Substrate input platform 321 Degreasing cleaning tank 331 Silicate film forming tank 341 rinse tank 351 drying tank 361 Substrate unloading platform 371 Transfer Arm 372 movement mechanism 375 Conveyor rail 373 chucking mechanism 374 air cylinder 4100 deposition equipment 4111 Reaction vessel 4112 base 4113 heater 4114 Introductory pipe 4115 Matching Box 4116 plumbing 4117 valve 4118 valve 4119 vacuum gauge 4200 supply device 4211 Mass Flow Controller 4212 Mass Flow Controller 4213 Mass Flow Controller 4214 Mass Flow Controller 4215 Mass Flow Controller 4216 Mass Flow Controller 4221 cylinder 4222 cylinder 4223 cylinder 4224 cylinder 4225 cylinder 4226 cylinder 4231 valve 4232 valve 4233 valve 4234 valve 4235 valve 4236 valve 4241 valve 4242 valve 4243 valve 4244 valve 4245 valve 4246 valve 4251 valve 4252 valve 4253 valve 4254 valve 4255 valve 4256 valve 4260 valve 4261 Pressure regulator 4262 Pressure regulator 4263 Pressure regulator 4264 Pressure regulator 4265 Pressure regulator 4266 Pressure regulator

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 5/08 334 G03G 5/08 334 335 335 5/10 5/10 B (72) Inventor Hosoi Hitoshi Tokyo 3-30-2 Shimomaruko, Ota-ku, Tokyo F term in Canon Inc. (reference) 2H068 CA32 CA34 DA05 DA08 DA12 DA14 DA19 DA23 DA56 DA57 DA62 DA64 DA69 DA72 FC03

Claims (8)

[Claims] 1. An electrophotographic photoreceptor for negative charging, comprising an aluminum or aluminum alloy substrate, and at least a coating and a light-receiving layer laminated in this order, the coating having a thickness of 0.5 nm or more and 15 nm or less. It is thick and mainly comprises aluminum, silicon and oxygen, and contains 0.1 atomic part or more and 1 atomic part or less of silicon and 1 atomic part or more and 5 atomic parts or less of oxygen with respect to 1 atomic part of aluminum, The light-receiving layer comprises a lower charge injection blocking layer made of a non-single-crystal silicon film containing at least nitrogen and oxygen and made of silicon as a base and not doped with impurities, and a light-receiving layer made of a non-single-crystal silicon film having silicon as a base. A conductive layer,
An upper charge injection blocking layer formed of a non-single-crystal silicon film containing carbon and a Group 13 atom as a base and silicon, and a surface protection layer formed of a non-single-crystal silicon film containing carbon as a base of silicon are laminated in this order. An electrophotographic photosensitive member for negative charging, which is characterized in that 2. The electrophotographic photoreceptor for negative charging according to claim 1, wherein the film is formed by using water containing an inhibitor. 3. The electrophotographic photoreceptor for negative charging according to claim 2, wherein the inhibitor is a silicate. 4. The negative charging electrophotographic photosensitive member according to claim 1, wherein the coating film contains nitrogen of 1 atom ppm or more and 10 atom% or less with respect to aluminum. 5. The negative charging electrophotographic photosensitive member according to claim 1, wherein a non-single crystal carbon film is provided on the surface protective layer. 6. In the upper charge injection blocking layer, the group 13 atom is boron, and the content of the boron is 10 atom ppm or more and 10000 atom ppm with respect to silicon.
The electrophotographic photosensitive member for negative charging according to any one of claims 1 to 5, wherein: 7. The content of carbon in the upper charge injection blocking layer is in the range of 10 atomic% or more and 70 atomic% or less with respect to the sum of silicon and carbon, and is lower than the content of carbon in the surface protective layer. Claim 1 characterized by being small
7. The electrophotographic photosensitive member for negative charging according to any one of 1 to 6. 8. The sum of nitrogen and oxygen contained in the lower charge injection blocking layer is 0.1 atomic% or more of silicon and 40% or more.
8. The negative charging electrophotographic photosensitive member according to claim 1, wherein the content is at most atomic%.