WO2013038467A1 - 電子写真感光体の製造方法 - Google Patents
電子写真感光体の製造方法 Download PDFInfo
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- WO2013038467A1 WO2013038467A1 PCT/JP2011/070695 JP2011070695W WO2013038467A1 WO 2013038467 A1 WO2013038467 A1 WO 2013038467A1 JP 2011070695 W JP2011070695 W JP 2011070695W WO 2013038467 A1 WO2013038467 A1 WO 2013038467A1
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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
- G03G5/02—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
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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
- G03G5/02—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
- G03G5/08214—Silicon-based
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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
- G03G5/02—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
- G03G5/08214—Silicon-based
- G03G5/08278—Depositing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32018—Glow discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32018—Glow discharge
- H01J37/32036—AC powered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
- H01J37/32449—Gas control, e.g. control of the gas flow
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32715—Workpiece holder
Definitions
- the present invention relates to a method for producing an electrophotographic photoreceptor by a plasma CVD (plasma chemical vapor deposition) method.
- a plasma CVD plasma chemical vapor deposition
- an electrophotographic photoreceptor using amorphous silicon (hereinafter also referred to as “a-Si”) is manufactured by forming a deposited film such as a photoconductive layer on a cylindrical substrate.
- a deposited film As a method for forming a deposited film, there is widely used a method in which a raw material gas for forming a deposited film is decomposed by glow discharge using high frequency in the RF band, and the decomposition product is deposited on a cylindrical substrate, so-called RF plasma CVD method. It has been adopted.
- the frequency is high, a standing wave corresponding to the wavelength is generated, and a portion with a small electric field is formed in the plasma, or the plasma is generated due to uneven propagation due to the impedance of the plasma CVD apparatus used. In some cases, it becomes non-uniform, which is a problem in improving the uniformity of the deposited film.
- the electric field to be used is a cross-seeding electric field, charged particles (ions and electrons) in the plasma reciprocate due to the electric field, and other charged particles, neutral active species, source gases and secondary gases are reciprocated during the reciprocation. In some cases, a reaction occurred, resulting in a powdery substance. Incorporation of this powdery substance into the deposited film has been a problem in improving the characteristics of the deposited film.
- a glow discharge at a low frequency is studied to improve the uniformity of the deposited film so that the influence of the standing wave and the impedance of the plasma CVD apparatus is reduced.
- all the voltages are adjusted to be either positive or negative, that is, the voltage of one polarity. It has been studied to discharge only by applying only.
- applying and discharging only positive or negative polarity voltage is referred to as “one-sided polarity discharge”, and alternately applying both positive and negative polarity voltage to discharge. Indicated as “Bipolar discharge”.
- Patent Document 1 discloses a technique that uses a rectangular wave voltage of only one of positive and negative polarity at a frequency of 300 kHz or less. According to Patent Document 1, the uniformity of the deposited film is improved by setting the frequency to 300 kHz or lower. In addition, even when the frequency is 300 kHz or less, the secondary reaction can occur in the case of bipolar discharge as disclosed in Patent Document 2, but in the case of unipolar discharge, charged particles (ions and electrons) However, the secondary reaction is suppressed.
- the image defect referred to here is a solid black (for example, when a toner other than black is used, it is expressed as “solid black” for the sake of convenience).
- a white dot appears on the image, or a black dot appears on the solid white image.
- a toner other than black is used, it is expressed as a “black dot” for the sake of convenience.
- This is what is called “pochi”.
- the peeled film piece adheres to the cylindrical substrate, and in the deposited film formed on the cylindrical substrate starting from that, In some cases, a film defect is generated, and this also leads to an image defect (pocket).
- the film defect mentioned here is a part where the characteristics of the deposited film are locally degraded due to electrical damage caused by minute sparks, or a minute film peeling part of the deposited film formed on the cylindrical substrate by minute sparks. Or it is a protrusion produced when the peeled film piece adheres to the cylindrical substrate.
- the adverse effect caused by such charge-up is that the low voltage portion of the rectangular wave in the technique disclosed in Patent Document 1 is set to 0 V, and the incident of charged particles to the cylindrical substrate is stopped intermittently. It is not improved sufficiently.
- the adverse effects caused by this charge-up can be improved by adopting a bipolar discharge as disclosed in Patent Document 2, but the secondary reaction is likely to occur, so the characteristics of the deposited film are reduced. End up.
- An object of the present invention is to provide a method for producing an electrophotographic photosensitive member that achieves both suppression of charge-up and suppression of secondary reactions at a high level.
- the present invention (I) a step of installing a cylindrical substrate in a reaction vessel having an electrode inside and capable of being depressurized and spaced apart from the electrode; (Ii) introducing a source gas for forming a deposited film into the reaction vessel; (Iii) A cross wave voltage of a rectangular wave having a frequency of 3 kHz or more and 300 kHz or less is applied between the electrode and the cylindrical substrate so that the other potential with respect to one of the electrode and the cylindrical substrate is alternately positive and negative.
- the uniformity of the deposited film and the characteristics of the deposited film are good, the image defect is suppressed, and an electrophotographic photosensitive member capable of outputting a high-quality electrophotographic image is provided. Can be manufactured.
- the present invention (I) a step of installing a cylindrical substrate in a reaction vessel having an electrode inside and capable of being depressurized and spaced apart from the electrode; (Ii) introducing a source gas for forming a deposited film into the reaction vessel; (Iii) A cross wave voltage of a rectangular wave having a frequency of 3 kHz or more and 300 kHz or less is applied between the electrode and the cylindrical substrate so that the other potential with respect to one of the electrode and the cylindrical substrate is alternately positive and negative.
- a method for producing an electrophotographic photosensitive member by a plasma CVD method having: One of the absolute value of the potential difference between the electrode and the cylindrical base when the positive and the absolute value of the potential difference between the electrode and the cylindrical base when the negative is less than the absolute value of the sustaining voltage ( V1) and the other is a value (V2) equal to or greater than the absolute value of the discharge start voltage.
- FIGS. 1A and 1B are diagrams for explaining the cross-seeding voltage of a rectangular wave.
- the electrode potential is constant at the ground potential, and a rectangular wave cross-seeding voltage is applied between the electrode and the cylindrical substrate so that the potential of the cylindrical substrate with respect to the electrode potential is alternately positive and negative.
- the absolute value of the potential difference between the electrode and the cylindrical substrate when the potential of the cylindrical substrate with respect to the potential of the electrode is positive is a value (V1) less than the absolute value of the discharge sustaining voltage.
- the absolute value of the potential difference between the electrode and the cylindrical substrate is a value (V2) that is equal to or greater than the absolute value of the discharge start voltage.
- V2 the absolute value of the potential difference between the electrode and the cylindrical substrate.
- T in FIG. 1A represents the period of the rectangular wave and is determined by the frequency (pulse frequency) of the rectangular wave.
- a rectangular wave having a frequency of 3 kHz to 300 kHz is used, and a rectangular wave having a frequency of 10 kHz to 100 kHz is preferably used.
- t1 in FIG. 1A represents the time (period) during which the absolute value of the potential difference between the electrode and the cylindrical substrate is V1
- t2 is the absolute value of the potential difference between the electrode and the cylindrical substrate.
- the time (period) which is V2 is represented.
- a value obtained by dividing t2 by T (t2 / T) is defined as a duty ratio (%). In the example of FIG. 1A, the duty ratio is 30%.
- Such a rectangular wave cross-seeding voltage is a voltage at which the absolute value of the potential difference between the electrode and the cylindrical substrate is V1 when the potential of the cylindrical substrate is positive with respect to the electrode potential, and a cylindrical shape with respect to the electrode potential.
- a voltage at which the absolute value of the potential difference between the electrode and the cylindrical substrate when the substrate potential becomes negative is V2 is generated from the DC power source, and the switch element is ON / OFF controlled to time-divide the voltage from the DC power source. It can be obtained by pulsing.
- the switch element include those using a semiconductor switch element such as an IGBT (Insulated Gate Bipolar Transistor) and a MOSFET. According to these switch elements, the duty ratio and frequency can be changed.
- FIGS. 2A and 2B are schematic views showing an example of a manufacturing apparatus (plasma CVD apparatus) for carrying out the manufacturing method of the electrophotographic photosensitive member of the present invention.
- 2A is a longitudinal sectional view
- FIG. 2B is a transverse sectional view.
- a cross wave voltage of a rectangular wave having a frequency of 3 kHz or more and 300 kHz or less is applied to the electrode so that the potential of the cylindrical substrate 212 (212A, 212B) with respect to the potential of the electrode 214 is alternately positive and negative.
- the cross wave voltage of the rectangular wave output from the power source 231 and applied between the electrode 214 and the cylindrical base body 212 (212A, 212B) disposed apart from the electrode 214 is obtained by the control unit 230 by using the frequency and duty ratio. Etc. are controlled.
- the frequency of the cross wave voltage of the rectangular wave is set in the range from 3 kHz to 300 kHz, which is from the VLF band to the LF band. If the frequency is too low, abnormal discharge such as arc or spark is likely to occur, and film defects are likely to occur in the deposited film.
- the frequency becomes too high, a standing wave corresponding to the wavelength is generated, and a portion with a small electric field is formed in the plasma, or the plasma becomes non-uniform due to uneven propagation due to the influence of the impedance of the plasma CVD apparatus. As a result, the uniformity of the deposited film tends to decrease.
- the absolute value of the potential difference between the electrode 214 and the cylindrical substrate 212 is a value (V2) that is equal to or greater than the absolute value of the discharge start voltage. Discharge occurs between the substrate 212 (212A and 212B) and plasma is generated. Neutral active species and cations in the plasma reach the cylindrical substrate 212 (212A, 212B), and a deposited film is formed on the cylindrical substrate 212 (212A, 212B). In this process, the cylindrical base body 212 (212A, 212B) is charged to a positive potential due to the positive charge of the cation. Note that “plasma is generated” means that a discharge occurs between the electrode and the cylindrical substrate, and the source gas is ionized to generate charged particles (ions and electrons). .
- the discharge disappears and the plasma cannot be maintained.
- the charged particles (ions and electrons) generated in the period t2 do not disappear instantaneously but remain for a while while gradually decaying in the period t1.
- This state is generally called afterglow, and no new charged particles (ions or electrons) are generated.
- the lifetime of this afterglow is about several tens of microseconds to several milliseconds. Afterglow life varies with pressure. The higher the pressure, the easier it is to collide with gas molecules and the like, so the life of the afterglow tends to be shortened.
- the negatively charged particles, that is, electrons and anions in the afterglow are cylindrical substrates. 212 (212A, 212B) is reached. In this process, the positive charge-up of the cylindrical substrate 212 (212A, 212B) is alleviated by the negative charges of the electrons and the anions.
- the image defect is suppressed because the charge-up of the cylindrical substrate is suppressed as described above, and the minute spark is suppressed.
- the cylindrical substrate 212 (212A, 212B) is also used as a holder (hereinafter referred to as “substrate holder”) 213 for holding the cylindrical substrate 212 (212A, 212B). Therefore, the same phenomenon as that of the cylindrical base body 212 (212A, 212B) occurs also in the base body holder 213.
- FIG. 1A the switching from V2 to V1 and the switching from V1 to V2 are shown to be performed instantaneously.
- switching from V2 to V1 is performed due to the limitation of power supply circuit characteristics. It takes some time to switch from V1 to V2.
- the time required for the switching is about 1 ⁇ sec or less in a general commercial power supply.
- the lifetime of the afterglow is about several tens of microseconds to several milliseconds, which is longer than 1 microsecond, so that the time required for such switching does not affect the effect of the present invention.
- the power source as shown in FIG.
- time at 0V is required when switching from V2 to V1 and when switching from V1 to V2, but this time at 0V is 0.5 ⁇ m. Since it is less than a second and is sufficiently shorter than the lifetime of the afterglow, the effect of the present invention is not affected.
- FIG. 1A a complete rectangular wave is shown.
- the edge of the rectangular wave is rounded, or slightly sharp due to overshoot, or becomes V1 or V2. Sometimes ringing may occur. Even in such a case, the effect of the present invention can be obtained.
- the discharge start voltage and the discharge sustain voltage will be described in detail.
- a small amount of electrons existing between the electrode and the cylindrical substrate are carried to the positive potential side by the electric field, and collide with gas molecules on the way to ionize it.
- the ⁇ action that generates electrons and ions continues.
- the energy of electrons at the time of collision needs to be equal to or higher than the ionization energy of gas molecules.
- the energy when electrons collide with gas molecules increases as the electric field increases, that is, as the voltage applied between the electrode and the cylindrical substrate increases.
- the voltage applied between the electrode and the cylindrical substrate is gradually increased, and when the energy when the electrons collide with the gas molecule reaches the ionization energy of the gas molecule, the ionization of the gas molecule causes the electrode and the cylindrical substrate to Electrons existing during the period increase, and gas molecules continue to be ionized due to collisions, thereby starting discharge.
- the voltage at the beginning of this discharge is called the discharge start voltage.
- the discharge sustain voltage is usually lower than the discharge start voltage. This is because the number of electrons in the discharge space is larger in the state where the discharge occurs than in the state where the discharge is not occurring, and the absolute value of the applied voltage between the electrode and the cylindrical substrate is the absolute value of the discharge start voltage. This is because even if the value is less than the value, if the absolute value of the discharge sustaining voltage is not less than the absolute value of the discharge sustaining voltage, there are more electrons than the number necessary for maintaining the discharge.
- ⁇ action is one of the reasons why the discharge sustain voltage is lower than the discharge start voltage.
- the ⁇ action is a phenomenon in which secondary electrons are emitted from ions generated by ionization of gas molecules when they collide with an electrode or a cylindrical substrate. After the discharge occurs, the electrons generated by this ⁇ action also contribute to the ionization of the gas molecules, so that the discharge can be maintained at a voltage lower than the discharge start voltage.
- the discharge start voltage and the discharge sustain voltage are dominated by the ionization voltage of the gas molecules and the energy when the electrons collide with the gas molecules.
- the ionization voltage of gas molecules is determined once the gas type is determined.
- the energy of electrons when colliding with gas molecules is a function of the electric field strength and the distance traveled until the electrons collide with gas molecules. In other words, it is a function of the applied voltage, the distance between the electrode and the cylindrical substrate, and the distance traveled until the electrons collide with the gas molecules.
- the moving distance until the electrons collide with the gas molecules is a function of gas density, in other words, a function of pressure.
- the gas mixing ratio as well as the ionization voltage of each gas is an element that determines the discharge start voltage and the discharge sustain voltage.
- Electrode surface material Other factors that affect the discharge starting voltage and the sustaining voltage include the electrode surface material, shape, and temperature. These include the ionization voltage, the applied voltage, the distance between the electrode and the cylindrical substrate, and Impact is small compared to pressure.
- the discharge start voltage and the discharge sustaining voltage vary depending on the gas type, the mixing ratio of the gas, the distance between the electrode and the cylindrical substrate, and the pressure. Will have a value. That is, if the plasma CVD apparatus to be used and the gas conditions to be used are determined, the discharge start voltage and the discharge sustain voltage are uniquely determined.
- the discharge is caused by a positive or negative electric field rather than the values of the discharge start voltage and the discharge sustaining voltage, and then the discharge is not maintained by the electric field having the opposite polarity. It is important to get an effect. Therefore, although the values of the discharge start voltage and the discharge sustain voltage themselves vary depending on the gas conditions used and the configuration of the plasma CVD apparatus, the effects of the present invention can be obtained if the conditions of the present invention are satisfied. For example, when a mixed gas of silane gas and hydrogen gas is used and when a mixed gas of silane gas, hydrogen gas, and methane gas is used, the discharge start voltage and the discharge sustain voltage are different. However, in either case, the effects of the present invention can be obtained by satisfying the conditions of the present invention.
- the value (V1) less than the absolute value of the discharge sustaining voltage is preferably 20% or more with respect to the value (V2) greater than or equal to the absolute value of the discharge starting voltage from the viewpoint of suppressing charge-up.
- the value (V1) less than the absolute value of the sustaining voltage is increased, the force that causes charged particles (ions and electrons) in the afterglow to reach the cylindrical substrate increases, thereby suppressing charge-up. This is because the incident density of charges per unit time is increased.
- the effect of suppressing the charge-up is only slightly improved.
- the value (V1) less than the absolute value of the sustaining voltage is preferably 95% or less with respect to the absolute value of the sustaining voltage from the viewpoint of stably obtaining the effect of the present invention.
- the absolute value of the sustaining voltage even if there is a fluctuation in the power supply output or a temporary electric field fluctuation in the discharge space due to peeling of deposits from the inner wall surface of the reaction chamber of the plasma CVD apparatus Therefore, the effects of the present invention can be obtained stably and easily.
- Whether the discharge has started and whether the discharge has been maintained includes, for example, a method of judging from voltage-current characteristics and a method of judging by detecting plasma emission.
- FIG. 4A and 4B are diagrams for explaining a method for measuring the discharge start voltage and the discharge sustain voltage.
- FIG. 4A is a diagram showing voltage-current characteristics when a voltage is applied between an electrode and a cylindrical substrate and a discharge start voltage is obtained using the plasma CVD apparatus shown in FIG.
- FIG. 4B is a diagram showing voltage-current characteristics when the discharge sustaining voltage is obtained using the plasma CVD apparatus shown in FIG. 2, as in FIG. 4A. From such voltage-current characteristics, it is possible to determine whether or not the discharge has started and whether or not the discharge is maintained, and obtain the discharge start voltage and the discharge sustain voltage.
- the output waveform was controlled under the conditions of a frequency of 25 kHz and a duty ratio of 30% as a rectangular wave voltage (pulse voltage) that repeats the set voltage with 0V. Then, the set voltage was increased from 0V in the negative direction in increments of 10V (0V ⁇ ⁇ 10V ⁇ ⁇ 20V%), And the current change at that time was measured. As shown in FIG. 4A, when the set voltage is gradually increased from 0 V in the negative direction, a point at which the current suddenly increases is observed. The voltage at that time is the discharge start voltage.
- the set voltage is increased to +650 V to cause discharge between the electrode and the cylindrical substrate. From this state, when the set voltage is decreased in increments of 10 V in the direction of 0 V (+650 V ⁇ + 640 V ⁇ + 630 V...), A point where the current suddenly decreases is observed. The voltage immediately before the current suddenly decreases is the discharge sustaining voltage. In FIG. 4B, the current when the set voltage is +650 V is shown as 100%.
- the duty ratio of the rectangular wave is preferably 20% or more and 80% or less from the viewpoint of achieving both productivity and suppression of charge-up.
- the duty ratio increases, the ratio of the period t2 during which the source gas is ionized increases, and the productivity tends to improve.
- the duty ratio decreases, the ratio of the period t1 during which the charge-up of the cylindrical substrate is relaxed increases, and the level for suppressing the charge-up tends to increase.
- the afterglow has a lifetime and the amount of charged particles (ions and electrons) in the afterglow is limited, even if the duty ratio is decreased and the period of t1 is increased, the length of the afterglow is increased to some extent. The level to suppress charge-up will not change.
- the cycle T is slightly over 333 ⁇ sec.
- the duty ratio becomes small and the period of t1 becomes long, the afterglow may disappear in the middle of the period of t1, but the period of t2 is short because the period of t1 is long.
- the amount of charge-up of the cylindrical substrate during the period t2 becomes small, so that the charge-up can be sufficiently mitigated during the lifetime of the afterglow.
- the cycle T is slightly over 3.3 ⁇ sec.
- the duty ratio is increased under such a high frequency condition, the period of t1 is shortened.
- the period of t2 is shorter than when the frequency is low, and the amount of charge-up of the cylindrical substrate in the period of t2 is small. Therefore, the charge-up can be sufficiently eased.
- the electric potential of the electrode is kept constant at the ground potential, and a rectangular wave cross-seeding voltage is applied between the electrode and the cylindrical substrate so that the potential of the cylindrical substrate is alternately positive and negative with respect to the electrode potential.
- the absolute value of the potential difference between the electrode and the cylindrical substrate when the potential of the cylindrical substrate becomes positive with respect to the electrode potential becomes a value (V1) less than the absolute value of the sustaining voltage, and the electrode and the cylinder when negative.
- the potential of the electrode may be constant at a potential other than the ground potential
- the potential of the cylindrical substrate may be constant at the ground potential or other potential
- the potential of the electrode and the cylindrical substrate may be constant. Neither of these potentials may be constant.
- the absolute value of the potential difference between the electrode and the cylindrical substrate when positive is a value (V2) that is equal to or greater than the absolute value of the discharge start voltage
- the absolute value of the potential difference between the electrode and cylindrical substrate when negative You may make it become the value (V1) less than the absolute value of a discharge maintenance voltage.
- an electrophotographic photosensitive member is manufactured by forming a deposited film on a cylindrical substrate (the outer peripheral surface of the cylindrical substrate) by a plasma CVD method.
- the deposited film include a lower charge injection blocking layer, a photoconductive layer, an upper charge injection blocking layer, and a surface layer. These layers are sequentially stacked from the cylindrical substrate side to manufacture an electrophotographic photosensitive member. It is common.
- the lower charge injection blocking layer is a layer for suppressing (blocking) charge injection from the cylindrical substrate to the photoconductive layer, and is formed of, for example, an a-Si-based material.
- the photoconductive layer is a layer for generating charges by irradiating an electrophotographic photosensitive member with image exposure light such as laser light, and is formed of, for example, an a-Si material.
- the film thickness of the photoconductive layer is preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 10 ⁇ m or more and 60 ⁇ m or less.
- the upper charge injection blocking layer is a layer for suppressing (blocking) injection of charges on the surface of the electrophotographic photosensitive member into the photoconductive layer when the surface of the electrophotographic photosensitive member is charged.
- a-Si It is formed of a system material.
- the material of the upper charge injection blocking layer is preferably a material containing a-Si containing carbon (C), boron (B), nitrogen (N) or oxygen (O).
- the thickness of the upper charge injection blocking layer is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
- the surface layer is a layer for protecting the surface of the electrophotographic photosensitive member from abrasion, for example, by (hydrogenated) amorphous silicon carbide, (hydrogenated) amorphous silicon nitride, (hydrogenated) amorphous carbon, etc. It is formed.
- the surface layer preferably has a sufficiently wide optical band gap with respect to the image exposure light so that the image exposure light applied to the electrophotographic photosensitive member is not absorbed. Moreover, it is preferable to have a resistance value (preferably 10 11 ⁇ ⁇ cm or more) that can sufficiently hold the electrostatic latent image.
- the electrophotographic photosensitive member can be manufactured by using, for example, a plasma CVD apparatus shown in FIG.
- the plasma CVD apparatus shown in FIG. 2 has a cylindrical shape for forming a deposited film on the cylindrical substrate 212 (upper cylindrical substrate 212A, lower cylindrical substrate 212B) (the outer peripheral surface of the cylindrical substrate 212) by plasma processing. And a heater 216 for heating the cylindrical base body 212 (212A, 212B). Further, base holders 213A and 213B for holding the cylindrical base 212 (212A, 212B), and a gas block 235 for introducing a raw material gas into the reaction vessel 211 are provided.
- the gas block 235 has a structure that can be detached (removable) from the electrode 214.
- connection between the gas block 235 and the gas supply system is connected via a joint member 236.
- FIGS. 3A to 3D are schematic views showing examples of gas blocks that can be used in a manufacturing apparatus (plasma CVD apparatus) for carrying out the method for manufacturing an electrophotographic photosensitive member of the present invention.
- FIG. 3A is an external view of the gas block
- FIGS. 3B to 3D are cross-sectional views of the gas block.
- the gas block 300 includes a tubular cavity 303, a source gas discharge hole 304, and a source gas introduction joint member 317, and the source gas discharge hole 304 is attached so as to be disposed on the inner surface of the reaction vessel 211. .
- the source gas can be introduced into the reaction vessel 211.
- the gas block 235 (300) becomes a part of the electrode 214 when attached to the reaction vessel 211.
- the gas block 235 (300) is preferably attached to the reaction vessel 211 so as to have the same potential as other portions of the electrode 214.
- the entire side wall surface in the reaction vessel 211 including the gas block 235 serves as an electrode, and more uniform plasma can be generated.
- the material of the gas block 235 is preferably a conductive metal, and aluminum and stainless steel are more preferable from the viewpoint of ease of processing and cost.
- a method of attaching the gas block 235 for example, a method of fixing with a conductive screw can be mentioned.
- the shape of the gas block 235 a shape in which a step with respect to the inner surface of the other part of the electrode 214 is reduced is preferable.
- the surface of the gas block (surface on the gas discharge hole side) that forms the same surface as the inner surface of the other part of the electrode 214 may be a flat surface, but when the other inner surface of the electrode 214 is a curved surface, it has the same curvature. A curved surface is preferred.
- a back plate 302 may be provided so as to be separable from the main body 301 of the gas block.
- FIG. 3D is a schematic view of a state where the back plate 302 of the gas block having the main body 301 and the back plate 302 is removed.
- the main body 301 and the back plate 302 are structured to be kept airtight by an O-ring 305.
- the internal tubular cavity 303 is opened, so that the gas path inside the gas block can be easily cleaned. If a residue during formation of a deposited film or a residue that cannot be removed during etching remains in the gas path, it causes image defects in the electrophotographic photosensitive member.
- the diameter of the gas discharge hole of the gas block is preferably in the range of 0.5 to 2.0 mm. Furthermore, the accuracy of each gas discharge hole is preferably within ⁇ 20% of the diameter. Depending on the accuracy of the gas discharge hole, not only the longitudinal unevenness (axial direction) of the electrophotographic photosensitive member but also the circumferential unevenness of the electrophotographic photoreceptor when the deposited film is formed while rotating the cylindrical substrate. May cause.
- an insulating ceramic as the material in the vicinity of the gas discharge hole of the gas block.
- the plasma may tend to concentrate near the gas discharge hole due to the influence of the gas flow (protrusion pressure), so the use of insulating ceramic is effective in suppressing this.
- the gas block 235 can be detached from the electrode 214 (can be detached), the gas block can be processed by itself, so that the tubular ceramic component can be easily embedded in the vicinity of the gas discharge hole.
- the ceramic material include alumina, zirconia, mullite, cordierite, silicon carbide, boron nitride, and aluminum nitride. Among these, alumina, boron nitride, and aluminum nitride are preferable from the viewpoint of insulation resistance, and alumina is more preferable from the viewpoint of cost and workability.
- a space (discharge space) that can be depressurized by the electrode 214, the base plate 219, and the upper lid 220 is formed.
- the electrode 214 is preferably at a constant potential, and more preferably at ground potential (grounded). By setting the electrode 214 to a constant potential, the potential difference between the electrode 214 and the other part in the reaction vessel 211 can be kept constant, so that the reproducibility of the characteristics of the electrophotographic photoreceptor to be manufactured is improved. Further, by grounding the electrode 214, the plasma CVD apparatus can be easily handled.
- the base plate 219 and the upper lid 220 are grounded and the electrode 214 is not grounded, it is preferable to provide an insulating member between the electrode 214 and the base plate 219 and the upper lid 220. In the plasma CVD apparatus shown in FIG. 2, all of the electrode 214, the base plate 219, and the upper lid 220 are grounded.
- the plasma CVD apparatus shown in FIG. 2 includes a source gas mixing device 225 and a source gas inflow valve 224 that include a mass flow controller (not shown) for adjusting the flow rate of the source gas.
- the substrate holders 213A and 213B that hold the cylindrical substrate 212 (212A, 212B) are rotatably supported.
- the rotation support mechanism includes a support shaft 222 and a motor 221 connected to the support shaft 222 with a gear.
- the joining electrodes 217A and 217B are joined inside the base holders 213A and 213B.
- the joining electrodes 217A and 217B are connected to the power source 231 via the support shaft 222.
- the electrode 214, the cylindrical base body 212 (212A, 212B), and the base body holders 213A, 213B are arranged so that their central axes coincide.
- the outer surface of the heater 216 is grounded, and the insulating member 215A is provided between the heater 216 and the cylindrical base body 212 (212A, 212B), so that the heater 216 and the cylindrical base body 212 (212A, 212B) Is insulated.
- an insulating member 215B is installed between the support shaft 222 and the heater 216 and the support shaft 222 are insulated.
- the plasma CVD apparatus shown in FIG. 2 has an exhaust pipe 226 communicated with an exhaust port of the reaction vessel 211, an exhaust main valve 227, and a vacuum pump 228 as an exhaust system.
- the vacuum pump include a rotary pump and a mechanical booster pump.
- the output from the power source 231 is controlled by the control unit 230.
- the control unit 230 controls the output of the power source 231 to apply a rectangular wave cross-seeding voltage having a frequency of 3 kHz to 300 kHz between the electrode 214 and the cylindrical base body 212 (212A, 212B). .
- the discharge space (decompressible space) for forming the deposited film includes a grounded electrode 214, an insulating plate 218B attached to the grounded base plate 219, and an insulating plate 218A attached to the grounded upper lid 220. It is prescribed by.
- the distance D between the cylindrical substrate 212 (212A, 212B) and the electrode 214 will be described. If the distance D is 5 mm or more, the variation of the distance D for each lot caused by the coaxial deviation between the cylindrical substrate 212 (212A, 212B) and the electrode 214 when the cylindrical substrate 212 (212A, 212B) is installed. Stable reproducibility can be easily obtained because the influence is difficult to occur. However, since the reaction container 211 becomes larger as the distance D is larger, the productivity per unit installation area is lowered. For this reason, it is preferable that the distance D is 5 mm or more and 300 mm or less.
- a cylindrical substrate 212 (212A, 212B) having a mirror-finished surface using a lathe or the like is mounted on the substrate holder 213A, 213B so as to include a heater 216 for heating the cylindrical substrate in the reaction vessel 211. Install in the reaction vessel 211.
- the raw material gas inflow valve 224 is opened and the exhaust main valve 227 is opened to serve as exhaust in the gas supply device, and the reaction vessel 211 and the gas block 235 are exhausted.
- a predetermined pressure for example, 0.67 Pa or less
- an inert gas for heating for example, argon gas
- the flow rate of the inert gas for heating, the opening of the exhaust main valve 227, the exhaust speed of the vacuum pump 228, and the like are adjusted so that the inside of the reaction vessel 211 becomes a predetermined pressure.
- a temperature controller (not shown) is operated to heat the cylindrical base body 212 (212A, 212B) by the heater 216, and the temperature of the cylindrical base body 212 (212A, 212B) is set to a predetermined temperature (for example, 20 to 500 ° C.). ) To control. When the cylindrical base body 212 (212A, 212B) is heated to a predetermined temperature, the inert gas is gradually stopped.
- a source gas for forming a deposited film (amorphous film) for example, silicon hydride gas such as SiH 4 and Si 2 H 6 , hydrocarbon gas such as CH 4 and C 2 H 6, etc.
- a doping gas for example, B 2 H 6 , PH 3, etc.
- each source gas is adjusted to a predetermined flow rate by a mass flow controller (not shown) in the source gas mixing device 225.
- the opening of the exhaust main valve 227 and the exhaust speed of the vacuum pump 228 are adjusted while looking at the vacuum gauge 223 so that the inside of the reaction vessel 211 is maintained at a predetermined pressure (for example, 1 to 100 Pa).
- the deposited film is formed on the cylindrical substrate 212 (212A, 212B).
- the power source 231 is set to a predetermined voltage and controlled.
- the unit 230 sets a predetermined frequency and duty ratio.
- a rectangular wave cross-seeding voltage is applied between the cylindrical base body 212 (212A, 212B) and the electrode 214 through the support shaft 222 and the base body holders 213A, 213B to cause glow discharge.
- Each source gas introduced into the reaction vessel 211 is decomposed by the energy of this discharge, and a predetermined deposited film is formed on the cylindrical substrate 212 (212A, 212B).
- the cylindrical substrate 212 (212A, 212B) may be rotated at a predetermined speed by the motor 221 while the deposited film is being formed.
- An electrophotographic photoreceptor can be produced by repeating the above operation.
- Example 1 and Comparative Example 1 the potential of the electrode is constant at the ground potential, the potential of the cylindrical substrate is alternately positive and negative with respect to the electrode potential, and the potential of the cylindrical substrate is positive with respect to the electrode potential.
- the absolute value of the potential difference between the electrode and the cylindrical substrate is less than the absolute value of the sustain voltage (V1), and the absolute value of the potential difference between the electrode and the cylindrical substrate is the absolute value of the discharge start voltage.
- the frequency (C2) of the rectangular wave applied between the electrode and the cylindrical substrate is set to 60 V, the duty ratio is set to 50%, and the photoconductive layer is deposited.
- the dependence of electrophotographic characteristics on V1 was investigated. Since the electrode potential is the ground potential (0 V), V1 and V2 are the absolute value of the potential of the cylindrical substrate when the absolute value of the potential difference between the electrode and the cylindrical substrate is V1 and V2, respectively. It is the same value.
- a deposited film is formed under the conditions shown in Table 1 on a cylindrical substrate (a cylindrical substrate made of aluminum having a diameter of 84 mm, a length of 381 mm, and a thickness of 3 mm).
- a deposited film was formed in the order of the lower injection blocking layer, the photoconductive layer, the upper injection blocking layer, and the surface layer.
- the discharge start voltage and the discharge sustain voltage were as shown in Table 1.
- the conditions shown in Table 2 were used for V1 when forming the deposited film of the photoconductive layer.
- a total of 10 electrophotographic photoreceptors were manufactured in 5 batches (5 cases), 1 batch per case and 2 batches per batch.
- the discharge start voltage (negative potential) and the discharge sustain voltage (positive potential) are values measured in advance by the method described above under the pressure and gas conditions in the reaction vessel when the deposited films of the respective layers are formed.
- V1 (440V) of Comparative Example 1-1 in Table 2 is equal to the absolute value (440V) of the sustaining voltage, it is not exactly V1, but is a value to be compared with V1 of the example. V1 ”. The same applies hereinafter.
- Example 1 10 electrophotographic photoreceptors produced in Example 1 and Comparative Example 1 were evaluated by the following methods. The evaluation results are shown in Table 3.
- the manufactured electrophotographic photosensitive member was installed in a modified machine of a copying machine (trade name: iRC6800) manufactured by Canon Inc., which was modified to a negatively charged, reversal developing method.
- a surface potential meter (a surface potential meter (trade name: Model 344) and a probe (trade name: Model 555-P) manufactured by Trek) is installed, and an electrophotographic photosensitive member is installed. The surface potential was measured.
- a solid white image (electrostatic latent image forming laser non-exposed) is output, the dark part potential of the surface of the electrophotographic photosensitive member is measured, the primary current of the primary charger and the grid voltage are adjusted, and electrophotographic photosensitive The dark part potential of the body surface was adjusted to ⁇ 450V.
- the fog density was measured according to the following procedure, and an image for evaluation was output under development conditions where the fog density was in the range of 0.4 to 0.8%.
- the reflectance of the evaluation image was measured, and the reflectance of unused paper was further measured.
- the reflectance value of the evaluation image was subtracted from the reflectance value of unused paper to obtain the fog density.
- the reflectance was measured by attaching an amber filter to a white photometer (trade name: TC-6DS) manufactured by Tokyo Denshoku.
- Image output was performed in a normal temperature and humidity environment with a temperature of 23 ° C./humidity of 60% RH. The same applies to the following.
- the number of spots is counted for each of the two output images, the average value of the evaluation number is calculated, and the number after the decimal point is rounded up to an integer. Indicated by value.
- rank D was performed according to the following criteria. A ... 8 or less B ... 9 or more and 16 or less C ... 17 or more and 29 or less D ... 30 or more In rank D, it was judged that the effect of the present invention was not obtained. .
- optical memory The optical memory was evaluated as follows.
- the manufactured electrophotographic photosensitive member was installed in the modified machine, and the surface potential of the electrophotographic photosensitive member was measured.
- the light portion potential of the surface of the electrophotographic photosensitive member is measured, and the amount of light of the electrostatic latent image forming laser is adjusted to produce an electronic
- the light portion potential on the surface of the photographic photoreceptor was adjusted to -100V.
- the average value of the potential difference at each axial position was calculated, and the value with the largest potential difference was defined as optical memory.
- ranking was performed according to the following criteria.
- rank D an output image It was determined that the difference in density was clearly confirmed above, and the effect of the present invention was not obtained.
- the film thickness of the electrophotographic photosensitive member was measured at the following measurement points.
- the center position of the electrophotographic photosensitive member in the axial direction is set to 0 cm, and 9 points ( ⁇ 2 cm, ⁇ 4 cm, ⁇ 6 cm, ⁇ 8 cm, ⁇ 10 cm, ⁇ 12 cm, ⁇ 14 cm, ⁇ 16 cm, ⁇ 2 cm on both sides) 18 cm), a total of 19 points including the 0 cm position, and 12 points at 30 ° intervals in the circumferential direction at each axial position, and a total of 228 points were measured positions.
- the value obtained by dividing the difference between the maximum value and the minimum value of the film thickness at each measurement point by the average film thickness was defined as film thickness uniformity.
- the measurement was performed by an eddy current method with a probe ETA3.3H attached to FISCHERSCOPEmms (trade name) manufactured by HELMUTFISCHER.
- the value of the larger one of the two electrophotographic photosensitive members was adopted as the value of the film thickness uniformity in each example and comparative example.
- rank D Since the density difference according to the film thickness unevenness may be confirmed in the output image, it was determined that the effect of the present invention was not obtained.
- Example 1-2 and 1-3 in which V1 is 20% or more of V2, the number of image defects is reduced as compared with Example 1-1 in which V1 is less than 20% of V2. It is considered that the effect of suppressing charge-up has been improved.
- Table 9 shows the results of ranking.
- Example 2 the dependency of electrophotographic characteristics on V1 at the time of forming a deposited film of the photoconductive layer was examined at a frequency of 10 kHz.
- Table 8 shows the evaluation results.
- Example 3 the dependency of the electrophotographic characteristics on V1 at the time of forming the deposited film of the photoconductive layer was examined at a frequency of 100 kHz.
- Table 8 shows the evaluation results.
- Table 9 shows the results of ranking.
- Examples 1-1, 2-1, and 3-1 in which V1 is 100 V have a lower image defect evaluation rank than Examples in which V1 is 20% or more of V2. From this, it can be seen that it is preferable to set V1 to 20% or more of V2 with respect to the image defect level improvement effect by suppressing the charge-up.
- the film thickness uniformity tends to decrease slightly when the frequency is increased to 100 kHz, it is considered that the film thickness uniformity is sufficient and good discharge uniformity is obtained.
- Example 4 and Comparative Example 4 From Example 1 and Comparative Example 1, the internal pressure was changed to 400 Pa, the frequency was changed to 10 kHz, the duty ratio was changed to 80%, and a deposited film was formed under the conditions shown in Table 10 to produce an electrophotographic photosensitive member. did. The conditions shown in Table 11 were used for V1 when forming the deposited film of the photoconductive layer.
- Example 4 the dependency of electrophotographic characteristics on V1 during formation of the deposited film of the photoconductive layer was examined at an internal pressure of 400 Pa, a frequency of 10 kHz, and a duty ratio of 80%.
- Table 14 shows the evaluation results.
- Example 5 the dependency of the electrophotographic characteristics on V1 during the formation of the deposited film of the photoconductive layer was examined at an internal pressure of 400 Pa and a frequency of 60 kHz.
- Table 14 shows the evaluation results.
- Table 15 shows the result of ranking.
- Example 6 and Comparative Example 6 From Example 1 and Comparative Example 1, the internal pressure was changed to 40 Pa, the frequency was changed to 10 kHz, the duty ratio was changed to 20%, and a deposited film was formed under the conditions shown in Table 16 to produce an electrophotographic photosensitive member. did. The conditions shown in Table 17 were used for V1 when forming the deposited film of the photoconductive layer.
- Example 6 the dependence of the electrophotographic characteristics on V1 during the formation of the deposited film of the photoconductive layer was examined at an internal pressure of 40 Pa, a frequency of 10 kHz, and a duty ratio of 20%.
- Example 7 the dependency of the electrophotographic characteristics on V1 at the time of forming the deposited film of the photoconductive layer was examined at an internal pressure of 40 Pa and a frequency of 60 kHz.
- Examples 4 to 7 the case where the duty ratio and the internal pressure are changed is considered. Considering the amount of charge-up, the amount of charge-up during one cycle increases as the duty ratio increases and V2 increases. This is because as the period of t2 is longer and V2 is larger, the charge density in the plasma is higher and the amount of charge-up is larger. Further, even in Examples 4 and 5 which are high pressure conditions (400 Pa) in which the life of the afterglow is shortened, a sufficient charge-up suppressing effect is obtained. On the other hand, when the internal pressure is lowered, the life of the afterglow is extended, so that more charge components can be attracted than when the internal pressure is high, and the effect of suppressing the charge-up is easily obtained.
- Example 8 and Comparative Example 8> Using the same plasma CVD apparatus as in Example 1 and Comparative Example 1, a cylindrical substrate having a diameter different from that of Example 1 (a cylindrical substrate made of aluminum having a mirror finish of 108 mm in diameter, 358 mm in length, and 5 mm in thickness) ) A deposited film was formed under the conditions shown in Table 22 above to produce an electrophotographic photosensitive member.
- Example 8 the dependence of the electrophotographic characteristics on V1 when the deposited film of the photoconductive layer was formed when the distance between the electrode and the cylindrical substrate was reduced was examined.
- a modified copier (trade name: iR-7086N) manufactured by Canon Inc. modified to a negative charging and reversal developing system was used.
- this remodeling machine can adjust the voltage conditions of charging, developing, and transferring and the laser light quantity for image exposure.
- the black developing unit of the copying machine is removed, and a surface potential meter (a surface potential meter (trade name: Model 344) and a probe (trade name: Model 555-P) manufactured by Trek) is installed, and an electrophotographic photosensitive member is installed. The surface potential was measured.
- the optical memory was evaluated in the same manner as in Example 1. However, the evaluation device was changed to the above-mentioned copying machine (trade name: iR-7986N), and the range of the solid black portion was 339 mm, which is a length corresponding to one turn from the diameter of 263 mm to the diameter of the electrophotographic photosensitive member 108 mm. Changed to
- Evaluation of film thickness uniformity was performed in the same manner as in Example 1 except that the length of the electrophotographic photosensitive member was 358 mm, and the measurement positions were as follows.
- the center position in the axial direction of the electrophotographic photosensitive member is 0 cm, and 8 points ( ⁇ 2 cm, ⁇ 4 cm, ⁇ 6 cm, ⁇ 8 cm, ⁇ 10 cm, ⁇ 12 cm, ⁇ 14 cm, ⁇ 16 cm) at 2 cm intervals on both sides, A total of 17 points including the 0 cm position were set, and 12 points at 30 ° intervals in the circumferential direction at each axial position, and a total of 204 points were set as measurement positions.
- a cylindrical substrate (a cylinder made of aluminum having a mirror finish of a diameter of 84 mm, a length of 370 mm, and a thickness of 3 mm).
- a deposited film was formed on the substrate) under the conditions shown in Table 25 to produce an electrophotographic photosensitive member.
- the temperature, film thickness and frequency of the cylindrical substrate when forming the deposited film of the lower injection blocking layer, photoconductive layer, upper injection blocking layer and surface layer were the same as in Example 1.
- FIG. 5 a plasma CVD apparatus shown in FIGS. 5A and 5B
- 515A is an insulating member for insulating the heater 516 and the cylindrical base body 512 (512A, 512B), and 515B is an insulating member for insulating the heater 516 and the support shaft 522.
- Reference numerals 517A and 517B denote joining electrodes joined to the inside of the base holders 513A and 513B
- 518A denotes an insulating plate attached to the upper lid 520
- 518B denotes an insulating plate attached to the base plate 519.
- Reference numeral 519 denotes a grounded base plate
- reference numeral 520 denotes a grounded upper lid.
- Reference numeral 521 denotes a motor for rotating the cylindrical substrate 512 (512A, 512B) at a predetermined speed.
- 523 is a vacuum gauge
- 524 is a raw material gas inflow valve
- 525 is a raw material gas mixing device
- 526 is an exhaust pipe communicated with the exhaust port of the reaction vessel 511
- 527 is an exhaust main valve.
- 528 is a vacuum pump.
- the control unit 530 is a control unit for controlling the output of the power supply 531.
- Reference numerals 533A and 533B denote vacuum-tight and insulating members (vacuum-tight and insulating ceramics), and 535 denotes a gas block. Except as otherwise noted, the components function in the same manner as the elements of the plasma CVD apparatus shown in FIG.
- Example 9 the dependency when the frequency was changed to 3 kHz, 60 kHz, and 300 kHz was examined.
- a DC pulse is applied to the cylindrical substrate 512 (512A, 512B) by turning on / off the DC voltage and repeating a predetermined voltage and 0V with a rectangular wave. Further, a DC voltage is applied from the power source 534 to the electrode 514 on the container wall surface side. Thus, the potential of the cylindrical substrate with respect to the potential of the electrode is alternately made positive and negative.
- FIG. 6A and 6B are diagrams illustrating an example of a cross wave voltage of a rectangular wave.
- FIG. 6A shows that the electrode potential is constant at a potential other than the ground potential, and the rectangular wave cross-seeding voltage between the electrode and the cylindrical substrate is set so that the potential of the cylindrical substrate with respect to the electrode potential is alternately positive and negative. It is a figure which shows the change of the electric potential of the cylindrical base
- the solid line in FIG. 6A is the potential of the cylindrical substrate, and the broken line in FIG. 6A is the potential of the electrode.
- FIG. 6B is a diagram showing a change in potential difference between the electrode and the cylindrical substrate. The broken line in FIG. 6B is the potential difference between the electrode and the cylindrical substrate.
- the discharge start voltage (negative potential) and the discharge sustain voltage (positive potential) are values measured in advance by the method described above under the pressure and gas conditions in the reaction vessel when the deposited films of the respective layers are formed. The measurement results are shown in Table 25.
- the frequency and discharge sustaining voltage when forming the deposited film of the photoconductive layer were the conditions shown in Table 25.
- a total of 6 electrophotographic photosensitive members were produced in 3 batches (3 cases), 1 batch per case and 2 electrophotographic photoreceptors per batch.
- the produced electrophotographic photoreceptor was evaluated in the same manner as in Example 1 and Comparative Example 1.
- Example 9-2 shows the same result as Example 1-2. From this, it can be seen that the effect of the present invention can be obtained by satisfying the conditions of the present invention even if the voltage application method is different.
- Example 9-1 since the frequency is as low as 3 kHz, the period of t2 in one cycle is long. For this reason, the amount of charge-up is increased, and it is considered that image defects are slightly increased as compared with Example 2-3 and Example 9-2.
- Example 9-3 having a frequency of 300 kHz, although the film thickness uniformity is slightly lowered, the effect of the present invention is obtained.
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Abstract
Description
(i)内部に電極を有する減圧可能な反応容器の内部に、前記電極と離間させて円筒状基体を設置する工程と、
(ii)前記反応容器の内部に堆積膜形成用の原料ガスを導入する工程と、
(iii)前記電極および前記円筒状基体の一方の電位に対する他方の電位が交互に正と負になるように、周波数3kHz以上300kHz以下の矩形波の交播電圧を前記電極と前記円筒状基体との間に印加して、前記原料ガスを分解し、前記円筒状基体上に堆積膜を形成する工程と、
を有するプラズマCVD法によって電子写真感光体を製造する方法において、
前記正になるときの前記電極と前記円筒状基体の電位差の絶対値および前記負になるときの前記電極と前記円筒状基体の電位差の絶対値の一方が放電維持電圧の絶対値未満の値(V1)であって、他方が放電開始電圧の絶対値以上の値(V2)であることを特徴とする電子写真感光体の製造方法である。
(i)内部に電極を有する減圧可能な反応容器の内部に、前記電極と離間させて円筒状基体を設置する工程と、
(ii)前記反応容器の内部に堆積膜形成用の原料ガスを導入する工程と、
(iii)前記電極および前記円筒状基体の一方の電位に対する他方の電位が交互に正と負になるように、周波数3kHz以上300kHz以下の矩形波の交播電圧を前記電極と前記円筒状基体との間に印加して、前記原料ガスを分解し、前記円筒状基体上に堆積膜を形成する工程と、
を有するプラズマCVD法によって電子写真感光体を製造する方法において、
前記正になるときの前記電極と前記円筒状基体の電位差の絶対値および前記負になるときの前記電極と前記円筒状基体の電位差の絶対値の一方が放電維持電圧の絶対値未満の値(V1)であって、他方が放電開始電圧の絶対値以上の値(V2)であることを特徴としている。
図1Aは、電極の電位をアース電位で一定とし、電極の電位に対する円筒状基体の電位が交互に正と負になるように矩形波の交播電圧を電極と円筒状基体との間に印加した場合の円筒状基体の電位の変化を示す図である。図1Aの例では、電極の電位に対する円筒状基体の電位が正になるときの電極と円筒状基体の電位差の絶対値が放電維持電圧の絶対値未満の値(V1)となっており、負になるときの電極と円筒状基体の電位差の絶対値が放電開始電圧の絶対値以上の値(V2)となっている。図1Aの例では、電極の電位を一定としているため、円筒状基体の電位が図1Aに示すように矩形状に変化する。
電極と円筒状基体との間の放電は、電極と円筒状基体との間にわずかながら存在している電子が電界によって正電位側に運ばれ、その途中でガス分子に衝突してこれを電離させて、電子とイオンを生成するα作用が継続することによって始まる。この電離を生じさせるためには、衝突時の電子のエネルギーが、ガス分子の電離エネルギー以上であることが必要となる。電子がガス分子に衝突する際のエネルギーは、電界が大きくなるほど、すなわち、電極と円筒状基体との間に印加する電圧が大きくなるほど大きくなる。電極と円筒状基体との間に印加する電圧を徐々に上げていき、電子がガス分子に衝突する際のエネルギーがガス分子の電離エネルギーに達すると、ガス分子の電離によって電極と円筒状基体との間に存在する電子が増加して、衝突によるガス分子の電離が継続して起こることで放電が始まる。この放電が始まる時点の電圧を放電開始電圧という。
旋盤などを用いて表面に鏡面加工を施した円筒状基体212(212A、212B)を、基体ホルダー213A、213Bに装着し、反応容器211内の円筒状基体加熱用のヒーター216を包含するように反応容器211内に設置する。
実施例1および比較例1では、電極の電位をアース電位で一定とし、電極の電位に対する円筒状基体の電位が交互に正と負になるようにし、電極の電位に対する円筒状基体の電位が正になるときの電極と円筒状基体の電位差の絶対値が放電維持電圧の絶対値未満の値(V1)、負になるときの電極と円筒状基体の電位差の絶対値が放電開始電圧の絶対値以上の値(V2)となるようにし、電極と円筒状基体との間に印加する矩形波の交播電圧の周波数を60kHzとし、Duty比を50%として、光導電層の堆積膜形成時のV1に対する電子写真特性の依存性を調べた。なお、電極の電位がアース電位(0V)であるため、V1、V2は、それぞれ、電極と円筒状基体の電位差の絶対値がV1、V2となったときの円筒状基体の電位の絶対値と同じ値である。
画像欠陥については、以下のように評価した。
A・・・8個以下
B・・・9個以上16個以下
C・・・17個以上29個以下
D・・・30個以上
ランクDでは、本発明の効果が得られていないと判断した。
光メモリーについては、以下のように評価した。
A・・・0.0V以上1.0V未満
B・・・1.0V以上2.0V未満
C・・・2.0V以上3.0V未満
D・・・3.0V以上
ランクDでは、出力画像上で濃度差が明確に確認できるレベルであり、本発明の効果が得られていないと判断した。
電子写真感光体の膜厚を以下の測定点で測定した。
A・・・3.0%未満
B・・・3.0%以上4.0%未満
C・・・4.0%以上5.0%未満
D・・・5.0%以上
ランクDでは、膜厚ムラに応じた濃度差が出力画像で確認できる場合があるため、本発明の効果が得られていないと判断した。
総合評価として、画像欠陥、光メモリーおよび膜厚均一性のそれぞれのランクで最も低い評価ランクを総合評価として示す。
下部注入阻止層、光導電層、上部注入阻止層および表面層の堆積膜形成時の周波数を10kHzに変更した以外は、実施例1と同様にして電子写真感光体を製造した。ただし、光導電層の堆積膜形成時のV1については、表5に示す条件とした。
下部注入阻止層、光導電層、上部注入阻止層および表面層の堆積膜形成時の周波数を100kHzに変更した以外は、実施例1と同様にして電子写真感光体を製造した。ただし、光導電層の堆積膜形成時のV1については、表7に示す条件とした。
実施例1および比較例1から内圧を400Paに変更し、周波数を10kHzに変更し、Duty比を80%に変更して、表10に示す条件で堆積膜を形成し、電子写真感光体を製造した。光導電層の堆積膜形成時のV1については、表11に示す条件とした。
下部注入阻止層、光導電層、上部注入阻止層および表面層の堆積膜形成時の周波数を60kHzに変更した以外は、実施例4と同様にして電子写真感光体を製造した。ただし、光導電層の堆積膜形成時のV1については、表13に示す条件とした。
実施例1および比較例1から内圧を40Paに変更し、周波数を10kHzに変更し、Duty比を20%に変更して、表16に示す条件で堆積膜を形成し、電子写真感光体を製造した。光導電層の堆積膜形成時のV1については、表17に示す条件とした。
下部注入阻止層、光導電層、上部注入阻止層および表面層の堆積膜形成時の周波数を60kHzに変更した以外は、実施例6と同様にして電子写真感光体を製造した。ただし、光導電層の堆積膜形成時のV1については、表19に示す条件とした。
実施例1および比較例1と同じプラズマCVD装置を用いて、実施例1とは直径が異なる円筒状基体(直径108mm、長さ358mm、厚さ5mmの鏡面加工を施したアルミニウム製の円筒状基体)上に表22に示す条件で堆積膜を形成し、電子写真感光体を製造した。
図5AおよびB(以下まとめて「図5」とも表記する。)に示すプラズマCVD装置を用いて、円筒状基体(直径84mm、長さ370mm、厚さ3mmの鏡面加工を施したアルミニウム製の円筒状基体)上に表25に示す条件で堆積膜を形成し、電子写真感光体を製造した。なお、下部注入阻止層、光導電層、上部注入阻止層および表面層の堆積膜形成時の円筒状基体の温度、膜厚および周波数に関しては、実施例1と同様にした。また、図5中、515Aはヒーター516と円筒状基体512(512A、512B)とを絶縁するための絶縁部材であり、515Bはヒーター516と支軸522とを絶縁するための絶縁部材である。また、517Aおよび517Bは基体ホルダー513Aおよび513Bの内側に接合している接合電極であり、518Aは上蓋520に取り付けられた絶縁板であり、518Bはベースプレート519に取り付けられた絶縁板である。また、519は接地されたベースプレートであり、520は接地された上蓋である。521は円筒状基体512(512A、512B)を所定の速度で回転させるためのモーターである。また、523は真空計であり、524は原料ガス流入バルブであり、525は原料ガス混合装置であり、526は反応容器511の排気口に連通された排気配管であり、527は排気メインバルブであり、528は真空ポンプである。制御部530は電源531の出力を制御するための制御部である。533Aおよび533Bは真空気密兼絶縁部材(真空気密兼絶縁セラミック)であり、535はガスブロックである。特記した点以外は、図2に示すプラズマCVD装置の各要素とそれぞれ同様の働きをする。
図6Aは、電極の電位をアース電位以外の電位で一定とし、電極の電位に対する円筒状基体の電位が交互に正と負になるように矩形波の交播電圧を電極と円筒状基体との間に印加した場合の円筒状基体の電位の変化を示す図である。図6A中の実線が円筒状基体の電位であり、図6A中の破線が電極の電位である。図6Bは、電極と円筒状基体の電位差の変化を示す図である。図6B中の破線が電極と円筒状基体の電位差である。放電開始電圧(負電位)および放電維持電圧(正電位)は、あらかじめ、それぞれの層の堆積膜を形成する際の反応容器内の圧力およびガス条件で、前述した方法により測定した値である。測定結果を表25に示す。
V2 放電開始電圧の絶対値以上の値
t1 電極と円筒状基体の電位差の絶対値がV1となっている時間(期間)
t2 電極と円筒状基体の電位差の絶対値がV2となっている時間(期間)
T 矩形波の周期
Claims (8)
- (i)内部に電極を有する減圧可能な反応容器の内部に、前記電極と離間させて円筒状基体を設置する工程と、
(ii)前記反応容器の内部に堆積膜形成用の原料ガスを導入する工程と、
(iii)前記電極および前記円筒状基体の一方の電位に対する他方の電位が交互に正と負になるように、周波数3kHz以上300kHz以下の矩形波の交播電圧を前記電極と前記円筒状基体との間に印加して、前記原料ガスを分解し、前記円筒状基体上に堆積膜を形成する工程と、
を有するプラズマCVD法によって電子写真感光体を製造する方法において、
前記正になるときの前記電極と前記円筒状基体の電位差の絶対値および前記負になるときの前記電極と前記円筒状基体の電位差の絶対値の一方が放電維持電圧の絶対値未満の値(V1)であって、他方が放電開始電圧の絶対値以上の値(V2)であることを特徴とする電子写真感光体の製造方法。 - 前記V1が、前記V2に対して20%以上の値である請求項1に記載の電子写真感光体の製造方法。
- 前記V1が、前記放電維持電圧の絶対値に対して95%以下の値である請求項1または2に記載の電子写真感光体の製造方法。
- 前記工程(iii)において、前記電極の電位が一定である請求項1~3のいずれか1項に記載の電子写真感光体の製造方法。
- 前記工程(iii)において、前記電極の電位がアース電位である請求項4に記載の電子写真感光体の製造方法。
- 前記矩形波が、周波数10kHz以上100kHz以下の矩形波である請求項1~5のいずれか1項に記載の電子写真感光体の製造方法。
- 前記原料ガスの少なくとも1種が水素化ケイ素ガスであり、前記堆積膜がアモルファス膜である請求項1~6のいずれか1項に記載の電子写真感光体の製造方法。
- 前記電極が、前記反応容器の内壁の少なくとも一部を構成している請求項1~7のいずれか1項に記載の電子写真感光体の製造方法。
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