JP2006058532A - Method for manufacturing electrophotographic photoreceptor, electrophotographic photoreceptor and image forming apparatus using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the occurrence of image defects attributed to abnormally grown parts called protrusions on a surface of an electrophotographic photoreceptor. <P>SOLUTION: A method for manufacturing an electrophotographic photoreceptor by forming a layer comprising a non-single-crystal material in a vacuum-sealable film deposition furnace provided with an exhaust system and a raw gas feeding device comprises: a step of setting a substrate at least a surface of which is conductive in the film deposition furnace and forming a first layer comprising a non-single-crystal material on the substrate; a step of taking out the substrate, once from the film deposition furnace, on which the first layer has been deposited; a step of polishing the outermost surface of the first layer; a step of setting the substrate, again in the film deposition furnace, on which the first layer after the polishing has been deposited; a step of decomposing gas containing at least oxygen atoms with high-frequency power and subjecting the outermost surface of the first layer after the polishing to plasma treatment; and a step of depositing a second layer comprising a non-single-crystal material on the substrate after the plasma treatment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an amorphous silicon electrophotographic photosensitive member with few image defects, the electrophotographic photosensitive member, and an electrophotographic apparatus.

  Amorphous silicon photoconductors (hereinafter abbreviated as a-Si) have characteristics such as excellent wear resistance, heat resistance, photosensitivity, and pollution-free property.

  However, the a-Si film deposited by the plasma CVD method grows abnormally with the dust as a nucleus during film formation when dust of the order of several μm is adhered to the surface of the substrate, so-called “protrusions” are generated. It may end up. The protrusion has a shape obtained by reversing the conical shape as shown in FIG. 1 starting from dust, and the protrusion portion has a very large number of localized levels, so that the resistance is reduced and the charged charge escapes to the substrate side. It has the nature of For this reason, in the case of the reversal development method, the portion with the protrusion causes a black dot in the solid white image, that is, an image defect called “pochi”.

  As a countermeasure against image defects, the conventional a-Si electrophotographic photosensitive member manufacturing method takes out the substrate after deposition of the first layer from the reaction furnace, and then returns to the reaction furnace again to deposit the second layer. In addition, the substrate surface taken out from the reactor after the first layer deposition can be contacted with water, and further the surface can be lightly etched to improve adhesion (for example, patents) Reference 1).

  Further, the protrusions existing on the photoconductor are polished and flattened, and then the corona discharge is used to oxidize the protrusions where the surface layer is removed and the photoconductive layer is exposed. The occurrence of defects can be suppressed (see, for example, Patent Document 2).

  As a method for charging the a-Si photoconductor, a corona charging method using corona charging, a roller charging method in which charging is performed by direct discharge using a conductive roller, a sufficient contact area by magnetic particles, etc., are used to charge the material. There is an injection charging method in which charging is performed by directly injecting the photosensitive member surface. Among these, since the corona charging method and the roller charging method use discharge, discharge products are likely to adhere to the surface of the photoreceptor. In addition, since the a-Si photoconductor has a surface layer that is much harder than organic photoconductors, discharge products are likely to remain on the surface, and discharge is generated by adsorption of moisture in high-humidity environments. There is a case where an object and moisture are combined to reduce the resistance of the surface, and the electric charge on the surface easily moves to cause an image flow phenomenon. For this reason, various devices such as a surface rubbing method and a temperature control method for the photoreceptor may be required.

On the other hand, the injection charging method does not actively use discharge, and is a charging method in which charges are directly injected from a portion in contact with the surface of the photoreceptor, and therefore, a phenomenon such as image flow hardly occurs. In addition, the injection charging method, which is contact charging, has a merit that the unevenness of the charging potential can be made relatively small because the corona charging method is a voltage control type while the corona charging method is a current control type. In the conventional injection charging method, charging performance can be improved by bringing a contact charging member of magnetic brush-like particles made of a magnetic material and magnetic particles into contact with the surface of the photoreceptor (see, for example, Patent Document 3).
JP2003-149841 JP 7-64312 A, etc. JP-A-8-6353

  The conventional electrophotographic photoreceptor manufacturing method has made it possible to obtain an electrophotographic photoreceptor having a practical image quality to some extent.

  However, the demand for image defects is becoming stricter year by year in order to improve the image quality of color copying machines, and a higher quality electrophotographic photoreceptor is desired.

  Therefore, it is required to establish a manufacturing technique that can further reduce image defects as compared with conventional electrophotographic photosensitive members.

  In addition, as described above, the injection charging method has various merits. For example, in the contact injection charging method using a magnetic brush charger, the magnetic brush directly rubs the surface of the photosensitive member. It is necessary to produce an electrophotographic photosensitive member having good adhesion with careful management of the layer forming method.

  An object of the present invention is to overcome the problems in the conventional electrophotographic photosensitive member as described above without sacrificing electrical characteristics, and to provide a method for producing a highly durable electrophotographic photosensitive member with few image defects. It is an object to provide a photographic photoreceptor and an electrophotographic apparatus.

  In order to solve the above-mentioned problems, the present inventors have earnestly realized an electrophotographic photosensitive member having no adverse effect on electrical characteristics, greatly improving image defects such as spots, and having high durability. As a result of repeated research, the inventors have found that the above object can be satisfactorily achieved and have reached the present invention.

That is, the present invention relates to a method for producing an electrophotographic photosensitive member including a layer made of a non-single crystal material, and as a first step, a vacuum-tight film forming furnace provided with an exhaust unit and a source gas supply unit. A step of installing a cylindrical substrate having a conductive surface, decomposing the source gas with high frequency power, and depositing a first layer made of a non-single crystal material on the substrate, and a second step, the first step The substrate on which the layer is deposited is once removed from the film forming furnace, the third step is a polishing process on the outermost surface of the first layer, and the fourth step is a first step after the polishing process. A substrate on which the layer is deposited, a gas containing at least oxygen atoms is decomposed by high-frequency power, and a plasma treatment is performed on the outermost surface of the first layer after the polishing, and as a fifth step, Non-single crystal on substrate after plasma treatment A second layer of charges, a process for producing an electrophotographic photosensitive member characterized by having a step of re-depositing. The plasma treatment of the fourth step is a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ), oxygen (O ₂ ), dinitrogen monoxide (N ₂ O), carbon dioxide (CO ₂ ) as a source gas. It is preferable that one is selected from the above. Further, the mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) preferably has a mixing ratio of oxygen (O ₂ ) of 15 Vol. Furthermore, it is preferable that plasma treatment of hydrogen (H ₂ ) or inert gas is subsequently performed after the plasma treatment in the fourth step. Furthermore, before proceeding to the fourth step, it is preferable that a treatment for bringing the surface of the first layer into contact with water is performed.

  According to the present invention, a first layer made of a non-single-crystal material and a second layer made of a non-single-crystal material are stacked on a cylindrical substrate having at least a conductive surface. In the electrophotographic photosensitive member, the protrusion in the first layer stops growing on the surface of the first layer, and oxygen atoms are contained in the interface region with the second layer. An electrophotographic photoreceptor. The oxygen atom contained in the interface region with the second layer preferably has a peak in the oxygen atom content distribution in the thickness direction of the interface region.

  As described above, according to the present invention, a plasma treatment is performed on the projection after polishing using a gas containing at least oxygen atoms, and a second layer is formed, thereby causing the projection. This reduces the effect of reducing image defects. Moreover, by performing the above-mentioned plasma treatment, adhesion is improved and high durability is possible.

  By adopting the above configuration, the electrophotographic photosensitive member of the present invention maintains high durability, and image defects due to protrusions existing on the surface of the photosensitive member are drastically reduced.

  The present inventors have studied improvement of image defects caused by protrusions, which is an important problem in a photoreceptor made of a non-single crystal material, particularly an a-Si photoreceptor. In particular, intensive efforts have been made to prevent image defects caused by protrusions caused by film peeling from the reaction furnace walls and structures in the furnace during the formation of the deposited film.

  As described above, the reason why the protrusion becomes an image defect such as a spot is that there are many localized levels of the protrusion portion, the resistance is lowered, and the charged charge is released to the substrate side. However, the protrusion generated by the dust attached during the film formation grows from the middle of the deposited film, not from the substrate. Therefore, charge injection from the substrate is blocked, and if a layer with some charge blocking is provided on the surface of the protrusion to prevent injection of charged charge, it may not cause image defects even if the protrusion exists. There is. For example, it is preferable to use surface oxidation of the protrusion surface as a layer having charge blocking from the protrusion surface. However, the long-term stability of image defects may be impaired. Therefore, it is necessary to provide a method for producing an electrophotographic photosensitive member that can stably maintain a reduction in image defects over a long period of time in any electrophotographic process. For example, a second layer having a certain degree of hardness is provided. Is effective.

  Therefore, the present inventors select a film forming condition in which protrusions grow from the middle of the deposited film, polish the surface of the photoconductor manufactured under this condition, perform a plasma treatment on the surface after polishing, and perform the second processing. An experiment was conducted to provide a layer. As a result, it has been clarified that there is a difference in the adhesion and the effect of reducing image defects depending on the presence or absence of the plasma treatment, and further on the conditions of the plasma treatment. Specifically, it has been found that adhesion can be improved and image defects can be reduced by using a gas containing at least oxygen atoms as plasma processing conditions. Although the details of the reason why the effect is obtained are unknown, it is considered that the formation of the oxidized region has an influence at the interface between the first layer and the second layer. That is, the improvement of adhesion can function as an oxygen atom strengthening bond between silicon atom and carbon atom, and the further reduction of image defects can function as a charge injection blocker due to the bond between oxygen atom and silicon atom. , It is inferred as one of the reasons.

  Hereinafter, a description will be given with reference to FIG. The top of the protrusion is flattened by polishing on the first layer 202 on which the protrusion is grown, and then the second layer 203 is formed. As a result, the protrusion is formed on the first layer 202, but the protrusion due to the protrusion is not formed on the second layer 203. In this state, in order to reduce image defects by the second layer 203, it is necessary to prevent the slipping of charges at the protrusions as much as possible so that the charged charges are sufficiently retained. For this reason, the inventors focused on the joint between the protrusion 211 and the second layer 203, formed an oxidized region in the joint so that the charging performance was as good as possible, and evaluated the image defect. It has been found that the effect is improved. Specifically, with regard to the plasma treatment performed on the surface of the projection 211 after polishing, by decomposing a gas containing at least oxygen atoms and performing the plasma treatment, charge slippage at the projection is reduced, and image defects are reduced. The effect was improved.

In addition, the present inventors have earnestly combined various electrophotographic processes and various photoconductor manufacturing conditions in order to achieve higher image quality and higher durability for the combination of an electrophotographic apparatus and an electrophotographic photoconductor. investigated.
Regarding the electrophotographic apparatus using the electrophotographic photosensitive member of the present invention, the contact charging method using a magnetic brush charger is a voltage control method, so that it is possible to reduce the width of the surface potential drop, and image defects are conspicuous. I found it difficult. For this reason, it has been found that the combination with the electrophotographic photosensitive member of the present invention makes it possible to achieve a high degree of compatibility with image defect defect suppression and high durability without peeling.

  Hereinafter, the present invention will be described in detail with reference to the drawings as necessary.

<A-Si photoconductor according to the present invention>
An example of the electrophotographic photoreceptor and the manufacturing method according to the present invention will be described with reference to FIG.

  The electrophotographic photosensitive member shown in FIG. 2A has a lower blocking layer 204 made of a non-single crystalline material containing at least silicon atoms as a first step on a base 201 made of a conductive material such as aluminum (Al). Then, a photoconductive layer 205 and an intermediate layer 206 made of a non-single-crystal material containing at least carbon atoms and silicon atoms are stacked as the first layer 202. Thereafter, as a second step, the substrate on which the first layer 202 is once laminated is taken out from the film forming furnace, and then, as a third step, the top of the protrusion is flattened by polishing the surface of the first layer. Then, as a fourth step, a substrate on which the first layer after polishing is deposited is installed, a gas containing at least oxygen atoms is decomposed by high-frequency power, and plasma treatment is performed on the outermost surface of the first layer after polishing. Apply. Thereafter, as a fifth step, the second layer 203 is laminated on the substrate after the plasma treatment. The second layer 203 includes a silicon carbide layer containing at least carbon atoms and silicon atoms, a non-single-crystal material containing carbon atoms as a base material, such as amorphous carbon containing hydrogen atoms (a-C (H)). Notation).

  By manufacturing in this way, the second layer 203 can be deposited with the protrusion 211 generated in the first layer 202 sandwiching the oxidized region, and even if the protrusion 211 is present, the surface direction from the surface to the substrate It is possible to drastically prevent slipping of charged charges to the image, and to reduce image defects.

  In the electrophotographic photosensitive member shown in FIG. 2B, on the substrate 201, as a first step, a lower blocking layer 204 made of at least a non-single crystalline material, a photoconductive layer 205, a non-single substance containing at least carbon atoms and silicon atoms. An upper blocking layer 207 and an intermediate layer 206 made of a crystalline material are stacked as the first layer 202. Thereafter, as a second step, the substrate on which the first layer 202 is once laminated is taken out from the film forming furnace, and then, as a third step, the top of the protrusion is flattened by polishing the surface of the first layer. Then, as a fourth step, a substrate on which the first layer after polishing is deposited is installed, a gas containing at least oxygen atoms is decomposed by high-frequency power, and plasma treatment is performed on the outermost surface of the first layer after polishing. Apply. Thereafter, as a fifth step, the second layer 203 is laminated on the substrate after the plasma treatment. The second layer 203 is a silicon carbide layer containing at least carbon atoms and silicon atoms, or a non-single-crystal material having carbon atoms as a base material, for example, aC (H).

  By manufacturing in this way, the second layer 203 can be deposited with the protrusion 211 generated in the first layer 202 sandwiching the oxidized region, and even if the protrusion 211 is present, the surface direction from the surface to the substrate It is possible to drastically prevent slipping of charged charges to the image, and to reduce image defects.

  Further, the first blocking layer 202 is provided with a lower blocking layer 204 and an upper blocking layer 207. The lower blocking layer 204 and the upper blocking layer 207 can contain a group 13 atom, a group 15 atom, or the like as a dopant to control the charging polarity such as positive charging and negative charging.

  Specific examples of group 13 atoms that serve as dopants include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), with B and Al being particularly preferred. is there. Specific examples of Group 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). P is particularly preferred.

<Material of the substrate according to the present invention>
As the base material, conductive materials such as aluminum (Al) and stainless steel are generally used. For example, various conductive materials such as various plastics, glass, ceramics, etc., which have no electrical conductivity, are at least a light receiving layer. It is also possible to use a material imparted with conductivity by vapor deposition on the surface on the side where the film is formed.

<First layer according to the present invention>
The photoconductive layer 205 constituting the first layer 202 of the present invention is a film made of amorphous silicon (also abbreviated as a-Si (H)), which is a non-single-crystal material containing silicon atoms as a base and further containing hydrogen atoms. Is used.

  The a-Si (H) film of the photoconductive layer 205 can be formed by a plasma CVD method, a sputtering method, an ion plating method, etc., but a film formed by using the plasma CVD method is a particularly high quality film. Since it is obtained, it is preferable.

By using silicon hydride (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like as a raw material gas as a raw material gas, and decomposing with high frequency power Can be created. Further, SiH ₄ and Si ₂ H ₆ are preferable from the viewpoint of easy handling at the time of layer preparation, good Si supply efficiency, and the like. Further, it is preferable to mix a gas containing hydrogen (H ₂ ) to form a deposited film in order to improve characteristics.

  At this time, the temperature of the substrate is preferably 150 to 350 ° C., more preferably about 180 to 300 ° C. in view of characteristics. This is for accelerating the surface reaction on the substrate surface and sufficiently relaxing the structure.

Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, 1 × 10 ⁻² to 1 × 10 ³ Pa, preferably 5 × 10 ^{−2 to} 5 × 10 ² Pa, More preferably, it is set to 1 × 10 ⁻¹ to 1 × 10 ² Pa.

  The layer thickness of the first layer 202 is not particularly limited, but about 15 to 50 μm is appropriate in consideration of manufacturing costs and the like.

  Further, the lower blocking layer 204 provided as necessary is generally based on a-Si (H), and is a group 13 atom of the periodic table (hereinafter also simply referred to as group 13 atom), group 15 of the periodic table. By containing a dopant such as an atom (hereinafter also simply referred to as a Group 15 atom), it is possible to improve the ability to prevent carriers from being injected from the substrate. In this case, if necessary, the stress can be adjusted by containing at least one atom selected from C, N, and O to have a function of improving the adhesion of the photosensitive layer.

As group 13 atoms and group 15 atoms used as the dopant for the lower blocking layer 204, those described above are used. Further, as 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 Examples thereof include boron hydrides such as ₆ H ₁₂ and B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . Among these, B ₂ H ₆ is one of the preferred raw materials from the viewpoint of handling.

Effectively used as a raw material for introducing Group 15 atoms are phosphorus hydrides such as PH ₃ and P ₂ H ₄ , PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , Examples thereof include phosphorus halides such as PBr ₃ and PI ₃ , and PH ₄ I.

The content of dopant atoms is 1 × 10 ⁻² to 1 × 10 ⁴ atoms ppm, more preferably 5 × 10 ^{−2 to} 5 × 10 ³ atoms ppm with respect to the total amount of constituent atoms in the lower blocking layer 204. Optimally, it is 1 × 10 ⁻¹ to 1 × 10 ³ atoms ppm.
Further, the upper blocking layer 207 provided as necessary is preferably composed of a silicon carbide layer containing at least silicon atoms and carbon atoms in the present invention. For example, amorphous silicon carbide containing hydrogen atoms (a-SiC) (H)). Further, it is necessary to appropriately include a group 13 atom or a group 15 atom.

As the group 13 atom or group 15 atom in the present invention, those described above are used.
The content of the Group 13 or Group 15 dopant atoms contained in the upper blocking layer 207 cannot be generally determined depending on the composition and manufacturing method of the upper blocking layer 207, but in general, in the upper blocking layer 207 It is preferable to be 100 atom ppm or more and 30000 atom ppm or less with respect to the total amount of constituent atoms.

  The group 13 or group 15 dopant atoms contained in the upper blocking layer 207 may be uniformly distributed in the upper blocking layer 207 or may be unevenly distributed in the layer thickness direction. It may contain. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to uniformly contain the material in a uniform distribution from the viewpoint of uniform characteristics in the in-plane direction.

  Further, the carbon atoms contained in the upper blocking layer 207 may be uniformly distributed in the layer, or may be contained in a non-uniformly distributed state in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to uniformly contain the material in a uniform distribution from the viewpoint of uniform characteristics in the in-plane direction.

  Further, the content of carbon atoms contained in the entire layer region of the upper blocking layer 207 is appropriately determined so that the object of the present invention can be effectively achieved, but with respect to the sum of silicon atoms and carbon atoms. A range of 10 atomic% to 40 atomic% is preferable.

  In addition, it is necessary that the upper blocking layer 207 contains hydrogen atoms. This compensates for dangling bonds of silicon atoms, and improves layer quality, in particular, photoconductivity and charge retention characteristics. It is indispensable to. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms.

  In addition, an intermediate layer 206 made of a non-single-crystal material containing at least carbon atoms and silicon atoms is formed as the uppermost layer of the first layer 202 provided as necessary. The intermediate layer 206 is, for example, a-SiC (H).

  The carbon atoms contained in the intermediate layer 206 may be uniformly distributed in the layer or may be contained in a non-uniformly distributed state in the layer thickness direction. When the thickness is at least 10 nm, the polishing processability is good and the sensitivity is good when the total amount of carbon atoms and silicon atoms is 50 atom% or more and 90 atom% or less.

  In addition, it is preferable that the intermediate layer 206 contains hydrogen, and by containing hydrogen, dangling bonds of constituent atoms such as silicon atoms are compensated for, thereby improving layer quality, in particular, photoconductivity characteristics and charge retention characteristics. Can be improved. From this point of view, the hydrogen content is preferably 30 atomic% or more and 70 atomic% or less, more preferably 35 atomic% or more and 65 atomic% or less, and still more preferably 40 based on the total amount of constituent atoms in the outermost surface. Atom% or more and 60 atom% or less.

Substances that can be carbon supply gases used in the intermediate layer 206 forming the outermost surface of the upper blocking layer 207 and the first layer 202 include CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H _6. , C ₃ H ₈ , C ₄ H _{10 and} other hydrocarbons that can be gasified or that can be gasified can be used effectively. In addition, the layer is easy to handle and the carbon supply efficiency is good. And CH ₄ , C ₂ H ₂ , and C ₂ H ₆ are preferable. Further, these raw material gases for supplying carbon may be diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

  The thickness of the intermediate layer 206 is usually 10 nm or more and 5000 nm or less, preferably 50 nm or more and 2000 nm or less, and most preferably 100 nm or more and 1000 nm or less. When the layer thickness is 10 nm or more, scratches and the like do not occur even when the surface of an a-Si photoconductor is polished. If the layer thickness is 5000 nm or less, the residual potential remaining on the photoconductor after the toner image is formed by the electrostatic latent image on the surface of the photoconductor and the toner image is transferred to a copy sheet or the like increases. There is no.

<Plasma treatment according to the present invention>
The plasma treatment process according to the present invention is once taken out of the film forming furnace after the first layer 202 is formed, and is performed after polishing by a surface polishing apparatus.

The processing gas used in the plasma processing of the present invention uses a gas containing at least oxygen atoms, decomposes the processing gas with high-frequency power, and is subjected to the outermost surface processing by generating plasma ions. As a processing gas, a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ), oxygen (O ₂ ), nitrogen monoxide (NO), dinitrogen monoxide (N ₂ O), nitrogen dioxide (NO ₂ ). ), Carbon monoxide (CO), carbon dioxide (CO ₂ ) and the like are preferable. In particular, a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ), oxygen (O ₂ ), dinitrogen monoxide (N ₂ O), and carbon dioxide (CO ₂ ) are preferable in terms of ease of handling. . With respect to a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ), a mixing ratio of 15 vol.% Or more is preferable in that an oxidized region can be effectively formed.

Here, the plasma treatment may be performed without heating the substrate on which the first layer after polishing is deposited, or the plasma treatment may be performed after heating to a desired temperature.
In addition, it is desirable to clean the substrate on which the first layer is formed before setting it again in the film forming furnace in order to improve the adhesion of the second layer 203 and reduce dust adhesion. As a specific cleaning method, the surface may be wiped with a clean cloth or paper, but precision cleaning is preferably performed by organic cleaning or water cleaning. In particular, water washing is more preferable from recent environmental considerations.

In the present invention, it is more preferable to perform plasma treatment with hydrogen or an inert gas after plasma treatment containing at least oxygen atoms from the viewpoint of improving adhesion.
FIG. 7 shows an example of the depth profile of the oxygen atom content in the electrophotographic photosensitive member produced by performing the plasma treatment according to the present invention. In addition, a measurement is measured by SIMS (CAMECA company_made, apparatus name: IMS-4F). As measurement conditions, Cs ⁺ having primary ion energy of 14.5 keV was used, and negative ions were detected as secondary ions. At the end of the measurement, the depth of the sputter crater was measured with a stylus type step gauge, and the horizontal axis of the measurement data was converted from time to depth using the obtained sputter rate. From FIG. 7 obtained in this way, it can be seen that the content distribution of oxygen atoms has a peak at the interface between the first layer and the second layer, and a region where oxygen atoms are present is formed. It was.

<Second layer according to the present invention>
In addition, the second layer 203 of the present invention is a silicon carbide layer containing at least carbon atoms and silicon atoms, or a non-single crystal material based on carbon atoms, for example, aC (H). preferable. The second layer 203 is provided to prevent fusion, scratches, and wear during long-term use.

  In the present invention, the second layer 203 needs to contain hydrogen atoms, which compensates for dangling bonds of silicon atoms, and improves layer quality, in particular, photoconductivity and charge retention characteristics. Indispensable to improve. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms.

Examples of a substance that can be a silicon (Si) supply gas used in the formation of the second layer 203 include gas states such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ , or gasification. The obtained silicon hydride (silanes) can be used effectively, and SiH ₄ and Si ₂ H ₆ are preferable from the viewpoint of ease of handling at the time of layer formation, good Si supply efficiency, and the like. . Further, these Si supply source gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like if necessary.

Examples of substances that can serve as a carbon supply gas include CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H _{10 and} other hydrocarbons that can be gasified or gasified. CH ₄ , C ₂ H ₂ , and C ₂ H ₆ are preferable from the viewpoints of ease of handling during layer formation and good carbon supply efficiency. Further, these raw material gases for supplying carbon may be diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, 1 × 10 ⁻² to 1 × 10 ³ Pa, preferably 5 × 10 ^{−2 to} 5 × 10 ² Pa, Optimally, it is preferably 1 × 10 ⁻¹ to 1 × 10 ² Pa.
Further, the optimum range of the substrate temperature is appropriately selected according to the layer design. In general, it is more preferable to set the substrate temperature lower than the substrate temperature at the time of forming the first layer from the viewpoint of improving adhesion. Specifically, when the silicon carbide layer is formed, it is desirable that the temperature is 100 ° C. to 330 ° C., more preferably 150 ° C. to 270 ° C. In the case of a non-single crystal material having a carbon atom as a base material, for example, a-C (H), it is preferable to select 20 ° C. or more and 50 ° C., preferably about room temperature, for example, 25 ° C.

  The carbon content of the silicon carbide layer is preferably in the range of 50% to 90% with respect to the sum of silicon atoms and carbon atoms.

<A-Si Photosensitive Film Forming Apparatus According to the Present Invention>
FIG. 3 schematically shows an example of a film forming apparatus for a photoreceptor by an RF plasma CVD method using an RF band high-frequency power source for forming the first layer and the second layer.

  This apparatus is roughly composed of a film forming apparatus (3100), a source gas supply apparatus (3200), and an exhaust apparatus (not shown) for reducing the pressure inside the cathode electrode (3111). A cylindrical substrate (3112) having a conductive surface, a substrate heating heater (3113), and a source gas introduction pipe (3114) are installed in the cathode electrode (3111) of the film forming apparatus (3100), and further a high frequency A matching box (3115) is connected.

The raw material gas supply device (3200) includes SiH ₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other raw material gas cylinders (3221 to 3226) and valves (3231 to 3236, 3241 to 3246, 3251 to 3256) and a mass flow controller (3211 to 3216), each source gas cylinder is connected to a source gas introduction pipe (3114) in the cathode electrode (3111) via a valve (3260).

  Formation of the deposited film using this apparatus can be performed as follows, for example.

  First, a cylindrical substrate (3112) having a conductive surface is installed in the cathode electrode (3111), and the cathode electrode (3111) is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical substrate (3112) having a conductive surface is controlled to a predetermined temperature of 150 ° C. to 350 ° C. by the substrate heating heater (3113).

  In order to flow the source gas for forming the deposited film into the cathode electrode (3111), confirm that the gas cylinder valve (3231 to 3236) and the reaction vessel leak valve (3117) are closed, and the inflow valve (3241-3246), outflow valve (3251-3256), auxiliary valve (3260) is confirmed to be open, first the main valve (3118) is opened, the cathode electrode (3111) and the gas pipe (3116 ).

  Next, when the reading of the vacuum gauge (3119) becomes about 0.1 Pa or less, the auxiliary valve (3260) and the outflow valves (3251 to 3256) are closed. Thereafter, each gas is introduced from the gas cylinder (3221 to 3226) by opening the valve (3231 to 3236), and each gas pressure is adjusted to 0.2 MPa by the pressure regulator (3261 to 3266). Next, the inflow valves (3241 to 3246) are gradually opened to introduce each gas into the mass flow controller (3211 to 3216).

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

When the cylindrical substrate (3112) having a conductive surface reaches a predetermined temperature, necessary ones of the outflow valves (3251 to 3256) and the auxiliary valve (3260) are gradually opened, and gas cylinders (3221 to 3266) Then, a predetermined gas is introduced into the cathode electrode (3111) through the gas introduction pipe (3114). Next, it adjusts so that each source gas may become a predetermined | prescribed flow volume by a massflow controller (3211-3216). At that time, the opening of the main valve (3118) is adjusted while looking at the vacuum gauge (3119) so that the pressure in the cathode electrode (3111) becomes a predetermined pressure of 1 × 10 ² Pa or less. When the internal pressure is stabilized, high frequency power to be applied is introduced into the cathode electrode (3111) through the high frequency matching box (3115) by introducing high frequency power having a frequency of 1 MHz to 50 MHz, for example, 13.56 MHz, to cause glow discharge. By this discharge energy, the source gas introduced into the reaction vessel is decomposed, and a deposited film containing a predetermined silicon atom as a main component is formed on the cylindrical substrate (3112) having a conductive surface. After the formation of the desired film thickness, the supply of RF power is stopped, the outflow valve is closed, the gas flow into the reaction vessel is stopped, and the formation of the deposited film is completed.

  By repeating the same operation a plurality of times, a desired multilayered light-receiving layer is formed. When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and the respective gas flows from the outflow valves (3251 to 3256) into the cathode electrode in the cathode electrode (3111). In order to avoid remaining in the pipe leading to (3111), close the outflow valve (3251-3256), open the auxiliary valve (3260), and then fully open the main valve (3118) to temporarily high vacuum the system If necessary, perform the exhausting operation.

  In order to make the film formation uniform, it is also effective to rotate the cylindrical substrate (3112) having a conductive surface at a predetermined speed by a driving device (not shown) during the layer formation. It is.

  Furthermore, it goes without saying that the gas species and valve operations described above are changed according to the production conditions of each layer.

  The heating method of the substrate may be any heating element that is vacuum specification. More specifically, the heating resistance of a sheathed heater, an electric resistance heating element such as a plate heater, a ceramic heater, a halogen lamp, an infrared lamp, etc. Examples of the heating element include a radiation lamp heating element, a liquid, a gas, and the like as a heating medium and a heat exchange means. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat resistant polymer resin, and the like can be used.

  In addition to this, there is used a method in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the substrate is transported in a vacuum in the reaction container.

<Surface polishing apparatus according to the present invention>
FIG. 4 shows an example of a surface processing apparatus used for surface processing in the manufacturing process of the electrophotographic photosensitive member of the present invention, specifically, an example of a surface polishing apparatus used for polishing as surface processing. Show. In the configuration example of the surface polishing apparatus shown in FIG. 4, a workpiece (deposited film surface on a cylindrical substrate) 400 is a cylindrical substrate having a first layer made of a-Si deposited on the surface thereof. Yes, attached to the elastic support mechanism 420. In the apparatus shown in FIG. 4, for example, a pneumatic holder is used as the elastic support mechanism 420, and specifically, a pneumatic holder manufactured by Bridgestone (trade name: air pick, model number: PO45TCA * 820) is used. The pressure elastic roller 430 winds the polishing tape 431 and presses the surface of the workpiece 400 on the a-Si photoconductive layer or the silicon carbide layer. The polishing tape 431 is supplied from the feed roll 432 and collected by the take-up roll 433. The feed speed is adjusted by the fixed feed roll 434 and the capstan roller 435, and the tension is also adjusted. As the polishing tape 431, what is usually called a wrapping tape is preferably used. When the outermost surface portion of the first layer is processed, SiC, Al ₂ O ₃ , Fe ₂ O ₃ or the like is used as abrasive grains for the lapping tape. Specifically, Fuji Film Lapping Tape LT-C2000 was used. The roller portion of the pressure elastic roller 430 is made of a material such as neoprene rubber or silicon rubber. In addition, the roller part shape is preferably such that, in the longitudinal direction, the diameter of the central part is slightly larger than the diameters of both end parts, for example, the diameter difference between the two is 0.0 to 0.6 mm, more preferably 0.2 to 0.4 mm. The shape which becomes is more preferable. The pressure elastic roller 430 is a polishing tape 431, for example, the lapping described above, while pressing the rotating workpiece (deposited film surface on the cylindrical substrate) 400 in a pressure range of 9.8 kPa to 980 kPa. The tape is fed to polish the surface of the deposited film.

  For the surface polishing performed in the present invention, it is also possible to use a wet polishing means such as buff polishing in addition to the means using the polishing tape. Further, when using a wet polishing means, a step of washing and removing the liquid used for polishing is provided after the polishing process, and at that time, the surface is brought into contact with water and cleaned. be able to.

<Electrophotographic apparatus according to the present invention>
An example of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention is shown in FIG.

  FIG. 5 is a schematic view showing an example of an image forming process of the electrophotographic apparatus, and the photoconductor 501 rotates to perform a copying operation. Around the photosensitive member 501, there are a magnetic brush injection charger 503, a developing device 504, a transfer paper supply system 505, a transfer charger 506 (a), a separation charger 506 (b), a cleaning unit 507, a transport system 508, a charge eliminating device. A light source 509 and the like are provided.

  Hereinafter, the image forming process will be described more specifically. The photoconductor 501 is uniformly charged by the magnetic brush charger 503. Next, an electrostatic latent image is formed by light emitted from the laser unit 518 and passing through the mirror 519, and negative polarity toner is supplied from the developing device 504 to the latent image to form a toner image. For control of the laser unit 518, a signal from the CCD unit 517 is used. That is, the light emitted from the lamp 510 is reflected by the original 512 placed on the original platen glass 511, passes through the mirrors 513, 514, 515, is imaged by the lens of the lens unit 516, and is then output by the CCD unit 517. The signal converted into is derived.

  On the other hand, the transfer material P that is adjusted in the leading edge timing by the registration roller 522 through the transfer paper supply system 505 and is supplied in the direction of the photoconductor 501 is transferred between the transfer charger 506 (a) to which the high voltage is applied and the photoconductor 501. A positive electric field having a polarity opposite to that of the toner is applied from the back surface in the gap, whereby a negative polarity toner image on the surface of the photoreceptor is transferred to the transfer material P. Next, the separation charger 506 (b) to which a high-voltage AC voltage is applied causes the transfer material P to pass through the transfer conveyance system 508 to the fixing device 524, where the toner image is fixed and carried out of the device.

<Water cleaning apparatus used in the present invention>
In the production process of the electrophotographic photosensitive member of the present invention, it is preferable to provide a treatment for bringing the surface into contact with water after the polishing process. This water contact treatment corresponds to water washing, and the procedure and conditions of the water washing are disclosed in, for example, Japanese Patent No. 2786756. FIG. 6 shows an example of a water cleaning apparatus used in the manufacturing process of the electrophotographic photosensitive member of the present invention.

The processing apparatus shown in FIG. 6 includes a processing unit 602 and a processing target member transport mechanism 603. The processing unit 602 includes a processing member input table 611, a processing member cleaning tank 621, a pure water contact tank 631, a drying tank 641, and a processing member carry-out table 651. Each of the cleaning tank 621 and the pure water contact tank 631 is provided with a temperature control device (not shown), and is configured to keep the liquid temperature used in each tank constant. The transfer mechanism 603 includes a transfer rail 665 and a transfer arm 661. The transfer arm 661 moves on the rail 665, and a chuck that holds a conductive substrate on which a deposited film, which is a member to be processed 601, is formed. It comprises a king mechanism 663 and an air cylinder 664 for moving the chucking mechanism 663 up and down. The member to be processed 601 placed on the input table 611 is transferred to the cleaning tank 621 by the transfer mechanism 603. In the cleaning tank 621, for example, a cleaning liquid 622 made of a surfactant aqueous solution is placed, and the object 601 is immersed in the cleaning tank 601 and subjected to ultrasonic cleaning processing, for example, foreign matter attached to the surface, for example, The oil and powder are cleaned and removed. Next, the cleaned member 601 is transported to the pure water contact tank 631 by the transport mechanism 603, and pure water having a predetermined liquid temperature, for example, 25 ° C. and having a resistivity of 17.5 MΩ · cm is nozzleed. Sprayed at a pressure of 632 to 50 kg · f / cm ² . By this pure water spray, the cleaning liquid remaining in the previous process is washed away. The member to be treated 601 after the pure water contact process is moved to the drying tank 641 by the transport mechanism 603, and dried by blowing high-temperature high-pressure air from the nozzle 642. The member to be processed 601 after the drying process is carried to the carry-out table 651 by the carrying mechanism 603.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these.

[Example 1]
A first film composed of a lower blocking layer, a photoconductive layer, and an intermediate layer is formed on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 1 using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. A substrate deposited to layer was prepared.

  Next, the substrate deposited up to the first layer was once taken out from the film forming furnace, and the surface of the substrate was processed. For surface processing, surface polishing was performed using a lapping tape (trade name: LT-C2000) manufactured by Fuji Film Co., Ltd. with the polishing apparatus shown in FIG. Next, the substrate was returned to the RF plasma a-Si photosensitive film forming furnace different from the film forming furnace in which the first film shown in FIG. 3 was deposited. Thereafter, plasma treatment is performed on the outermost surface of the first layer under the conditions shown in Table 2, and then a surface layer, which is the second layer, is deposited under the conditions shown in Table 3. A positively charged electrophotographic photosensitive member having a layer structure was prepared.

In this embodiment, as shown in Table 2, the oxygen mixing ratio of the carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) mixed gas was changed as the plasma treatment condition.

  Further, the produced electrophotographic photosensitive member was measured for the depth profile of the oxygen atom content by SIMS (manufactured by CAMECA, apparatus name: IMS-4F), and the interface portion between the first layer and the second layer was measured. The maximum content of oxygen atoms in the thickness direction was calculated. The results are shown in Table 2.

As SIMS measurement conditions, Cs ⁺ whose primary ion energy was 14.5 keV was used, and negative ions were detected as secondary ions. At the end of the measurement, the sputter crater depth was measured with a stylus type step gauge to obtain the sputtered film thickness. Next, the sputtering rate was calculated from the film thickness and the SIMS sputtering time. The horizontal axis of the measurement data was converted from time to depth using the obtained sputtering rate, and the depth from the outermost surface of the second layer was determined.

  The photoreceptor obtained by the above procedure is a photoreceptor used for positive charging, and was evaluated as follows.

(Image defect)
A magnetic brush charger was adopted as the primary charger, and the electrophotographic photosensitive member produced in this example was mounted on an electrophotographic apparatus provided with a cleaning blade as a cleaner for image formation. Specifically, the Canon iR6000 (process speed 265mm / sec) modified for charging the magnetic brush is applied with AC voltage (1.2kVpp, 1.0kHz) to the magnetic brush charger, and a DC voltage of + 550V is applied. Superposed. The image thus obtained was observed, and the number of black spots appearing on the image due to the protrusion was counted.

The obtained results were ranked by relative comparison when the value in Comparative Example 1 described later was 100%.
◎ ・ ・ ・ 35% to less than 65% ○ ・ ・ ・ 65% to less than 95% △ ・ ・ ・ 95% to less than 105% × ... 105% or more

(Adhesion evaluation)
First, the produced photoreceptor was set in an electrophotographic apparatus using a magnetic brush charger as a primary charger and a cleaner provided with a cleaning blade, and 1 million sheets of A4 paper was passed through. Specifically, the Canon iR6000 (process speed 265mm / sec) modified for charging the magnetic brush is applied with AC voltage (1.2kVpp, 1.0kHz) to the magnetic brush charger, and a DC voltage of + 550V is applied. Superposed.

After the endurance, the electrophotographic photosensitive member is left in a container adjusted to a temperature of −30 ° C. for 48 hours, and then immediately left in a container adjusted to a temperature of + 150 ° C. for 48 hours. The surface of the electrophotographic photosensitive member was observed after a heat shock test in which this cycle was repeated 10 times. Further, the surface of the electrophotographic photosensitive member was observed after a vibration test in which a vibration of 10 Hz to 10 kHz consisting of an acceleration of 7 G was repeated 5 cycles with a sweep time of 2.2 minutes. Evaluation is based on the following criteria.

◎: Very good with no film peeling after heat shock test and even after vibration test ○: No film peeling after heat shock test, after film vibration test, a minute film at the edge of non-image area Peeling is partially observed but there is no practical problem. △: After heat shock test, some minute film peeling is observed at the edge of the non-image area, but there is no practical problem. ×: Relatively large film after heat shock test. Peeling is partly observed and there are practical problems.

(Comprehensive evaluation)
A: All evaluation items consist of A, which is a very good level.
○: For all evaluation items, it consists of ◎ and ○, which is a good level.
Δ: For all evaluation items, at least one Δ is included, but it is at a level that does not cause a problem in practice.

<Comparative Example 1>
Using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. 3, a substrate having a first layer deposited on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 1 was produced. Next, the deposited substrate was once taken out from the film forming furnace, and surface polishing was performed under the same conditions as in Example 1. Next, the film is returned to the RF plasma a-Si photosensitive film forming furnace different from the film forming furnace in which the first film shown in FIG. 2 is deposited, and the surface layer as the second layer is formed under the conditions shown in Table 3. The positively charged electrophotographic photosensitive member having the layer structure of FIG. 2A was deposited.

  In this comparative example, the plasma treatment was not performed before the second layer was deposited.

  The photoreceptor obtained by the above procedure was evaluated in the same manner as in Example 1.

The results of Example 1 and Comparative Example 1 are shown in Table 4. As is clear from the results in Table 4, the effect of reducing image defects and improving the adhesion was obtained in Example 1 in which plasma treatment was performed, compared to Comparative Example 1 in which plasma treatment was not performed. Furthermore, from the observation result of peeling, it was found that the reduction of image defects was particularly good when the oxygen mixing ratio of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) was 15 Vol.

[Example 2]
Using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. 3, the lower blocking layer, the photoconductive layer, the upper blocking layer, and the intermediate layer are formed on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 5. A substrate deposited up to the first layer was produced.

Next, the substrate deposited up to the first layer was once taken out from the film forming furnace, and the surface of the substrate was processed. For surface processing, surface polishing was performed with a lapping tape (trade name: C2000) manufactured by Fuji Film Co., Ltd. with the polishing apparatus of FIG. 4 to flatten the top of the protrusion. Next, using the cleaning apparatus shown in FIG. 6, ultrasonic cleaning is performed in a surfactant aqueous solution according to the above-described cleaning procedure, and pure water having a liquid temperature of 25 ° C. and a resistivity of 17.5 MΩ · cm is high pressure (4.9 Mpa). Washed with water under the conditions of rinsing by spraying and drying by blowing hot gas. Thereafter, the substrate after the water cleaning was returned to the RF plasma a-Si photosensitive film forming furnace after the ClF ₃ gas cleaning process, which was the same as the film forming furnace in which the first film shown in FIG. 3 was deposited. Thereafter, the substrate is heated to a substrate temperature of 260 ° C., and plasma treatment is applied to the outermost surface of the first layer under the conditions shown in Table 6, followed by the second layer under the conditions shown in Table 7. A surface layer was deposited to produce a negatively charged electrophotographic photosensitive member having the layer structure of FIG.

In this embodiment, as shown in Table 2, the oxygen mixing ratio of the mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) is 25 Vol.

The produced electrophotographic photosensitive member was measured for the depth profile of the oxygen atom content by SIMS (manufactured by CAMECA, device name: IMS-4F) in the same manner as in Example 1, and the first layer and the second layer were measured. As a result of calculating the maximum content of oxygen atoms in the thickness direction of the interface with the layer, it was 6.4 × 10 ²¹ atoms / cm ³ .

  The photoreceptor obtained by the above procedure is a photoreceptor used for negative charging, and was evaluated as follows.

(Image defect)
A magnetic brush charger was adopted as the primary charger, and the electrophotographic photosensitive member produced in this example was mounted on an electrophotographic apparatus provided with a cleaning blade as a cleaner for image formation. Specifically, it is modified to image exposure based on Canon iR6000 (process speed 265mm / sec), AC voltage (1.2kVpp, 1.0kHz) is applied to the magnetic brush charger for negative charging, and- A DC voltage of 550 V was superimposed. The image thus obtained was observed, and the number of black spots appearing on the image due to the protrusion was counted.

The obtained results were ranked by relative comparison when the value in Comparative Example 2 described later was 100%.

◎ ・ ・ ・ 35% to less than 65% ○ ・ ・ ・ 65% to less than 95% △ ・ ・ ・ 95% to less than 105% × ... 105% or more

(Adhesion evaluation)
First, the produced photoreceptor was set in an electrophotographic apparatus using a magnetic brush charger as a primary charger and a cleaner provided with a cleaning blade, and 1 million sheets of A4 paper was passed through. Specifically, it is modified to image exposure based on Canon iR6000 (process speed 265mm / sec), AC voltage (1.2kVpp, 1.0kHz) is applied to the magnetic brush charger for negative charging, and- A DC voltage of 550 V was superimposed.

After the endurance, the electrophotographic photosensitive member is left in a container adjusted to a temperature of −30 ° C. for 48 hours, and then immediately left in a container adjusted to a temperature of + 150 ° C. for 48 hours. The surface of the electrophotographic photosensitive member was observed after a heat shock test in which this cycle was repeated 10 times. Further, the surface of the electrophotographic photosensitive member was observed after a vibration test in which a vibration of 10 Hz to 10 kHz consisting of an acceleration of 7 G was repeated 5 cycles with a sweep time of 2.2 minutes. Evaluation is based on the following criteria.

◎: Very good with no film peeling after heat shock test and even after vibration test ○: No film peeling after heat shock test, after film vibration test, a minute film at the edge of non-image area Peeling is partially observed but there is no practical problem. △: After heat shock test, some minute film peeling is observed at the edge of the non-image area, but there is no practical problem. ×: Relatively large film after heat shock test. Peeling is partly observed and there are practical problems.

(Comprehensive evaluation)
A: All evaluation items consist of A, which is a very good level.
○: For all evaluation items, it consists of ◎ and ○, which is a good level.
Δ: For all evaluation items, at least one Δ is included, but it is at a level that does not cause a problem in practice.

<Comparative example 2>
Using the RF plasma a-Si photosensitive film-forming apparatus shown in FIG. 3, a substrate having a first layer deposited on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 5 was produced. Next, the deposited substrate is once taken out of the film forming furnace, surface-polished and washed with water under the same conditions as in Example 1, and then a surface layer as a second layer is deposited under the conditions shown in Table 7. A negatively charged electrophotographic photosensitive member having the layer structure (B) was produced.

  In this comparative example, the plasma treatment was not performed before the second layer was deposited.

  The photoreceptor obtained by the above procedure was evaluated in the same manner as in Example 2.

  The results of Example 2 and Comparative Example 2 are shown in Table 8. As is apparent from the results in Table 8, the electrophotographic photosensitive member produced in this example was excellent in the effect of reducing image defects and was also good in adhesion.

[Example 3]
Using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. 3, a lower blocking layer, a photoconductive layer, an upper blocking layer, and an intermediate layer are formed on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 9. A substrate deposited up to the first layer was produced.

Next, the substrate deposited up to the first layer was once taken out from the film forming furnace, and the surface of the substrate was processed. For surface processing, surface polishing was performed using a lapping tape (trade name: LT-C2000) manufactured by Fuji Film Co., Ltd. with the polishing apparatus shown in FIG. Next, using the cleaning apparatus shown in FIG. 6, ultrasonic cleaning is performed in a surfactant aqueous solution according to the above-described cleaning procedure, and pure water having a liquid temperature of 25 ° C. and a resistivity of 17.5 MΩ · cm is high pressure (4.9 MPa). Washed with water under the conditions of rinsing by spraying and drying by blowing hot gas. Thereafter, the substrate after the water cleaning was returned to the RF plasma a-Si photosensitive film forming furnace after the ClF ₃ gas cleaning process, separately from the film forming furnace in which the first film shown in FIG. 3 was deposited. Thereafter, the substrate is heated to a substrate temperature of 260 ° C., and plasma treatment is performed on the outermost surface of the first layer under the conditions shown in Table 10, followed by the second layer under the conditions shown in Table 12. A surface layer was deposited to produce a negatively charged electrophotographic photosensitive member having the layer structure of FIG.

In this example, as shown in Table 10, plasma treatment with dinitrogen monoxide (N ₂ O) gas was performed as plasma treatment conditions, and plasma treatment with hydrogen was subsequently performed.
The produced electrophotographic photosensitive member was measured for the depth profile of the oxygen atom content by SIMS (manufactured by CAMECA, device name: IMS-4F) in the same manner as in Example 1, and the first layer and the second layer were measured. As a result of calculating the maximum content of oxygen atoms in the thickness direction of the interface with the layer, it was 3.8 × 10 ²¹ atoms / cm ³ .

  The photoreceptor obtained by the above procedure is a photoreceptor used for negative charging, and was evaluated in the same manner as in Example 2.

[Example 4]
Using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. 3, a lower blocking layer, a photoconductive layer, an upper blocking layer, and an intermediate layer are formed on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 9. A substrate deposited up to the first layer was produced.

Next, the substrate deposited up to the first layer was once taken out from the film forming furnace, and the surface of the substrate was processed. For surface processing, surface polishing was performed with a lapping tape (trade name: C2000) manufactured by Fuji Film Co., Ltd. with the polishing apparatus of FIG. 4 to flatten the top of the protrusion. Next, using the cleaning apparatus shown in FIG. 6, ultrasonic cleaning is performed in a surfactant aqueous solution according to the above-described cleaning procedure, and pure water having a liquid temperature of 25 ° C. and a resistivity of 17.5 MΩ · cm is high pressure (4.9 MPa). Washed with water under the conditions of rinsing by spraying and drying by blowing hot gas. Thereafter, the substrate after the water cleaning was returned to the RF plasma a-Si photosensitive film forming furnace after the ClF ₃ gas cleaning process, separately from the film forming furnace in which the first film shown in FIG. 3 was deposited. Thereafter, the substrate is heated to a substrate temperature of 260 ° C., and plasma treatment is performed on the outermost surface of the first layer under the conditions shown in Table 10, followed by the second layer under the conditions shown in Table 12. A surface layer was deposited to produce a negatively charged electrophotographic photosensitive member having the layer structure of FIG.

In this example, as shown in Table 11, plasma treatment with carbon dioxide (CO ₂ ) gas was performed as a plasma treatment condition, and plasma treatment with hydrogen was subsequently performed.

The produced electrophotographic photosensitive member was measured for the depth profile of the oxygen atom content by SIMS (manufactured by CAMECA, device name: IMS-4F) in the same manner as in Example 1, and the first layer and the second layer were measured. As a result of calculating the maximum content of oxygen atoms in the thickness direction of the interface with the layer, it was 7.7 × 10 ²¹ atoms / cm ³ .

  The photoreceptor obtained by the above procedure is a photoreceptor used for negative charging, and was evaluated in the same manner as in Example 2.

<Comparative Example 3>
Using the RF plasma a-Si photosensitive film forming apparatus shown in FIG. 3, a substrate having a first layer deposited on an Al substrate having an outer diameter of 80 mm under the conditions shown in Table 9 was produced. Then, the deposited substrate is once taken out from the film forming furnace, surface-polished and washed with water under the same conditions as in Example 2, and then a surface layer as the second layer is deposited under the conditions shown in Table 12. A negatively charged electrophotographic photosensitive member having the layer structure (B) was produced.

  In this comparative example, only the plasma treatment 1 was not performed under the conditions shown in Table 10 before the deposition of the second layer.

  The photoreceptor obtained by the above procedure was evaluated in the same manner as in Example 2.

  The results of Example 3, Example 4, and Comparative Example 3 are shown in Table 13 above. The relative comparison was ranked by relative comparison when the value in Comparative Example 3 was 100%. As is clear from the results in Table 13, the electrophotographic photosensitive member produced in this example was excellent in the effect of reducing image defects and was also good in adhesion.

It is a typical sectional view showing an example of a projection of an electrophotographic photosensitive member. 1 is a cross-sectional view schematically showing an example of the configuration of an electrophotographic photosensitive member of the present invention. FIG. 2 is a schematic cross-sectional view of an RF plasma a-Si photosensitive film forming apparatus. It is typical sectional drawing of the surface polishing apparatus used for this invention. 1 is a schematic cross-sectional view of an example of an electrophotographic apparatus of the present invention. It is a figure which shows typically an example of the washing | cleaning apparatus used for the water washing | cleaning in the manufacturing process of the electrophotographic photoreceptor of this invention. It is an example of the depth profile explaining the peak of oxygen atom content in the interface part of the 1st layer in the present invention, and the 2nd layer.

Explanation of symbols

101, 201 substrate
102, 202 1st layer
203 Second layer
104, 204 Lower blocking layer
105, 205 Photoconductive layer
106 Surface layer
206 Middle class
207 Upper blocking layer
210 dust
211 protrusion
3100 Deposition system
3110 reaction vessel
3111 Cathode electrode
3112 Substrate having a conductive surface
3113 Substrate heating heater
3114 Source gas introduction pipe
3115 high frequency matching box
3116 Gas piping
3117 Leak valve
3118 Main valve
3119 Vacuum gauge
3120 high frequency power supply
3121 Insulation material
3123 cradle
3200 Raw material gas supply equipment
3211-3216 Mass Flow Controller
3221-3226 cylinder
3231-3236 Valve
3241 to 3246 Inflow valve
3251-3256 Outflow valve
3260 Auxiliary valve
3261-3266 Pressure regulator
400 substrate
420 Elastic support mechanism
430 Pressure elastic roller
431 polishing tape
432 Feeding roll
433 Winding roll
434 Fixed feed roll
435 Capstan Roller
501 photoconductor
503 magnetic brush charger
504 Developer
505 Transfer paper supply system
506 (a) Transfer charger
506 (b) Separating charger
507 Cleaning unit
508 Transport system
509 Static elimination light source
510 Halogen lamp
511 Platen
512 manuscript
513 mirror
514 Mirror
515 Mirror
516 lens unit
517 CCD unit
518 Laser unit
519 Mirror
520 Potential sensor
521 Cleaning blade
522 Registration roller
524 fuser
601 substrate
602 processing unit
603 Processing member transport mechanism
611 Treatment material input stand
621 Processing member cleaning layer
622 Cleaning solution
631 Pure water contact tank
632 nozzle (for pure water ejection)
641 Drying tank
642 nozzle (for dry gas ejection)
651 Disposal base for processing materials
661 Transfer arm
662 Movement mechanism
663 Chucking mechanism
664 Air cylinder
665 Transport rail

Claims (13)

In a method for producing an electrophotographic photoreceptor including a layer made of a non-single crystal material,
As a first step, a cylindrical substrate having a conductive surface is placed in a vacuum-tight film-forming furnace equipped with an evacuation unit and a source gas supply unit, and the source gas is decomposed by high-frequency power, Depositing a first layer of non-single crystalline material;
As a second step, a step of once removing the substrate on which the first layer has been deposited from the film forming furnace;
As a third step, a step of polishing the outermost surface of the first layer;
As a fourth step, a substrate on which the first layer after the polishing process is deposited is installed, a gas containing at least oxygen atoms is decomposed by high-frequency power, and plasma is formed on the outermost surface of the first layer after the polishing process. A process of processing,
And a step of depositing a second layer made of a non-single crystal material on the substrate after the plasma treatment as a fifth step. The plasma treatment in the fourth step includes a mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ), oxygen (O ₂ ), dinitrogen monoxide (N ₂ O), carbon dioxide (CO _{2. The} method for producing an electrophotographic photosensitive member according to claim 1, wherein one is selected from ₂ ). 3. The electrophotography according to claim 1, wherein the mixed gas of carbon tetrafluoride (CF ₄ ) and oxygen (O ₂ ) has a mixing ratio of oxygen (O ₂ ) of 15 Vol.% Or more. A method for producing a photoreceptor. The method for producing an electrophotographic photosensitive member according to claim 1, wherein after the plasma treatment in the fourth step, plasma treatment with hydrogen (H ₂ ) or an inert gas is performed.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the surface of the first layer is brought into contact with water before proceeding to the fourth step.   6. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the outermost surface of the first layer is a silicon carbide layer containing at least carbon atoms and silicon atoms.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the second layer comprises a silicon carbide layer containing at least carbon atoms and silicon atoms.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the second layer is made of a non-single crystal material having a carbon atom as a base material.   An electrophotographic photosensitive member produced by the production method according to claim 1.   An electrophotographic apparatus using the electrophotographic photosensitive member according to claim 9.   11. The electrophotographic apparatus according to claim 10, wherein the charging means of the electrophotographic apparatus comprises contact charging means using a magnetic brush charger.   An electrophotographic photoreceptor in which a first layer made of a non-single-crystal material and a second layer made of a non-single-crystal material are stacked on a cylindrical substrate having at least a conductive surface. The electrophotographic photoreceptor, wherein the protrusions in the first layer stop growing on the surface of the first layer, and oxygen atoms are contained in the interface region with the second layer.   13. The electrophotographic photosensitive member according to claim 12, wherein oxygen atoms contained in an interface region with the second layer have a peak content distribution of oxygen atoms in the thickness direction of the interface region.

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