JPH11133640A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which does not give rise to fusion despite of any environment or the device constitution of an electrophotographic device body and to provide the electrophotographic photoreceptor optimum for the electrophotographic device which saves energy, is friendly to the global environment and consumes less electric power. SOLUTION: The extreme front surface of the photoreceptor comprises a non-single crystalline carbon film 101 contg. hydrogen of >=50 to <=700 mN in the critical weight at which a deposited film breaks when load is impressed on a diamond stylus of <=15 μm in radius of its front end while this stylus is moved at amplitude 20 to 100 μm, vibration period 30 Hz and feed speed 2 to 20 μm/sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive material which is subjected to an electrophotographic process and comprises a non-single-crystal carbon film containing hydrogen (hereinafter referred to as "a-C: H"). About the body.

[0002]

2. Description of the Related Art As a technique of an element member used for an electrophotographic photosensitive member, selenium, cadmium sulfide, zinc oxide, phthalocyanine, amorphous silicon (hereinafter referred to as "a-Si") are used.
Various materials have been proposed. A-
Non-monocrystalline deposited films containing silicon atoms typified by Si as a main component, for example, amorphous deposited films of a-Si or the like compensated with hydrogen and / or halogen (for example, fluorine, chlorine, etc.) have high performance and high durability. Have been proposed as non-polluting photoconductors, some of which have been put to practical use. Conventionally, as a method of forming such a deposited film, a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), a method of decomposing a source gas by light (photo CVD method), and a method of decomposing a source gas by plasma (plasma) Many methods are known. Among them, the plasma CVD method, that is, the raw material gas is decomposed by glow discharge such as direct current or high frequency (RF, VHF), microwave, etc., is formed into a thin film on a substrate such as glass, quartz, a heat-resistant synthetic resin film, stainless steel, or aluminum. The method of forming an a-Si deposited film for electrophotography and the like has been very practically used at present, and various apparatuses for forming the deposited film have been proposed.

[0003] For example, Japanese Patent Application Laid-Open No. 57-115551 discloses that silicon atoms and carbon atoms are formed on a photoconductive layer composed of an amorphous material mainly composed of silicon atoms and containing at least one of hydrogen atoms and halogen atoms. There is disclosed an example of a photoconductive member provided with a surface barrier layer composed of a non-photoconductive amorphous material containing a hydrogen atom as a base. Also, JP-A-61-219961
Japanese Patent Application Laid-Open Publication No. H11-163873 discloses an example of an electrophotographic photosensitive member composed of aC: H containing 10 to 40 atomic% of hydrogen atoms as a surface protective layer formed on an a-Si-based photosensitive layer. It has been disclosed. In Japanese Patent Application Laid-Open No. 6-317920, 20 MHz
Electrons composed of a photoconductive layer made of a non-single-crystal silicon-based material having silicon atoms as a base material and an aC: H surface protective layer having a hydrogen atom content of 8 to 45 atomic% using the above high frequencies. A method for manufacturing a photographic photoreceptor is disclosed.
Japanese Patent Application Laid-Open No. 60-186849 discloses a microwave (for example, a frequency of 2.45 G) as a decomposition source of a raw material gas.
A method and an apparatus for forming an electrophotographic device having a top blocking layer by a microwave plasma CVD method using H.sub.H) are disclosed. By these techniques, electrical, optical, photoconductive properties, use environment properties, and durability are improved, and image quality is also improved.

[0004]

However, in recent years,
Electrophotographic apparatuses have become faster and have a longer life. Under such an environment, for example, even if the electrophotographic photosensitive member has sufficiently exhibited its performance, for example, fusion may occur depending on the use environment and the configuration of the electrophotographic apparatus main body. Fusing is a process in which toner melts and adheres to the surface of an electrophotographic photosensitive member during long-term use, and depending on the degree of adhesion, fusing marks appear in a solid white image or a halftone image. It will cause trouble. When such fusion occurs and appears on the image, the serviceman must go to the customer and perform maintenance, which is costly. Further, since the photoconductor is detached from the main body of the electrophotographic apparatus and maintenance is performed, there is a risk that a dent scratch is made during the operation and the photoconductor becomes unusable. Furthermore, in recent years, as the development of OA equipment which is friendly to the global environment is being promoted under the initiative of the national government and the government, energy saving and resource saving have been called for in electrophotographic apparatuses more than ever.
Efforts have been made to save energy and resources in electrophotographic apparatuses from various fields. One of them is an attempt to reduce the power consumption of a fixing device that fixes toner on paper.
2. Description of the Related Art Conventionally, a fixing device has a built-in heater therein, and a fixing roller is constantly maintained at 150 ° C. to 200 ° C. to fix toner on paper by melting toner. The power consumption of the fixing device can be reduced by lowering the maintenance temperature of the fixing roller. In this case, a toner having a low melting point that is melted / fixed at a low temperature is used as the toner at the same time because a fixing failure of the toner occurs. In this case, the image quality,
There is no practical problem with respect to fixability. However, when such a low-melting toner is used, depending on the combination of the environment in which the electrophotographic apparatus is used, the components contained in the toner, the surface properties of the electrophotographic photoreceptor, the pressing pressure of the cleaner, and the process speed, etc. In some cases, the fusion described above is likely to occur. Further, since the color toner used in the full-color electrophotographic apparatus originally uses a low melting point toner, the environment has been more likely to cause fusion than before.

As a method of preventing the fusion, a method of polishing the surface of the electrophotographic photosensitive member and removing the fusion source together with the surface of the film can be considered. But a
-In the case of an electrophotographic photoreceptor having a high hardness of a Si system, the surface is not cut smoothly, and streaky uneven shaving occurs.
Since this striped uneven shaving appears on the image, a-
It has been common sense to use Si-based electrophotographic photoreceptors under conditions in which surface shaving does not occur. Further, as another method for preventing fusion, silica or the like may be added as an abrasive to the toner itself, components may be changed, or the amount may be increased. When the abrasive is included in the toner itself, the ability to rub the drum surface is increased, so that the melted toner is less likely to adhere. However, while this prevents fusion, as a side effect, the force of rubbing the surface of the photoreceptor is also increased, and it has been difficult to achieve a balance in a range where only fusion is improved without scraping the surface of the photoreceptor. Further, a method of increasing the pressing pressure of a cleaner to prevent fusion, scrape-cleaning all the toner, and preventing the toner from adhering to the surface may be used. However, a fine balance is still required to prevent the fusion while preventing the surface of the photoconductor from being polished, and it has been difficult to stably prevent the electrophotographic apparatus in all mass-produced electrophotographic apparatuses.

In view of the above, the present invention solves the above-mentioned problems in the conventional device, and in any environment or device configuration of the electrophotographic device main body in a recent electrophotographic device having a high speed and a long life. Another object of the present invention is to provide an excellent electrophotographic photoreceptor which does not cause fusion. Another object of the present invention is to provide an electrophotographic photoreceptor that is optimal for an electrophotographic apparatus that consumes less energy and is eco-friendly and consumes less power. Another object of the present invention is to provide an electrophotographic photoreceptor that can always maintain a good image without causing fusion of the toner even in an electrophotographic apparatus using any toner such as a low melting point toner. . Another object of the present invention is to provide an electrophotographic photoreceptor which is suitably used for a full-color electrophotographic apparatus and does not cause a problem such as fusion. In addition, the present invention does not cause toner fusion under any combination of environment, electrophotographic photosensitive member surface properties, cleaner pressing pressure, process speed, toner components, etc. It is an object of the present invention to provide an electrophotographic photoreceptor capable of maintaining the following. Still another object of the present invention is to provide an electrophotographic photoreceptor capable of maintaining a good image at a high resolution and a uniform density without causing uneven shaving on any cleaning system or toner. I do.

[0007]

In order to solve the above-mentioned problems, the present invention is characterized in that an electrophotographic photosensitive member is constituted as follows. That is, the electrophotographic photoreceptor of the present invention uses a diamond stylus having a tip radius of 15 μm or less with an amplitude of 20 to 100 μm, a vibration period of 30 Hz,
When a load is applied to the stylus while moving at a feed speed of 2 to 20 μm / sec, the outermost surface is composed of a hydrogen-containing non-single-crystal carbon film whose critical load at which the deposited film breaks is 50 mN to 700 mN. It is characterized by being. Also, in the electrophotographic photoreceptor of the present invention, the critical load at which the non-single-crystal carbon film breaks is 100 mN or more and 5 mN or more.
100 mN or less. Further, the electrophotographic photoreceptor of the present invention is characterized in that the non-single-crystal carbon film has a hydrogen content of 10% to 60%. Further, the electrophotographic photoreceptor of the present invention is characterized in that the non-single-crystal carbon film has an optical band gap of 1.2 to 2.2 eV. Further, the electrophotographic photoreceptor of the present invention comprises:
The non-single-crystal carbon film has a refractive index of 1.8 to 2.8. Further, in the electrophotographic photoreceptor of the present invention, the non-single-crystal carbon film has a thickness of 50 ° or more and 10,000 or more.
It is characterized in that it is less than or equal to or less than 100 and less than or equal to 2000. Further, the electrophotographic photoreceptor of the present invention is characterized in that the photosensitive layer is made of a non-single-crystal material mainly composed of silicon. Further, the electrophotographic photoreceptor of the present invention is characterized in that it has a three-layer structure of a lower blocking layer, a photosensitive layer, and an upper blocking layer. Further, the electrophotographic photoreceptor of the present invention is characterized in that it has a three-layer structure of a charge transport layer, a charge generation layer, and a surface protective layer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention realizes an excellent electrophotographic photoreceptor which does not cause fusing by the above-mentioned constitution, which is based on the following examination results of the present inventors. is there. The inventors of the present invention have studied the phenomenon of so-called fusion in which toner melts and adheres to the surface of an electrophotographic photosensitive member. This fusing of the toner is a phenomenon often seen particularly in the case of the low melting point toner. Low melting point toners are often used in order to prevent poor fixing even when the temperature setting of the fixing unit is lowered in order to reduce power consumption in response to recent demands for energy saving. In the course of the study, the so-called polishing power must be increased to prevent fusing, such as increasing the pressing pressure of the cleaning blade or increasing the silica component contained as an external additive of the toner. Has been found to be highly effective. However, this increase in polishing power has conventionally polished the electrophotographic photoreceptor itself, causing streak-like uneven scraping,
For this reason, a halftone image or a solid black image is damaged, and the image quality is extremely deteriorated.

For this reason, development of a material having a surface characteristic that is unlikely to cause fusion as a surface characteristic, or an increase in the blade pressure or an external additive added to the toner to increase the polishing force, such as a photoreceptor It was necessary to consider a material constituting the outermost surface of the electrophotographic photoreceptor, which does not cause smooth stripe-like unevenness even if the surface is scraped. In previous studies, such materials could not be found in conventionally used amorphous silicon carbide films, amorphous nitrogen carbide films, amorphous silicon oxide films, and the like.
However, the present inventors have made intensive studies and found that aC:
The material H was found to have high hardness, lubricity in itself, and was relatively suitable for these problems. When the fusing phenomenon of the toner was examined in various environments, fusing might occur depending on the manufacturing conditions even if the same aC: H film was formed, or a streak might occur due to a cleaning blade pressure or the like. It has been found that irregular shaving of the shape may occur.

As a result of further arranging these phenomena,
When a load is applied to a diamond stylus whose tip radius is 15 μm or less while moving the stylus with an amplitude of 20 to 100 μm, a vibration cycle of 30 Hz, and a feed speed of 2 to 20 μm / sec, the critical load is 50 mN or more and 700 mN or more.
In the case of the aC: H film in which the film forming conditions are set so that the film is broken within a load range of mN or less, no fusion of toner occurs and no streak-like uneven scraping occurs. It has been found that an optimal deposited film can be obtained for the purpose. When the aC: H film satisfying this specific condition was examined in more detail, it was found that the deposited film having appropriate hardness was slightly polished when used in an electrophotographic apparatus. Turned out to be. It is supposed that the adhesion of the toner was prevented by this slight polishing action, and no fusion occurred. The greatest feature of aC: H that satisfies this condition is that, despite the abrasion of such a film, no stripe or uneven scraping occurs at all, and the surface can be used for a long period of time. It is always smooth and does not cause image unevenness. We speculate that this may be related to the specific lubrication effect obtained only under this particular condition.

At present, the present inventors have not clearly understood why the characteristics of the electrophotographic photosensitive member are well reflected by such a scratch test in which specific conditions are determined. A simple scratch test does not simply measure the adhesion between the deposited film and the substrate, but also the coefficient of friction between the deposited film and the subtle stylus chatter determined by the material of the stylus, the surface shape and hardness of the deposited film, etc. It is measured including. Therefore, when the material and curvature of the stylus are limited and the conditions of the scratch test are strictly defined, the interaction of the contact portion with the aC: H film and the mechanism of friction and wear occur in the electrophotographic apparatus. It is thought that the object of the present invention will be achieved by controlling the film forming conditions so that the friction mechanism with the cleaning blade and the toner to be formed and the toner are within a certain range under the conditions.

An electrophotographic photosensitive member having an aC: H film on the outermost surface according to the present invention is, for example, an ordinary plasma CV.
It can be prepared by Method D. Generally plasma C
Since the VD method has a large apparatus dependence, it is not possible to uniformly define the film forming conditions for obtaining the aC: H film according to the present invention. , Gas mixing method, gas introduction method, adjustment of exhaust form,
By performing pressure adjustment, power adjustment, frequency adjustment, power waveform adjustment, DC bias adjustment, substrate temperature adjustment, film formation time adjustment, and the like, the characteristics of the deposited film formed greatly change. Therefore, according to the present invention, the control of the critical load in the scratch test under specific conditions,
By appropriately adjusting these parameters, it is possible to easily set conditions in any film forming apparatus. If the load at which the film on the outermost surface breaks is 50 mN or less, streak-like uneven scraping occurs during the durability test, and there is a problem in practical durability. Further, at 700 mN or more, there was no adverse effect such as uneven shaving, but depending on environmental conditions, toner fusion sometimes occurred. Therefore, the critical load is 50 mN to 700 mN.
It is important to keep within the range.

An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an electrophotographic photosensitive member according to the present invention. Reference numeral 101 denotes an outermost surface layer of the electrophotographic photosensitive member.
It is made of H film. 102 is a photoconductive layer mainly composed of silicon atoms, and 103 is a base. The surface layer 101 according to the present invention is made of aC: H, and is made of a hydrocarbon as a source gas, typically by a plasma CVD method. The content of hydrogen atoms contained in the a-C: H film is preferably H / (C + H) of 10% to 60%, more preferably 20% to 40%. When the amount of hydrogen is less than 10%, the optical band gap becomes narrow, which is not suitable in terms of sensitivity. On the other hand, if it exceeds 60%, the hardness is reduced, and shaving is liable to occur. The optical band gap is generally 1.2
A value of about eV to 2.2 eV can be suitably used, and it is more preferable to be 1.6 eV or more from the viewpoint of sensitivity. A refractive index of about 1.8 to 2.8 is suitably used. The film thickness is between 50 ° and 10000 °, preferably between 100 ° and 2000 °. If the thickness is less than 50 °, there is a problem in mechanical strength. If it exceeds 10,000 °, a problem occurs in light sensitivity. In any case, the value of the critical load in the scratch test is 50 mN to 700 mN.
Is important in terms of hardness and lubricity.

Substances that can serve as a carbon supply gas include:
The gaseous or gasifiable hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ can be used effectively. CH ₄ and C ₂ H ₆ are preferred in terms of good supply efficiency and the like. Further, these raw material gases for supplying carbon may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary. Further, the surface layer composed of aC: H of the present invention may contain a halogen atom, if necessary. Examples of substances that can serve as halogen atom supply gases include F ₂ , BrF, ClF, ClF ₃ , and Br.
Interhalogen compounds such as F ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. Further, CF ₄ , CHF ₃ , C ₂ F ₆ , Cl
Fluorine-containing gases such as F ₃ , CHClF ₂ , F ₂ , C ₃ F ₈ , and C ₄ F ₁₀ are preferably used. The substrate temperature is adjusted from room temperature to 350 ° C., but if the substrate temperature is too high, the band gap decreases and the transparency decreases, so a lower temperature setting is preferable. The high frequency power is preferably as high as possible because the decomposition of the hydrocarbon proceeds sufficiently. Specifically, 5 W / cc to the raw material gas of the hydrocarbon is preferable.
The above is preferable, but if the temperature is too high, abnormal discharge occurs and the characteristics of the electrophotographic photoreceptor deteriorate. Therefore, it is necessary to suppress the electric power to such an extent that abnormal discharge does not occur. Regarding the pressure in the discharge space, normal RF (typically 13.
56 Torr) When power is used, 0.1 Torr to 1
0 Torr, VHF band (typically 50 to 450 MH
0.1 mTorr to 100 mTo when z) is used
rr is maintained.

In the method of forming the photoconductive layer 102 according to the present invention, any material such as an organic photoreceptor, a Se photoreceptor, and a CdS photoreceptor can be suitably used as long as it is a non-monocrystalline film mainly composed of silicon atoms. As a condition for forming the non-single-crystal photoconductive layer mainly composed of silicon atoms, high-frequency power of any frequency or glow discharge plasma by microwave can be suitably used, and a source gas containing silicon atoms by the glow discharge plasma Is created by disassembly. In this schematic diagram, the photoconductive layer is made of a single layer that is not functionally separated, is composed of an amorphous material containing at least silicon atoms, and exhibits photoconductivity. In addition, as shown in FIG. 2, the surface layer is a
-C: a first surface layer 204 of amorphous silicon carbide, amorphous silicon nitride, amorphous silicon oxide, or the like is provided, if necessary, in addition to one layer of the H film;
An aC: H film 201 according to the present invention may be laminated thereon. The effect of the present invention can be obtained if the outermost layer is formed of an aC: H film having a critical load value of 50 mN to 700 mN in a scratch test. Further, as shown in FIG. 3, the photoconductive layer 302 is made of an amorphous material containing at least silicon atoms and has a photoconductive layer 304 and a lower blocking layer 305 for preventing carrier injection from the base 303. May be divided into two layers. Further, as shown in FIG. 4, a charge transport layer 405 in which the photoconductive layer 402 is made of an amorphous material containing at least silicon atoms and carbon atoms and a charge generation layer 404 made of an amorphous material containing at least silicon atoms are provided. It may be a function-separated type having a configuration in which layers are sequentially stacked. When the electrophotographic photosensitive member is irradiated with light, carriers mainly generated in the charge generation layer 404 are converted to the charge transport layer 405.
Through the conductive substrate 403. Needless to say, the effects of the present invention can be obtained even in the layer configuration shown in FIGS. 3 and 4 even when the surface layer has a two-layer configuration as shown in FIG. The thickness of the photoconductive layer is appropriately set in accordance with the charging ability and sensitivity required of the copying machine from 1 μm to 50 μm, but is usually 10 μm or more from the viewpoint of charging ability and sensitivity, and from the viewpoint of industrial productivity. Is preferably 50 μm or less.

FIG. 5 is a diagram schematically showing an example of a deposition apparatus by a plasma CVD method using a 13.56 MHz high frequency power supply for producing the electrophotographic photosensitive member of the present invention. This device is roughly composed of a deposition device and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. In the reaction vessel 501, a cylindrical deposition substrate 502 is placed on a conductive support 507 connected to the ground, and a heater 50 for heating the cylindrical deposition substrate.
3. A source gas introduction pipe 505 is provided. Further, the cathode electrode 506 is made of a conductive material, and is made of an insulating material 513.
Insulated by The cathode electrode is connected to a 13.56 MHz high frequency power supply 512 via a high frequency matching box 511. The cylinders of the constituent gases of the raw material gas supply device (not shown) are connected to a gas introduction pipe 505 in the reaction vessel 501 via a valve 509.

An example of a method for forming an electrophotographic photosensitive member using the apparatus shown in FIG. 5 will be described below. For example, the base 502 whose surface is mirror-finished using a lathe is
7 so as to include the substrate heating heater 503 in the reaction vessel 501. Next, the source gas introduction valve 509 is closed, the reaction vessel 501 is once evacuated by the exhaust device 508 through the exhaust port 515, and then the source gas introduction valve 509 is opened to open an inert gas for heating.
As an example, argon is introduced into the reaction vessel 501 from the gas supply pipe 505, and the exhaust speed of the exhaust device 508 and the flow rate of the heating gas are adjusted so that the inside of the reaction vessel 501 has a desired pressure. Thereafter, the temperature controller (not shown) is operated to heat the substrate 502 by the substrate heating heater 503, and the temperature of the cylindrical film-forming substrate 502 is set to 20 ° C. to 10 ° C.
Control to a predetermined temperature of 0 ° C. When the base 502 is heated to a desired temperature, the source gas introduction valve 509 is closed to stop the gas from flowing into the reaction vessel 501.

Next, the inflow valve 509 is opened, and the main valve 504 is opened to exhaust the reaction vessel 501 and the gas supply pipe 505, also serving as exhaustion of the gas supply device. Next, when the reading of the vacuum gauge 510 reaches 5 × 10 ⁻⁶ Torr, the inflow valve 509 is closed. To form a deposited film, the source gas introduction valve 509 is opened, and a predetermined source gas, for example, a material gas such as silane gas, disilane gas, methane gas, and ethane gas, and a doping gas such as diborane gas and phosphine gas are blocked from the source gas inlet 505. After mixing by the illustrated mixing panel, it is introduced into the reaction vessel 501. Next, each mass gas is adjusted by a mass flow controller (not shown) so as to have a predetermined flow rate.
At this time, the main valve 5 is checked while observing the vacuum gauge 510 so that the inside of the reaction vessel 501 has a predetermined pressure of 1 Torr or less.
Adjust the opening of 04. Next, from several mTorr to several Torr
The opening of the main valve 504 is adjusted while watching the vacuum gauge 510 so as to maintain the pressure at r.

After preparation for film formation is completed by the above procedure, a photoconductive layer is formed on the cylindrical substrate 502 for film formation. After confirming that the internal pressure has stabilized, the high-frequency power supply 512 is set to a desired power and the high-frequency power is supplied to the matching box 5.
11 to the cathode electrode 506 to generate a high-frequency glow discharge. At this time, the matching circuit 509 is adjusted,
Adjust so that the reflected wave is minimized. The value obtained by subtracting the reflected power from the high-frequency incident power is adjusted to a desired value. The respective source gases introduced into the reaction vessel 501 are decomposed by the discharge energy, and a predetermined deposited film is formed on the cylindrical substrate 502. After the desired film thickness is formed, the supply of the high-frequency power is stopped, the flow of each source gas into the reaction vessel 501 is stopped, and the deposition chamber is once pulled up to a high vacuum, and then the layer formation is completed. By repeating the above operations, the lower blocking layer and the photoconductive layer are formed.

Next, a surface layer made of aC: H of the present invention is formed. Once the inside of the reaction vessel 501 is pulled up to a high vacuum, a predetermined raw material gas, for example, a hydrocarbon gas such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H _{10 is} required through a raw material gas inlet 505. According to the above, material gases such as hydrogen gas, helium gas, and argon gas are mixed by a mixing panel (not shown), and then introduced into the reaction vessel 501. Next, each mass gas is adjusted by a mass flow controller (not shown) so as to have a predetermined flow rate. At that time, the reaction vessel 501
Vacuum gauge 5 so that the internal pressure becomes a predetermined pressure of 1 Torr or less.
Adjust the opening of the main valve 504 while looking at 10.
After confirming that the internal pressure has stabilized, the high-frequency power source 512 is set to a desired power, and the power is supplied to the cathode electrode 506 to generate a high-frequency glow discharge. At this time, matching circuit 509
Is adjusted so that the reflected wave is minimized. The value obtained by subtracting the reflected power from the high-frequency incident power is adjusted to a desired value. Each source gas introduced into the reaction vessel 501 is decomposed by this discharge energy, and a predetermined aC: H deposition film is formed on the photoconductive layer. After the desired film thickness is formed, the supply of the high-frequency power is stopped, and the reaction vessel 501 is stopped.
After the flow of each source gas into the chamber is stopped and the deposition chamber is once pulled up to a high vacuum, the layer formation is completed. At this time, aC:
When a load is applied to the H film while applying a load to the tip of the diamond stylus having a radius of 15 μm or less at an amplitude of 20 to 100 μm, a vibration cycle of 30 Hz, and a feed speed of 2 to 20 μm / sec, the critical load at which the film breaks is 50 m.
It is important to form an aC: H film so that the thickness is not less than N and not more than 700 mN. During the film formation, the cylindrical substrate 502 may be rotated at a predetermined speed by a driving device (not shown).

FIG. 6 shows a plasma C having a different form from that of FIG.
FIG. 3 is a schematic diagram of an example of an electrophotographic photoreceptor forming apparatus (mass production type) by a VD method, in which a high-frequency power supply is 50 to 450 MHz.
A VHF band power supply of z is used. In FIG. 6, reference numeral 601 denotes a reaction vessel, which has a vacuum tight structure. Also, 61
Reference numeral 5 denotes an exhaust pipe having one end opened into the reaction vessel 601 and the other end communicating with an exhaust device (not shown). Reference numeral 616 denotes a discharge space surrounded by the cylindrical substrate 602. The high frequency power supply 612 is connected to the high frequency matching box 6.
11 and is electrically connected to the cathode electrode 606. The cylindrical film-forming substrate 602 is set on the rotating shaft 603 while being set on the holder 607. The procedure of the method of forming an electrophotographic photosensitive member using the apparatus of FIG. 5 is such that the arrangement of the cathode and the base is different, and that the base is always a rotating motor 6.
It is basically the same as the method of the device of FIG. 5, except that it is driven by.

[0022]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 Using a plasma CVD apparatus shown in FIG. 5, a lower blocking layer and a photoconductive layer were sequentially laminated on a cylindrical AL substrate under the conditions shown in Table 1. The procedure of film formation followed the method described above. Then, according to the procedure shown in Table 2, aC:
The surface layers A to E made of H were laminated to form a total of five electrophotographic photosensitive members. Simultaneously, surface layers A to E were deposited on mirror-polished 7059 glass (manufactured by Corning Incorporated) under the same manufacturing conditions to prepare a sample for a scratch test.

[0023]

[Table 1]

[0024]

[Table 2] The electrophotographic photoreceptor and surface layer sample thus produced were evaluated as follows. Band gap and refractive index The band gap and the refractive index were determined using an ultraviolet to near-infrared spectroscope. Hydrogen content The hydrogen content in the film was determined from the infrared absorption spectrum and the film thickness. Scratch test The surface of the surface layer sample deposited on 7059 glass was
Using a diamond stylus with a radius of 5 μm at the tip,
Amplitude 50μm, vibration cycle 30Hz, feed speed 10μ
While moving at m / sec, a load was applied to the stylus, and it was observed how the film surface was broken and scratch noise was generated. Then, the critical load when the film was broken first was measured. Evaluation of fusing By setting the pressing pressure of the cleaning blade of an electrophotographic apparatus (NP6060 manufactured by Canon Inc.) to １ ／ times and setting the surface temperature of the drum to 60 ° C., the environment in which fusing is likely to occur is improved. I made it. An electrophotographic photoreceptor was installed in the modified acceleration tester in this way, and the durability of 100,000 sheets was performed. The halftone image after the endurance and the surface of the electrophotographic photosensitive member were observed under a microscope, and the presence or absence of fusion was observed. Regarding the evaluation of the fusion, ○ no fusion was observed at all over the entire surface of the photoreceptor, and it was very good △ slight fusion was observed, but there was no problem at a level not appearing in the image × fusion occurred in the image Occurred, indicating a practical problem. The film thickness of the surface layer of the electrophotographic photoreceptor for electrophotography which was durable in the evaluation of uneven shaving was measured by a reflection interferometer before and after the durability. Also, visually observe the halftone image and the electrophotographic photosensitive member surface,
It was observed whether streaking or wear of the surface layer occurred.
Regarding the evaluation of uneven scraping: ○ Both the photoreceptor surface and the image, no uneven scraping or streak scraping was observed, and very good △ Slight uneven shavings were observed on the photoreceptor surface but did not appear on the image × scratches appearing on the image Indicates that there is a problem in practice. Charging ability The electrophotographic photoreceptor is installed in an electrophotographic apparatus (NP-6060 manufactured by Canon) which has been modified for experiments, and in a dark state, a high voltage of +6 kV is applied to the charger to perform corona charging. The surface potential at this time was measured with a surface electrometer and evaluated. Sensitivity The electrophotographic photosensitive member is charged to a constant dark area surface potential.
Immediately, a filter is used to irradiate a halogen lamp light excluding light in a wavelength range of 600 nm or more, and the light amount is adjusted so that the light-surface potential of the electrophotographic photosensitive member becomes a predetermined value (for example, 50 V). At this time, the necessary light amount is converted from the lighting voltage of the halogen lamp light source. In this procedure, the sensitivity of the electrophotographic photosensitive member is measured and evaluated. Residual potential The electrophotographic photoreceptor is charged to a constant dark area surface potential.
Then, immediately, a relatively strong light of a constant light amount (for example, 2lux)
・ Sec) is irradiated. The light source uses a xenon lamp,
Light excluding light in a wavelength range of 600 nm or more was irradiated using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member was measured with a surface voltmeter, and the residual potential was evaluated. For each evaluation item of charging ability, sensitivity, and residual charge, it indicates ○ good △ same level as conventional × practical problem.

(Comparative Example 1) Plasma CVD shown in FIG.
Using an apparatus, a lower blocking layer and a photoconductive layer were sequentially laminated on an AL substrate under the conditions shown in Table 1. The procedure of film formation followed the method described above. Then, according to the procedure shown in Table 3, a-
The surface layers F to H made of C: H were laminated to prepare a total of three electrophotographic photosensitive members. Simultaneously, surface layers F to H were deposited on mirror-polished 7059 glass (manufactured by Corning) to prepare a sample for a scratch test.

[0026]

[Table 3] The electrophotographic photoreceptor and surface layer sample thus produced were evaluated in the same manner as in Example 1. Example 1, Comparative Example 1
Table 4 summarizes the results. When the critical load when the conditions of the scratch test were strictly determined was 50 mN to 700 mN, no fusion or uneven shaving occurred, and very good results were obtained. In addition, it was found that all the photoconductors had good electric characteristics as electrophotography, and that no harm would occur even if the aC: H film of the present invention was provided on the surface.

[0027]

[Table 4] Example 2 A charge transport layer and a charge generation layer were sequentially laminated on an AL substrate under the conditions shown in Table 5 using the plasma CVD apparatus shown in FIG. The procedure of film formation followed the method described above. Subsequently, according to the procedure shown in Table 6, the surface layers A to E made of aC: H were laminated to prepare a total of five electrophotographic photosensitive members. Simultaneously, surface layers A to E were deposited on mirror-polished 7059 glass (manufactured by Corning) to prepare a sample for a scratch test. The electrophotographic photoreceptor and surface layer sample thus produced were evaluated in the same manner as in Example 1.

[0028]

[Table 5]

[0029]

[Table 6] Comparative Example 2 A charge transport layer and a charge generation layer were sequentially laminated on an AL substrate using the plasma CVD apparatus shown in FIG. 6 under the conditions shown in Table 4. The procedure of film formation followed the method described above. Subsequently, according to the procedure shown in Table 7, the surface layers F to H made of aC: H were laminated to prepare a total of three electrophotographic photosensitive members. Simultaneously, surface layers F to H were deposited on mirror-polished 7059 glass (manufactured by Corning) to prepare a sample for a scratch test. The electrophotographic photoreceptor and surface layer sample thus produced were evaluated in the same manner as in Example 1. Table 8 summarizes the results of Example 1 and Comparative Example 1. It has been found that the effects of the present invention can be obtained without any problem even if the layer constitution of the photosensitive layer is a function separation type of the charge transport layer and the charge generation layer. It was also found that the use of H ₂ , He, Ar or the like as a diluent gas when forming the aC: H film of the present invention did not adversely affect the effects of the present invention.

[0030]

[Table 7]

[0031]

[Table 8] Example 3 An electrophotographic photoreceptor of the present invention was formed on an AL substrate under the conditions shown in Table 9 using the plasma CVD apparatus shown in FIG. The procedure of film formation followed the method described above. In the present embodiment, fluorine was contained in the outermost surface layer by CF ₄ gas. At the same time, 7059 glass (Corning), which is mirror-polished under the same
Was deposited to prepare a sample for a scratch test.

[0032]

[Table 9] The critical load of the scratch test sample thus produced was 100 mN. Further, when the electrophotographic photosensitive member was installed in the same copying machine as in Example 1 and the durability of 100,000 sheets was performed, no fusion was generated, and no streak was generated.
Very good images could be obtained stably over a long period of time.

[0033]

According to the present invention, a diamond stylus having a tip radius of 15 μm or less can be used with an amplitude of 20 to 100 μm.
Vibration cycle 30Hz, feed speed 2-20μm / sec
The outermost surface of the electrophotographic photoreceptor is composed of a hydrogen-containing non-single-crystal carbon film having a critical load at which the deposited film breaks when the load is applied to the stylus while moving at 50 mN or more and 700 mN or less. Fusing toner under any conditions such as environment, electrophotographic device, type of toner such as low melting point toner, surface properties of electrophotographic photoreceptor, pressing pressure of cleaner, process speed, components contained in toner, etc. An electrophotographic photoreceptor which does not generate any unevenness, does not remove unevenness, and can always maintain high resolution, uniform density, and maintain a good image can be realized.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic sectional view of an electrophotographic photosensitive member according to the present invention.

FIG. 3 is a schematic sectional view of an electrophotographic photosensitive member according to the present invention.

FIG. 4 is a schematic sectional view of an electrophotographic photosensitive member according to the present invention.

FIG. 5 is a schematic view of a deposition apparatus for forming the electrophotographic photosensitive member of the present invention.

FIG. 6 is a schematic view of a mass production type deposition apparatus for forming the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

101, 201, 301, 401: aC of the present invention: H
Surface layer 102, 202, 302, 402: Photoconductive layer mainly composed of silicon atoms 103, 203, 303, 403: Conductive substrate 204: First surface layer 304: Photoconductive layer 305: Lower blocking layer 404: Electric charge Generation layer 405: Charge transport layer 501, 601: Reaction container 502, 602: Substrate 503, 603: Heater for substrate heating 504: Main valve 505, 605: Gas introduction tube 506, 606: Cathode electrode 507, 607: Auxiliary substrate 508 : Exhaust system 509, 609: Gas supply valve 510, 610: Vacuum gauge 511, 611: High frequency matching box 512, 612: High frequency power supply 513: Insulating material 614: Substrate rotating motor 515, 615: Exhaust pipe 516: Leak valve 616: Discharge space

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // H01L 21/205 H01L 21/205

Claims (9)

[Claims] A diamond stylus having a radius of 15 μm or less at the tip is provided with an amplitude of 20 to 100 μm and a vibration period of 30 Hz.
When a load is applied to the stylus while moving at a feed speed of 2 to 20 μm / sec, the outermost surface is composed of a hydrogen-containing non-single-crystal carbon film whose critical load at which the deposited film breaks is 50 mN to 700 mN. An electrophotographic photoreceptor characterized in that: 2. The electrophotographic photoreceptor according to claim 1, wherein the non-single-crystal carbon film has a critical load at which it breaks from 100 mN to 500 mN. 3. The non-single-crystal carbon film has a hydrogen content of 10%.
3. The electrophotographic photosensitive member according to claim 1, wherein the amount of the electrophotographic photoreceptor is in the range of 1% to 60%. 4. The electrophotographic photosensitive member according to claim 1, wherein the non-single-crystal carbon film has an optical band gap of 1.2 to 2.2 eV. body. 5. The non-single-crystal carbon film has a refractive index of 1.8 to 1.8.
The electrophotographic photosensitive member according to claim 1, wherein the ratio is 2.8. 6. The non-single-crystal carbon film according to claim 1, wherein said non-single-crystal carbon film has a thickness of not less than 50 ° and not more than 10,000 ° or not less than 100 ° and not more than 2000 °.
13. The electrophotographic photoreceptor according to item 6. 7. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor has a photosensitive layer made of a non-single crystalline material mainly composed of silicon. . 8. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member has a three-layer structure of a lower blocking layer, a photosensitive layer, and an upper blocking layer. Electrophotographic photoreceptor. 9. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member has a three-layer structure of a charge transport layer, a charge generation layer, and a surface protective layer. The electrophotographic photosensitive member according to the above.