EP0872771A2 - Lichtempfindliches Element, Verfahren zu dessen Herstellung, Bildherstellungsapparat dieses lichtempfindliche Element umfassend, und Bildherstellungsverfahren - Google Patents

Lichtempfindliches Element, Verfahren zu dessen Herstellung, Bildherstellungsapparat dieses lichtempfindliche Element umfassend, und Bildherstellungsverfahren Download PDF

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Publication number
EP0872771A2
EP0872771A2 EP98106550A EP98106550A EP0872771A2 EP 0872771 A2 EP0872771 A2 EP 0872771A2 EP 98106550 A EP98106550 A EP 98106550A EP 98106550 A EP98106550 A EP 98106550A EP 0872771 A2 EP0872771 A2 EP 0872771A2
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EP
European Patent Office
Prior art keywords
photosensitive member
image forming
region
carbon film
photoconductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98106550A
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English (en)
French (fr)
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EP0872771B1 (de
EP0872771A3 (de
Inventor
Aoki Makoto
Ueda Shigenori
Hashizume Junichiro
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Canon Inc
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Canon Inc
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Publication date
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Publication of EP0872771A2 publication Critical patent/EP0872771A2/de
Publication of EP0872771A3 publication Critical patent/EP0872771A3/de
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Publication of EP0872771B1 publication Critical patent/EP0872771B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14773—Polycondensates comprising silicon atoms in the main chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/0433—Photoconductive layers characterised by having two or more layers or characterised by their composite structure all layers being inorganic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08285—Carbon-based

Definitions

  • This invention relates to a photosensitive member, a process for its production, an image forming apparatus having the photosensitive member and an image forming process carried out using the photosensitive member. More particularly, this invention relates, in an electrostatic image forming process including an electrophotographic process, to a photosensitive member as typified by an electrophotographic photosensitive member, that can obtain highly minute images in every environment, may cause no melt-adhesion of toner because of its high release properties even when used in a high-speed process, also has a running performance high enough to maintain such properties, has a high sensitivity, and can stably obtain high-grade images; and a process for its production, an image forming apparatus having such a photosensitive member and an image forming process carried out using the photosensitive member.
  • Such a-Si type photosensitive members have advantages that they have a high surface hardness, exhibit a high sensitivity to long-wavelength light of semiconductor lasers (770 nm to 800 nm) or the like and also are almost free from deterioration due to repeated use. Hence, they are put into use especially in photosensitive members for electrophotographic apparatus such as high-speed copying machines and LBPs (laser beam printers).
  • plasma enhanced CVD i.e., a process in which a source gas is decomposed by glow discharge produced by utilizing a direct current, a high-frequency (RF or VHF) or a microwave to form a deposited film on any desired substrate such as glass, quartz, heat-resistant synthetic film, stainless steel or aluminum is being widely put into practical use in the process for forming amorphous-silicon deposited films used in electrophotography. Apparatus therefor are also proposed in variety.
  • a plasma enhanced process making use of high-frequency power is widely used because of its various advantages such that it has a high discharge stability and can also be used to form insulating materials such as oxide films and nitride films.
  • plasma enhanced CVD carried out using a power source with a high frequency of 50 MHz or above using a diode parallel plate plasma enhanced CVD system, as reported in Plasma Chemistry and Plasma Processing, Vol. 7, No. 3 (1987), pp.267-273, has attracted notice, which shows a possibility of improving the deposition rate without a lowering of the performance of deposited films by making the discharge frequency higher than 13.56 MHz conventionally used. Making the discharge frequency higher in this way is also reported in respect of sputtering, and is widely studied in recent years.
  • the melt-adhesion may grow in the rotational direction with repetition of copying operations to come to cause line faulty images.
  • the melt-adhesion thus grown can only be removed by scraping the photosensitive member surface with alumina powder or the like to remove the melt-adhered toner. This, however, actually means that the photosensitive member must be changed for new one, resulting in a great increase in running cost. Accordingly, it is required to prevent the toner melt-adhesion from occurring and growing.
  • any sufficient attention has not been paid on the release properties or slipperiness of toner on the surface layer. More specifically, in order to cause no toner melt-adhesion, one may contemplate countermeasures such that the surface is modified so as to make the toner hardly adhere to the photosensitive member or the blade is made to have a higher hardness in order to enhance the ability to scrape the toner having adhered. Since, however, frictional force increases and abrasive force increase with an increase in process speed, there is a possibility that the photosensitive member surface is unwantedly scraped even if the surface has been modified to become more effective, unless materials are carefully selected.
  • electrophotographic photosensitive members are also required to have a higher sensitivity, to achieve a higher image quality and to have a thin-film thickness.
  • the surface layer that protects the photosensitive member surface is required to have a low loss and to be formed of a thin film. Accordingly, it has now been sought to provide surface-layer materials that have wide band gaps, have a durability of higher breakdown voltage and can be made into thin films.
  • An object of the present invention is to provide a photosensitive member that has solved the above problems, is improved in the release properties and slipperiness of toner on the surface layer (or surface region) so that no melt-adhesion of toner on the photosensitive member surface may occur in every environment and highly minute and high-grade images can be obtained, and has a superior durability.
  • Another object of the present invention is to provide a photosensitive member that has a high sensitivity, may not cause any faulty images due to a leak, and can stably obtain ghost-free, high-grade images without causing any changes with time.
  • the present invention provides a photosensitive member comprising a substrate having a conductive surface, and provided thereon a photoconductive region preferably comprising a non-single-crystal material mainly composed of silicon atom, and a surface region provided on the photoconductive region; the surface region being formed of a non-single-crystal carbon film having a low spin density and a short spin relaxation time and containing at least hydrogen atom.
  • the present invention also provides an image forming apparatus comprising:
  • the present invention still also provides an image forming process comprising the steps of:
  • the present invention further provides a process for producing a photosensitive member, comprising:
  • the spin density and spin relaxation time in the surface region is taken into account so that the toner can be improved in release properties and slipperiness and the toner can be prevented from melt-adhering to the photosensitive member surface.
  • the toner can be prevented from melt-adhering to the photosensitive member surface, it becomes easy to use toners with smaller particle diameters, so that a photosensitive member that can form more highly minute and high-quality images and also has a high durability can be provided.
  • Fig. 1A is a diagrammatic cross-sectional view of a single-layer type photosensitive member according to the present invention
  • Fig. 1B a diagrammatic cross-sectional view of a function-separated type photosensitive member according to the present invention.
  • Fig. 2 is a diagrammatic view for illustrating an example of a deposition system used to form a photosensitive layer on a substrate by PCVD.
  • Fig. 3 is a diagrammatic view for illustrating an example of a deposition system used to form a photosensitive layer on a substrate by VHF-PCVD.
  • Fig. 4 is a diagrammatic cross-sectional view of an electrophotographic apparatus as an image forming apparatus of the present invention.
  • the photosensitive member of the present invention has a conductive substrate, a photoconductive region provided on the substrate and a surface region further provided on the photoconductive region.
  • the surface region is formed of a non-single-crystal carbon film having a low spin density and a short spin relaxation time and containing at least hydrogen atoms.
  • the photoconductive region and the surface region may be a photoconductive layer and a surface layer, respectively.
  • the non-single-crystal carbon film may preferably have a spin density of 1 ⁇ 10 20 spins/cm 3 or below and a spin relaxation time of 10 -2 seconds or less.
  • the non-single-crystal carbon film may also preferably contain fluorine atoms in the film.
  • the non-single-crystal carbon film may also preferably have fluorine-carbon bonds on its surface or in the vicinity of the surface.
  • the non-single-crystal carbon film of the photosensitive member of the present invention may preferably be formed using a source gas containing fluorine atoms.
  • the non-single-crystal carbon film of the photosensitive member of the present invention may preferably be formed by etching carried out in a plasma originating from a source gas containing fluorine atoms.
  • the photosensitive member of the present invention may preferably be produced using CF 4 gas as the source gas containing fluorine atoms.
  • the surface layer may preferably be formed by decomposing the source gas by plasma enhanced CVD (chemical vapor deposition) employing a high frequency of from 1 to 450 MHz.
  • plasma enhanced CVD chemical vapor deposition
  • the surface layer may preferably be formed by decomposing the source gas by plasma enhanced CVD employing a high frequency of from 50 to 450 MHz.
  • the photosensitive member of the present invention may preferably be provided, between the photoconductive region (layer) and the surface region (layer), an intermediate region (layer) serving as a buffer region (layer), having composition intermediate between the both.
  • the present invention constituted as described above has been accomplished as a result of the following studies made by the present inventors.
  • non-single-crystal carbon films which can be considered to have much higher durability than any conventional surface layer materials, and made extensive studies thereon (herein the non-single-crystal carbon film is mainly meant by a film of amorphous carbon which is neither graphite nor diamond and in the state of a bond intermediate between them, and may be present together with polycrystal or microcrystal).
  • a non-single-crystal carbon film formed under specific conditions has enabled improvement of copying performances-in initial-stage compared with conventional surface layer materials.
  • Non-single-crystal carbon when formed under suitable conditions, terminates the surface with hydrogen atoms, so that the film is considered to have so low a surface free energy as to make substances hardly adhere thereto, i.e., to be improved in release properties.
  • films smooth on the atomic level can be formed by optimizing film-forming conditions or by making suitable treatment. This is presumed to be the cause of improvement in slipperiness.
  • non-single-crystal carbon film it is difficult to control its spin density compared with conventional a-Si or SiC. Under specific conditions, however, a film can be obtained which has a relatively low spin density for non-single-crystal carbon films, i.e., of about 1 ⁇ 10 20 spins/cm 3 or below.
  • the photosensitive member that may cause no melt-adhesion even after long-term service in a high-speed process is presumed to have been obtained because it has become possible to greatly improve the release properties and slipperiness at the initial stage by using the non-single-crystal carbon and by controlling its spin density to be 1 ⁇ 10 20 spins/cm 3 or below and also because it has become possible to maintain such properties by controlling its spin relaxation time to be 10 -2 seconds or less.
  • the film When the surface of the non-single-crystal carbon film is terminated with fluorine atoms, the film can have a much lower surface free energy and can be more improved in release properties and slipperiness. Such reinforcement of bonding energy more restrains surface atoms from coming off, and hence can make the melt-adhesion more hardly occur than the termination with elements such as hydrogen atoms.
  • Termination with fluorine atoms may be made by a method in which a fluorine-containing gas such as CF 4 is introduced to incorporate fluorine atoms into the film from the beginning of film formation or a method in which the surface is fluorinated with plasma of the fluorine-containing gas after the non-single-crystal carbon film has been formed.
  • a soft film may result if fluorine is in a too large proportion in film-forming gases, but the hardness can be maintained so long as the gas ratio is so set as to provide the spin density and spin relaxation time within the scope of the present invention.
  • any lowering of sensitivity that may be caused by the surface layer can be kept minimum, and also a phenomenon of ghost, i.e., a phenomenon in which an image having been copied last remains can be better prevented, and still also an improvement in breakdown voltage has made it possible to form the surface layer in a much smaller layer thickness.
  • FIGs. 1A and 1B are diagrammatic cross-sectional views illustrating the layer configuration of electrophotographic photosensitive members according to the present invention.
  • Fig. 1A shows a photosensitive member called a single-layer type, whose photoconductive layer is not functionally separated, and is a photosensitive member has a substrate 101 optionally provided thereon with a-charge injection blocking layer (charge injection blocking region) 102, and superposed thereon a photoconductive layer (photoconductive region) 103 formed of a-Si and containing at least hydrogen atom, and a surface layer (surface region) 104 formed of non-single-crystal carbon, having the characteristics within the scope of the present invention.
  • a photosensitive member called a single-layer type, whose photoconductive layer is not functionally separated, and is a photosensitive member has a substrate 101 optionally provided thereon with a-charge injection blocking layer (charge injection blocking region) 102, and superposed thereon a photoconductive layer (photoconductive region) 103 formed of a-Si and
  • Fig. 1B shows a photosensitive member called a function-separated type, whose photoconductive layer is functionally separated into a charge generation layer and a charge transport layer.
  • a charge injection blocking layer 102 is optionally provided, and a photoconductive layer 103 formed of a-Si and containing at least hydrogen atom, which is functionally separated into a charge generation layer 106 and a charge transport layer 105, is deposited thereon.
  • the charge generation layer 106 and the charge transport layer 105 may be used under any positional relationship.
  • the compositional change may be made in a continuous fashion.
  • each layer may have a continuous compositional change, or may have no distinctive interface.
  • the charge injection blocking layer 102 may be omitted as occasion calls.
  • an intermediate layer (intermediate region) 104 may also be optionally provided between the photoconductive layer 103 and the surface layer 104 formed of non-single-crystal carbon.
  • the intermediate layer may be formed of a material including SiC, to form a layer having composition intermediate between the photoconductive layer 103 and the surface layer 104, or may also be formed of SiO, SiN or the like.
  • the intermediate layer may also have composition continuously changed.
  • any frequency may be used.
  • RF frequency a high frequency of from 50 to 450 MHz, called VHF is used, the film can be more improved in both the transparency and the hardness, and is more preferred when used to form the surface layer.
  • the film can be formed by decomposing a carbon-containing gas by plasma.
  • the carbon-containing gas usable in that instance may include hydrocarbon gases such as CH 4 , C 2 H 6 , C 2 H 4 and C 2 H 2 ; gases prepared by bubbling alcohols such as CH 3 OH and C 2 H 5 OH with hydrogen; and halogenated hydrocarbon gases prepared by substituting hydrogen atoms of hydrocarbons such as CH 3 F, CH 2 F 2 and CH 3 Cl with halogen atoms; any of which may be used so long as active carbon radicals can be produced when formed into plasma.
  • Some of these can form films alone, while some must be diluted with hydrogen or dilute gas. Optimum conditions must be selected for each occasion.
  • a mixed gas of any of the above gases may also be used.
  • Fig. 2 diagrammatically illustrates an example of a deposition system for producing the photosensitive member by plasma enhanced CVD employing a high-frequency power source according to the present invention.
  • this system is constituted of a deposition system 2100, a source gas feed system 2200 and an exhaust system (not shown) for evacuating the inside of a reactor 2110.
  • a cylindrical film-forming substrate 2112 connected to a ground
  • a heater 2113 for heating the cylindrical film-forming substrate 2112 and a source gas feed pipe 2114 are provided.
  • a high-frequency power source 2120 is also connected to the reactor via a high-frequency matching box 2115.
  • the source gas feed system 2200 has gas cylinders 2221 to 2226 for source gases and etching gases, such as SiH 4 , H 2 , CH 4 , C 2 H 2 , NO, B 2 H 6 and CF 4 , valves 2231 to 2236, 2241 to 2246 and 2251 to 2256, and mass flow controllers 2211 to 2216.
  • the gas cylinders for the respective component gases are connected to the gas feed pipe 2114 in the reactor 2110 through a valve 2260.
  • high-frequency power source used in the present invention power sources having any output may be used so long as they can generate an output power suited for apparatus used within the range of from 10 W to 5,000 W or above.
  • degree of output variability of the high-frequency power source it may be of any value to obtain the effect of the present invention.
  • the high-frequency matching box 2115 used those having any constitution may preferably be used so long as they can make matching between the high-frequency power source 2120 and load.
  • it may preferably be automatically controlled, or may be controlled manually without any adverse effect on the present invention.
  • a cathode electrode inner sidewalls of the reactor to which the high-frequency power is to be applied
  • materials for a cathode electrode copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials may be used.
  • the cathode electrode may preferably have a cylindrical shape, and may optionally have an oval shape or a polygonal shape. Those having figures similar to the cross-sectional shape of the substrate 2112 are preferred because the distance between the substrate 2112 and the cathode electrode can be kept constant.
  • the cathode electrode may be optionally provided with a cooling means.
  • the electrode may be cooled with water, air, liquid nitrogen, Peltier devices or the like, which may be selected as occasion calls.
  • the cylindrical film-forming substrate 2112 may be made of any material and may have any shape in accordance with its uses. For example, with regard to its shape, it may preferably be cylindrical when electrophotographic photosensitive members are produced, or may optionally have the shape of a flat plate or any other shape. With regard to its material, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials, as well as insulating materials such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass, quartz, ceramics and paper which are coated with conductive materials may be used. Of course, these are selected in accordance with film-forming conditions, usage and so forth. Its surface may be shaped by cutting or dimple-working for the purpose of, e.g., preventing interference.
  • the cylindrical film-forming substrate 2112 is set in the reactor 2110, and the inside of the reactor 2110 is evacuated by means of an exhaust device (not shown; e.g., a vacuum pump). Subsequently, the temperature of the cylindrical film-forming substrate 2112 is controlled at a desired temperature within the range of from 20°C to 500°C by means of the heater 2113 for heating the cylindrical film-forming substrate.
  • an exhaust device not shown; e.g., a vacuum pump.
  • gas cylinder valves 2231 to 2236 and a leak valve 2117 of the reactor are checked to make sure that they are closed, and also flow-in valves 2241 to 2246, flow-out valves 2251 to 2256 and an auxiliary valve 2260 are checked to make sure that they are opened. Then, a main valve 2118 is opened to evacuate the insides of the reactor 2110 and a gas feed pipe 2116.
  • the auxiliary valve 2260 and the flow-out valves 2251 to 2256 are closed. Thereafter, gas cylinder valves 2231 to 2236 are opened so that gases are respectively introduced from gas cylinders 2221 to 2226, and each gas is controlled to have a pressure of 2 kg/cm 2 by operating pressure controllers 2261 to 2266. Next, the flow-in valves 2241 to 2246 are slowly opened so that gases are respectively introduced into mass flow controllers 2211 to 2216.
  • the photoconductive layer is first formed on the cylindrical film-forming substrate 2112.
  • the cylindrical film-forming substrate 2112 has had a desired temperature
  • some necessary flow-out valves among the flow-out valves 2251 to 2256 and the auxiliary valve 2260 are slowly opened so that desired source gases are fed into the reactor 2110 from the gas cylinders 2221 to 2226 through a gas feed pipe 2114.
  • the mass flow controllers 2211 to 2216 are operated so that each source gas is adjusted to flow at a desired rate.
  • the divergence of the main valve 2118 is so adjusted that the pressure inside the reactor 2110 comes to be a desired pressure of not higher than 1 Torr, while watching the vacuum gauge 2119.
  • a high-frequency power source 2120 is set at a desired electric power, and a high-frequency power is supplied to the cathode electrode through the high-frequency matching box 2115 to cause high-frequency glow discharge to take place.
  • the source gases fed into the reactor 2110 are decomposed by the discharge energy thus produced, so that a desired deposited layer mainly composed of silicon is formed on the cylindrical film-forming substrate 2112.
  • the supply of high-frequency power is stopped, and the flow-out valves 2251 to 2256 are closed to stop source gases from flowing into the reactor 2110. The formation of the photoconductive layer is thus completed.
  • the surface layer is formed on the photoconductive layer, basically the above operation may be repeated, where film-forming gases may be fed to start discharging.
  • film-forming gases may be fed to start discharging.
  • Types and mixing ratio of gases used, film-forming pressure, high-frequency power and its frequency, film-forming temperature and so forth must be set at suitable values before the non-single-crystal carbon film contributory to the effect of the present invention can be formed. This, however, does not mean that any special apparatus is required.
  • the film may be formed using any conventional plasma enhanced CVD system.
  • the mixing ratio of gases may differ depending on gas species and can not absolutely be prescribed. For example, there is a tendency that it is better for unsaturated hydrocarbon gases to be diluted with hydrogen gas and for saturated hydrocarbon gases not to be so much diluted with hydrogen gas.
  • films may be formed at a pressure within the same range as that of conventional film-forming conditions. It may differ depending on gas species and can not absolutely be prescribed. There is a tendency that it is better for the pressure to be set lower to restrain polymerization from taking place in the vapor phase.
  • high-frequency power C-H bonds can not be cut off and no radicals can be formed unless a discharge energy highr than a certain level is imparted.
  • a too high discharge energy is imparted, re-liberation and sputtering may occur to undesirably make film-forming rate extremely low.
  • a power of about 2,000 W or below is preferred.
  • frequency it is better to use higher frequency to form highly hard and low-loss films with ease, but use of a too high frequency may cause layer thickness distribution.
  • film-forming temperature films may be formed at a temperature within the same range as that of conventional film-forming conditions. If films are formed at a too high temperature, a narrow band gap may result to tend to cause an increase in loss, and hence it is preferable not to set temperature so much high.
  • the respective preset values are not so much different from those in conventional film-forming conditions.
  • the spin density and spin relaxation time have so great a dependence on film-forming parameters that it has been hitherto impossible to form precise films in a good reproducibility.
  • Some necessary flow-out valves among the valves 2251 to 2256 and the auxiliary valve 2260 are slowly opened so that source gases, e.g., CH 4 gas and H 2 gas, necessary for the surface layer are fed into the reactor 2110 from the gas cylinders 2221 to 2226 through a gas feed pipe 2114.
  • source gases e.g., CH 4 gas and H 2 gas
  • the mass flow controllers 2211 to 2216 are operated so that each source gas is adjusted to flow at a desired rate.
  • the divergence of the main valve 2118 is so adjusted that the pressure inside the reactor 2110 comes to be a desired pressure of not higher than 1 Torr, while watching the vacuum gauge 2119.
  • a high-frequency power source 2120 is set at a desired electric power, and a high-frequency power is supplied to the cathode electrode through the high-frequency matching box 2115 to cause high-frequency glow discharge to take place.
  • the source gases fed into the reactor 2110 are decomposed by the discharge energy thus produced, so that the surface layer is formed.
  • the supply of high-frequency power is stopped, and the flow-out valves 2251 to 2256 are closed to stop source gases from flowing into the reactor 2110. The formation of the surface layer is thus completed.
  • the cylindrical film-forming substrate 2112 may be rotated at a stated speed by means of a driving system (not shown).
  • a DC bias voltage may further be applied to the high frequency power through a low-pass filter (not shown).
  • its surface may be fluorinated by subjecting it to fluorine treatment or etching with plasma formed by decomposing a gas containing fluorine atoms.
  • fluorinated by fluorine plasma the effect of the present invention can be attained so long as the spin density and spin relaxation time as defined in the present invention are satisfied.
  • types and mixing ratio of gases used, film-forming pressure, high-frequency power and its frequency, processing temperature, processing time and so forth must be set at suitable values. This, however, does not mean that any special apparatus is required.
  • the surface may be treated using any conventional plasma enhanced CVD system.
  • usable gases are fluorine-containing gases as exemplified by CF 4 , CH 3 F, CH 2 F 2 , CHF 3 , C 2 F 4 , C 2 H 3 F, ClF 3 , SF 6 , HF and F 2 , and any gases may be used so long as active fluorine radicals can be produced when formed into plasma. These may be diluted with dilute gas when used. As a tendency, in the case of gases having strong ethcing properties, they may preferably be diluted in a large quantity.
  • the pressure may be set within the same range as that in conventional film-forming conditions. It may differ depending on gas species, and can not absolutely be prescribed. A too low pressure is not preferable in some cases because the surface roughness tends to increase.
  • high-frequency power C-F bonds can not be cut off and no fluorine radicals can be formed unless a discharge energy not lower than a certain level is imparted. On the other hand, it is not preferable to impart a too high discharge energy because etching may proceed to damage the surface to tend to produce dangling bonds.
  • a power of about 2,000 W or below is preferred.
  • Fig. 3 diagrammatically illustrates a preferred example of an apparatus for producing photosensitive members (electrophotographic photosensitive members) by plasma enhanced CVD according to an embodiment different from that of Fig. 2.
  • This Fig. 3 diagrammatically illustrates a partial cross section of the apparatus at the part of its reactor and the part of its substrate stand which has substrates.
  • reference numeral 300 denotes a deposition system; and 301, a reactor which is so set up that it can be kept in a vacuum atmosphere.
  • Reference numeral 302 denotes an exhaust tube that opens to the inside of a reactor 301 at one end thereof and communicates with an exhaust system (not shown) at the other end thereof.
  • Reference numeral 303 denotes a discharge space surrounded by a plurality of cylindrical film-forming substrates 304.
  • a high-frequency power source 305 is electrically connected to an electrode 307 via a high-frequency matching box 306.
  • the cylindrical film-forming substrates 304 are each provided around a rotating shaft 309 while being set on holders 308(a) and 308(b). These are so set as to be rotatable by means of a motor 310 if necessary.
  • a source gas feed system (not shown), the same system as the one shown in Fig. 2 may be used.
  • the component gases are mixed and are fed into the reactor 301 through a gas feed pipe 311 via a valve 312.
  • the high-frequency power source used in the present film-forming system power sources having any output may be used so long as they can generate an output power suited for apparatus used within the range of from 10 W to 5,000 W or above.
  • the degree of output variability of the high-frequency power source it may be of any value to obtain the effect of the present invention.
  • the high-frequency matching box 306 used those having any constitution may preferably be used so long as they can make matching between the high-frequency power source 305 and load.
  • it may preferably be automatically controlled, or may be controlled manually without any adverse effect on the present invention.
  • the electrode 307 to which the high-frequency power is to be applied copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials may be used.
  • the electrode may preferably have a cylindrical shape, and may optionally have an oval shape or a polygonal shape. The shape may preferably be determined in accordance with the shape of arrangement of the substrates 304.
  • the electrode 307 may be optionally provided with a cooling means.
  • the electrode may be cooled with water, air, liquid nitrogen, Peltier devices or the like, which may be selected as occasion calls.
  • the cylindrical film-forming substrates 304 may be made of any material and may have any shape in accordance with its uses, as previously described.
  • FIG. 4 schematically illustrates the constitution of an apparatus, for describing an example of an image forming process carried out by an electrophotographic apparatus as the image forming apparatus that utilizes electrostatic images.
  • a photosensitive member 401 is rotated in the direction of an arrow X.
  • a primary charging device 402 an electrostatic latent image forming portion 403, a developing device 404, a transfer medium feed system 405, a transfer charging device 406(a), a separation charging device 406(b), a cleaner 407, a transport system 408, a charge elimination light source 409, a transporting guide 419 and so forth are provided.
  • the photosensitive member 401 is uniformly electrostatically charged by means of the primary charging device 402, to which a high voltage is applied.
  • An electrostatic latent image is formed on the photosensitive member at its electrostatic latent image forming portion, i.e., the portion on which light is projected which is emitted from a lamp 410, reflects from an original 412 placed on an original glass plate 411, passes through mirrors 413, 414 and 415 to form an image through a lens 418 of a lens unit 417 and is then guided through a mirror 416.
  • a toner with a negative polarity is fed from the developing device 404 to form a toner image.
  • a transfer medium P is passed through the transfer medium feed system 405 and is fed in the direction of the photosensitive member 401 while adjusting its leading-part feed timing by means of resist rollers 422.
  • a positive electric field having a polarity reverse to that of the toner, is imparted to the transfer medium P on the back thereof at the gap between the transfer charging device 406(a) and the photosensitive member 401.
  • the transfer medium P is separated from the photosensitive member 401 by means of the separation charging device 406(b) to which a high-voltage AC voltage is applied.
  • the transfer medium P is passed through the transfer medium transport system 408 to reach a fixing device 424, where the toner image is fixed, and the transfer medium P with the fixed image is delivered out of the apparatus.
  • the toner remaining on the photosensitive member 401 is collected by a magnet roller 427 and a cleaning blade 421 which are provided in a cleaning unit 407, and the remaining electrostatic latent image is erased through means of the charge elimination light source 409.
  • Reference numeral 420 denotes a blank exposure light source provided in order to eliminate charges from part of the surface of the photosensitive member 401 so that the toner may not adhere to an unauthorized area of the photosensitive member 401.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1, and a surface layer was successively formed thereon under conditions shown in Table 2.
  • the flow rate of hydrogen gas and also the high-frequency power were varied to produce five photosensitive members A to E whose surface layers have different spin densities and spin relaxation times.
  • the values of the spin density and spin relaxation time of each film formed were as shown in Table 6.
  • drums produced in the manner as described above were mechanically rubbed on their surfaces at a certain strength as a substitute test for a durability test to be made using a copying machine, and thereafter were each mounted on the copying machine so that performances after long-term service were estimated.
  • the drum was rotated at a process speed of 400 mm/sec, and a polishing SiC tape (LT-C2000, available from Fuji Photo Film Co., Ltd.) having an average particle diameter (8 ⁇ m) substantially equal to that of toners was brought into contact with it, which was then held down with a parallel pin of 3 mm diameter and 20 mm wide at the contact area, thus the drum surface was rubbed under application of a load.
  • the polishing tape was always moved at about 1 mm/sec so that always virgin areas were fed to keep polishing force constant and also no polish tailings gave an adverse effect. Such forced friction was carried out for 80 minutes.
  • the five drums thus prepared were each mounted on a modified machine of a copying machine NP6062, manufactured by CANON INC.
  • a test chart available from CANON INC. (trade number: FY9-9058) was placed on the glass plate and its copies were taken on 10,000 sheets of A4-size paper under usual amount of exposure.
  • a toner having an average particle diameter of 8 ⁇ m was used as the toner
  • a cleaning blade having a hardness lower by 4 degrees as JIS hardness than usual ones was used as the cleaning blade
  • the blade pressure was set lower than usual so that the copies were taken in an environment tending to cause melt-adhesion.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1, and then a surface layer was deposited thereon.
  • the surface layer was formed under the same conditions as those shown in Table 2 except that the flow rate of hydrogen gas and the high-frequency power were so varied as to form surface layers having spin densities and spin relaxation times outside the scope of the present invention.
  • photosensitive members F and G were produced.
  • the values of the spin density and spin relaxation time are shown in Table 6.
  • the spin density and the spin relaxation time must be 1 ⁇ 10 20 spins/cm 3 or below and 10 -2 seconds or less, respectively.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1.
  • a surface layer was deposited under conditions as shown in Table 3 in which the gas flow rate and the high-frequency power were set at suitable values to incorporate fluorine atoms in the surface layer, thus photosensitive member H was produced.
  • the photosensitive member surface was exposed to fluorine plasma under conditions for fluorination as shown in Table 4 to effect fluorination, thus photosensitive member I was completed.
  • the surface was treated under conditions so selected that the surface layer had the spin density and spin relaxation time within the scope of the present invention.
  • the spin density and the spin relaxation time were as shown in Table 7.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1. Then, using the plasma enhanced CVD system shown in Fig. 2, a surface layer incorporated with fluorine atoms in the film was formed under conditions as shown in Table 3, thus photosensitive member J was produced. Also, after the surface layer was deposited under conditions shown in Table 2, the photosensitive member surface was exposed to fluorine plasma under conditions for fluorination as shown in Table 4 to effect fluorination, thus photosensitive member K was completed. Here, the surface was treated under conditions so selected that the surface layer had the spin density and spin relaxation time outside the scope of the present invention. The spin density and the spin relaxation time were as shown in Table 7.
  • a lower blocking layer and a photoconductive layer were successively superposed on a cylindrical aluminum substrate under conditions shown in Table 1.
  • a surface layer was formed under conditions as shown in Table 5.
  • discharge frequencies three kinds, 50, 100 and 200 MHz, were used, and the flow rate of hydrogen gas and the high-frequency power were set at suitable values to select film-forming conditions so that the spin density and the spin relaxation time were controlled within the scope of the present invention.
  • photosensitive members L, M and N were produced.
  • C Line marks of melt-adhesion are seen.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1, and then a surface layer was deposited thereon.
  • the surface layer was formed under conditions shown in Table 2 but changing the flow rate of hydrogen gas and the high-frequency power so as to form a surface layer under the same conditions as in Example 1 by which a spin density and a spin relaxation time is made within the scope of the present invention.
  • photosensitive member O was produced.
  • the sensitivity of the drum was measured.
  • the drum was rotated at a process speed of 400 mm/sec, and a corona charging device was operated so as to impart a charge potential of about 400 V to the surface.
  • the amount of light was changed at the exposure position, and surface potential was measured at the development position.
  • the amount of exposure light at the time when the surface potential is 50 V is indicated as the sensitivity.
  • the sensitivity was evaluated in comparison with that of a conventional surface layer.
  • a lower blocking layer and a photoconductive layer were deposited on a cylindrical aluminum substrate under conditions shown in Table 1, and then a surface layer was deposited thereon.
  • the surface layer was formed under conditions shown in Table 2 but changing the flow rate of hydrogen gas and the high-frequency power so as to form a surface layer under the same conditions as in Comparative Example 1 by which a spin density and a spin relaxation time is made outside the scope of the present invention.
  • photosensitive member P was produced.
  • Example 4 which was within the scope of the present invention, the sensitivity was found to less deteriorate than that of the conventional surface layer. This was an unexpected result, and was presumably because the dangling bonds decreased, and hence atoms contributing to bond increased, resulting in an increase in bonding energy on the whole to make band gaps greater and bring about a decrease in loss in the surface layer.
  • Comparative Example 3 which was outside the scope of the present invention, showed the same results as conventional photosensitive members.
  • Example 4 which was within the scope of the present invention, it was found that the ghost potential was smaller than that of conventional photosensitive members and the phenomenon of ghost hardly occurred. The reason therefor can not be explained with ease only by the surface layer of thousands of angstroms thick at most, and is unclear at present.
  • Comparative Example 3 which was outside the scope of the present invention, was found to give the same results as conventional photosensitive members.
  • Example 4 which was within the scope of the present invention, white spots were found to very less occur.
  • Comparative Example 3 leaks were observed to have occurred at the edges of spherical protrusions, whereas, in Example 4, marks of leaks were little observed around the spherical protrusions. This difference is presumed to be due to a good coverage for the non-single-crystal carbon film within the scope of the present invention and in addition an improved denseness of the film. As the result, the breakdown strength is considered to have been improved.
  • the surface region (layer) is formed of the non-single-crystal carbon film having a low spin density and a short spin relaxation time and containing at least hydrogen atom, so that the release properties and slipperiness of the toner are both improved.
  • the present invention can realized the photosensitive member that may cause no melt-adhesion of toner on drum surface in every environment and has a superior durability.
  • the present invention can also realize the photosensitive member that has a high sensitivity, may hardly cause the phenomenon of ghost, may not cause any faulty images due to leaks of surface charge, and can stably obtain high-grade images without causing any changes with time.
  • the surface layer of the photosensitive member is formed of a non-single-crystal carbon film having a low spin density and a short spin relaxation time and containing at least hydrogen atom, to thereby provide a photosensitive member that can form highly minute and high-grade images and has a superior durability and provide a photosensitive member that has a high sensitivity, may not cause any faulty images due to a leak, and can stably obtain ghost-free, high-grade images without causing any changes with time.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Chemical Vapour Deposition (AREA)
EP98106550A 1997-04-14 1998-04-09 Lichtempfindliches Element, Verfahren zu dessen Herstellung, Bildherstellungsapparat dieses lichtempfindliche Element umfassend, und Bildherstellungsverfahren Expired - Lifetime EP0872771B1 (de)

Applications Claiming Priority (3)

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JP113538/97 1997-04-14
JP11353897 1997-04-14
JP9113538A JPH10288852A (ja) 1997-04-14 1997-04-14 電子写真感光体

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EP0872771A2 true EP0872771A2 (de) 1998-10-21
EP0872771A3 EP0872771A3 (de) 1999-01-07
EP0872771B1 EP0872771B1 (de) 2001-07-18

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JP (1) JPH10288852A (de)
KR (1) KR100289479B1 (de)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108254913A (zh) * 2017-11-27 2018-07-06 湖南宏动光电有限公司 一种针对循环肿瘤细胞检测的荧光显微镜照明系统

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RU2007115914A (ru) 2004-10-27 2008-11-10 Мацусита Электрик Индастриал Ко., Лтд. (Jp) Кодер звука и способ кодирования звука
JP5121785B2 (ja) * 2008-07-25 2013-01-16 キヤノン株式会社 電子写真感光体および電子写真装置
JP5625399B2 (ja) * 2010-03-09 2014-11-19 富士通株式会社 電子デバイスの製造方法
CN112739837A (zh) * 2018-09-20 2021-04-30 西默有限公司 长寿命激光器腔室电极和具有该长寿命激光器腔室电极的激光器

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US4661427A (en) * 1983-07-27 1987-04-28 Canon Kabushiki Kaisha Amorphous silicon photoconductive member with reduced spin density in surface layer
JPS62113155A (ja) * 1985-11-13 1987-05-25 Fuji Electric Co Ltd 電子写真感光体
JPS63191152A (ja) * 1987-02-04 1988-08-08 Hitachi Ltd 電子写真感光体及び電子写真法
JPH01277243A (ja) * 1988-04-28 1989-11-07 Konica Corp 感光体
US5094929A (en) * 1989-01-04 1992-03-10 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor with amorphous carbon containing germanium

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US4661427A (en) * 1983-07-27 1987-04-28 Canon Kabushiki Kaisha Amorphous silicon photoconductive member with reduced spin density in surface layer
JPS62113155A (ja) * 1985-11-13 1987-05-25 Fuji Electric Co Ltd 電子写真感光体
JPS63191152A (ja) * 1987-02-04 1988-08-08 Hitachi Ltd 電子写真感光体及び電子写真法
JPH01277243A (ja) * 1988-04-28 1989-11-07 Konica Corp 感光体
US5094929A (en) * 1989-01-04 1992-03-10 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor with amorphous carbon containing germanium

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PATENT ABSTRACTS OF JAPAN vol. 12, no. 473 (P-799), 12 December 1988 & JP 63 191152 A (HITACHI), 8 August 1988 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 48 (P-997), 29 January 1990 & JP 01 277243 A (KONICA), 7 November 1989 *

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Publication number Priority date Publication date Assignee Title
CN108254913A (zh) * 2017-11-27 2018-07-06 湖南宏动光电有限公司 一种针对循环肿瘤细胞检测的荧光显微镜照明系统

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DE69801131T2 (de) 2001-11-15
DE69801131D1 (de) 2001-08-23
EP0872771B1 (de) 2001-07-18
CN1196504A (zh) 1998-10-21
JPH10288852A (ja) 1998-10-27
EP0872771A3 (de) 1999-01-07
KR100289479B1 (ko) 2001-05-02
CN1126991C (zh) 2003-11-05
KR19980081387A (ko) 1998-11-25

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