JPH08179531A - Image forming method - Google Patents

Abstract

(57) [Summary] [Purpose] To suppress changes in surface potential and changes in pixel density due to changes in the surrounding environment. In an electrophotographic image forming method using an image forming process including a charging process, an exposing process, a developing process, and a cleaning process, a conductive support 101 and a hydrogen atom and / or a halogen atom having a silicon atom as a base are included. A photoreceptive member having a photoconductive layer having photoconductivity and formed of a non-single-crystal material,
Using the light receiving member 100 in which the temperature characteristic of the charging ability of the light receiving member is -2 V / deg or more and 2 V / deg or less,
The image forming step is performed. A heating step of heating the light receiving member is provided before the start of the image forming step.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron sensitive to electromagnetic waves such as light (light in a broad sense, which means ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). The present invention relates to an image forming method using a photographic light receiving member.

More specifically, the temperature dependence of electrophotographic characteristics,
The present invention relates to an image forming method capable of providing a high-quality image using a so-called electrophotographic light-receiving member whose temperature characteristics are controlled.

[0003]

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

Hydrogenated amorphous silicon (hereinafter referred to as "a-Si:") is used as a photoconductive material which exhibits excellent properties in this respect.
“H”), for example, Japanese Patent Publication No. 60-350
JP-A 59-59 describes application as a light receiving member for electrophotography.

In such a light-receiving member for electrophotography, generally, a conductive support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method is applied to the support. Thermal CVD method, optical CVD method, plasma CV
A photoconductive layer made of a-Si is formed by a film forming method such as D method. Among them, the plasma CVD method, that is, the method of decomposing the source gas by direct current or high frequency or microwave glow discharge to form the a-Si deposited film on the support is put to practical use as a suitable one.

Further, in JP-A-54-83746, a conductive support and a-Si containing a halogen atom as a constituent element (hereinafter referred to as "a-Si: X").
A light-receiving member for electrophotography, which comprises a photoconductive layer, has been proposed. In the publication, 1 halogen atom is added to a-Si.
By containing 40 to 40 atomic%, high heat resistance,
Good electrical conductivity as a photoconductive layer of a light-receiving member for electrophotography,
It is said that optical characteristics can be obtained.

Further, in Japanese Patent Laid-Open No. 57-115556, a photoconductive member having a photoconductive layer made of an a-Si deposited film is electrically connected to a photoconductive member such as dark resistance, photosensitivity and photoresponsiveness. In order to improve the use environment characteristics such as optical and photoconductive characteristics and moisture resistance, and further the stability over time, silicon atoms and carbon are formed on the photoconductive layer composed of an amorphous material with silicon atoms as a base material. A technique for providing a surface barrier layer composed of a non-photoconductive amorphous material containing atoms is described. Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique for a photoconductor having a translucent insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine, and is disclosed in Japanese Patent Laid-Open No. 16816
Japanese Unexamined Patent Publication (Kokai) No. 1 discloses a technique of using, as the surface layer, an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% hydrogen atoms as constituent elements.

Furthermore, in JP-A-57-158650, hydrogen containing 10 to 40 atomic%, 0.2 absorption coefficient ratio of the absorption peak of 2100 cm ^-1 and 2000 cm ^-1 in the infrared absorption spectrum It is described that by using a-Si: H of 1.7 in the photoconductive layer, an electrophotographic photoreceptor having high sensitivity and high resistance can be obtained.

In Japanese Patent Laid-Open No. 172649/1984, hydrogen atoms are contained in an amount of 20 to 30 atomic%, an optical band gap is 1.5 to 1.85 eV and a density is 2.0.
It is described that by using a-Si: H of g / cm ³ or more for the photoconductive layer, an electrophotographic photoreceptor having high charging ability and small dark decay can be obtained.

On the other hand, in JP-A-60-95551, in order to improve the image quality of an amorphous silicon photoconductor, charging, exposure, development and transfer are performed while maintaining the temperature in the vicinity of the photoconductor surface at 30 to 40 ° C. By performing the image forming process as described above, there is disclosed a technique for preventing a decrease in surface resistance due to the adsorption of moisture on the surface of the photoconductor and a resulting image deletion.

Further, in Japanese Patent Laid-Open No. 63-261380, no special auxiliary mechanism is required by rotating the light receiving member while keeping the cleaner in the operating state for a certain period after the electrophotographic apparatus is powered on. Japanese Patent Application Laid-Open No. 2004-242242 discloses a technique for removing foreign matter on the surface of a light receiving member to obtain a high quality image.

These techniques have improved the electrical, optical and photoconductive properties of the light-receiving member for electrophotography and the environmental characteristics of use, and the image quality has been improved accordingly.

[0013]

However, the conventional photoreceptive member for electrophotography having a photoconductive layer formed of an a-Si-based material has a drawback in that the electrical resistance of dark resistance, photosensitivity, photoresponsiveness, etc. Although individual improvements have been made in terms of optical and photoconductive characteristics and operating environment characteristics, as well as in terms of temporal stability and durability, they have been further improved in order to improve overall characteristics. The reality is that there is room for improvement.

In particular, the high image quality, high speed, and high durability of electrophotographic devices are rapidly advancing, and in the photoreceptive member for electrophotography, with further improvement of electrical characteristics and photoconductive characteristics,
It is required to significantly extend the performance under all environments while maintaining the charging ability and sensitivity.

In order to improve the image characteristics of the electrophotographic apparatus, the optical exposure apparatus, the developing apparatus, the transfer apparatus, etc. in the electrophotographic apparatus have been improved. It has become necessary to improve.

Further, the space saving of the electrophotographic apparatus is advancing year by year, and therefore the light receiving member itself tends to be miniaturized and the diameter thereof should be reduced, and a drum heater for temperature control should be built in the light receiving member. Is getting difficult. Also, in order to save power, there is a trend toward omitting heaters and the like as much as possible.

Under such circumstances, although the above-mentioned prior art has made it possible to improve the characteristics to some extent with respect to the above problems, it cannot be said that the chargeability and the image quality are further improved. In particular, as a subject for improving the image quality of an electrophotographic apparatus using an amorphous silicon type light receiving member, it has been further required to reduce the variation of electrophotographic characteristics due to the change of ambient temperature.

For example, in order to prevent image deletion on the light receiving member, a surface temperature of the light receiving member is set by installing a drum heater in the copying machine as described in JP-A-60-95551. Was maintained at about 40 ° C. However, in the conventional light receiving member, the temperature dependency of the charging ability due to the generation of pre-exposed carriers and thermally excited carriers, that is, the so-called temperature characteristic is about 4 V / deg or more, and under the actual use environment in the copying machine, Inevitably, the receiving member had to be used in a state where the charging ability was lower than it originally had. In addition, conventionally, since the electrophotographic characteristics greatly change with respect to the temperature of the light receiving member, it is necessary to increase the accuracy of temperature control of the light receiving member, and the temperature adjusting means for that has to be expensive. It was

Further, conventionally, even when the copying machine is not used at night, the drum heater is energized to generate an image flow caused by the ozone product generated by the corona discharge of the charger being adsorbed on the surface of the light receiving member at night. I was trying to prevent it. However, nowadays, in order to save resources and power, the night-time energization of the copying machine is not performed as much as possible.
When copying is started in such a state, the ambient temperature of the light receiving member in the copying machine gradually rises, and accordingly, the charging ability lowers, causing a problem that the image density changes during copying.

On the other hand, image deletion due to ozone products and water adsorbed on the surface of the light receiving member at night is disclosed in Japanese Patent Laid-Open No. 63-26.
As described in Japanese Patent No. 1380, it is suppressed by rotating the light receiving member while keeping the cleaner in the operating state for a certain time after the electrophotographic apparatus is powered on, or by providing the heating step before the start of the image forming step. To obtain, it is not always necessary to constantly heat with a drum heater at rest. Further, once the image forming process is started, the temperature in the copying machine rises to the extent that image deletion does not occur, especially during continuous copying, so there is little need to install a drum heater.

Therefore, when designing the electrophotographic light-receiving member, the layer structure of the electrophotographic light-receiving member and the chemical composition of each layer should be taken into consideration in order to solve the above problems. It is necessary to improve the image forming method and to reduce the cost and power consumption of the image forming method.

(Purpose of the Invention) The present invention is based on the above a.
It is an object of the present invention to solve various problems in an image forming method using a light-receiving member for electrophotography having a conventional light-receiving layer composed of -Si. That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially always stable with little dependence on the use environment,
Provides an image forming method using a light-receiving member for electrophotography, which has excellent light fatigue resistance, does not cause a deterioration phenomenon during repeated use, has excellent durability and moisture resistance, has almost no residual potential observed, and has good image quality. To do.

In particular, in the present invention, a light receiving member having a photoconductive layer composed of a-Si, which has a temperature characteristic remarkably reduced as compared with the conventional one, is used, and the fluctuation of the potential characteristic and the image with respect to the change of the surrounding environment. An object of the present invention is to provide an image forming method in which fluctuations in density are suppressed and which has extremely excellent electric characteristics and image characteristics in a wide temperature range.

Further, a heating means for removing water and ozone products adhering to the surface of the light receiving member during the rest of the image forming apparatus is provided, and the influence on the image characteristics is substantially negligible. An object is to provide an image forming method.

Further, since the conventionally required drum heater can be omitted, the temperature control accuracy of the drum heater can be lowered, or the heating by the drum heater during the rest can be omitted, a large power saving and a low cost design can be realized. An image forming method is provided.

[0026]

In order to solve the above problems, the present inventors have paid attention to the behavior of carriers in the photoconductive layer, and have found that the localized state distribution in the band gap and the temperature dependence of the chargeability are dependent on each other. As a result of diligent studies on the relationship with the property, it was found that the above object can be achieved by using a light-receiving member in which the localized state distribution is controlled within a certain range in at least the light incident portion of the photoconductive layer. That is, in a light-receiving member having a photoconductive layer composed of a non-single-crystal material containing a silicon atom as a base and containing a hydrogen atom and / or a halogen atom, it is designed and created to specify its layer structure. The light-receiving member not only exhibits remarkably excellent characteristics in practical use, but also surpasses in all respects compared with the conventional light-receiving member, in particular, it has excellent characteristics as a light-receiving member for electrophotography. I found that I had it. In the image forming method using the light receiving member, the conventionally required drum heater can be omitted, the temperature control accuracy of the drum heater can be lowered, or the heating by the drum heater at rest can be omitted. We have found that significant power savings and low cost designs are possible.

The image forming method of the present invention comprises a conductive support and a photoconductive layer having photoconductivity which is composed of a non-single crystal material containing silicon atoms as a matrix and containing hydrogen atoms and / or halogen atoms. A light receiving member having a light receiving layer, wherein the temperature characteristic of charging ability of the light receiving member is -2V.
/ Deg or more and 2V / deg or less is used, and the temperature in the vicinity of the light receiving member is 0 to
The image forming step is performed in the range of 50 ° C.

Further, the image forming method of the present invention comprises a conductive support and a photoconductive layer having photoconductivity which is composed of a non-single crystal material containing silicon atoms as a matrix and containing hydrogen atoms and / or halogen atoms. And an image forming step using a light receiving member having a light receiving layer having the temperature characteristic of charging ability of −2 V / deg or more and 2 V / deg or less,
A heating step of heating the light receiving member is provided before the start of the image forming step, and further, the image forming step is performed at a temperature in the vicinity of the light receiving member of 0 to 50 ° C.

In general, within the band gap of a-Si: H, there are tail positions due to structural disorder of Si-Si bonds, and dangling bonds of Si. There are deep depressions due to structural defects. It is known that these steps act as traps for electrons and holes and as a recombination center to cause deterioration of device characteristics.

As a method for measuring the state of localized gradients in such a band gap, generally, deep gradient spectroscopy, isothermal capacitance transient spectroscopy, photothermal deflection spectroscopy, photoacoustic spectroscopy, constant photocurrent method, etc. Is used. Among them, the constant photocurrent method [C
instant Photocurrent Meth
od: hereinafter abbreviated as “CPM”] is a-Si: H
It is useful as a method for easily measuring the subgap optical absorption spectrum based on the localized tilt position of.

The present inventors have found that the characteristic energy of an exponential tail (Urback tail) (hereinafter abbreviated as "Eu") and the localized density of states (determined from the subband gap optical absorption spectrum measured by CPM) ( Below, "D
As a result of investigating the correlation between the "OS") and the characteristics of the photoconductor over various conditions, it was found that Eu and DOS are closely related to the temperature characteristics of the a-Si photoconductor.

The reason why the charging ability is lowered when the photosensitive member is heated by a drum heater or the like is that the thermally excited carriers are attracted to the electric field at the time of charging, and the localized tail position of the band hem or the deep local position in the band gap. It is possible that the surface charge is canceled by traveling to the surface while repeatedly capturing and releasing to the sitting position. At this time, the carriers that have reached the surface while passing through the charger have almost no effect on the decrease in charging ability, but the carriers that are captured in a deep descent position reach the surface after passing through the charger. It is observed as a temperature characteristic to cancel the surface charge. In addition, carriers that are thermally excited after passing through the charger also cancel the surface charge and cause a decrease in charging ability. Therefore, in order to improve the temperature characteristics, it is necessary to suppress the generation of thermally excited carriers in the operating temperature range of the photoconductor and to improve the traveling property of the carriers.

Therefore, as in the present invention, Eu, DOS
By controlling, the generation of thermally excited carriers can be suppressed, and the rate at which thermally excited carriers and photocarriers are trapped in the localized plateau can be reduced, so that the mobility of carriers is significantly improved. As a result, the temperature characteristics of the photoconductor in the operating temperature range are dramatically improved, the stability of the photoreceptive member in the operating environment is improved, and halftones are clearly visible and high-quality images with high resolution are displayed around It can be obtained stably regardless of temperature.

Therefore, according to the image forming method of the present invention having the above-mentioned constitution, all of the above-mentioned problems can be solved, and extremely excellent electric, optical and photoconductive properties can be obtained. The characteristics, image quality, durability and environmental characteristics of use are shown.

(Embodiment Example) An electrophotographic light-receiving member and an image forming apparatus according to the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic structural view for explaining the layer structure of the electrophotographic light-receiving member according to the present invention. In the electrophotographic light-receiving member 100 shown in FIG. 1A, a light-receiving layer 102 is provided on a support 101 for the light-receiving member. The light receiving layer 102 is a-Si: H, X.
And a photoconductive layer 103 having photoconductivity.

FIG. 1B is a schematic structural view for explaining another layer structure of the electrophotographic light-receiving member according to the present invention. Electrophotographic photoreceptive member 100 shown in FIG.
Is provided with a light receiving layer 102 on a support 101 for a light receiving member. The light receiving layer 102 is aS
i: a photoconductive layer 103 composed of H and X and having photoconductivity
And an amorphous silicon-based surface layer 104.

FIG. 1 (c) is a schematic structural view for explaining another layer structure of the electrophotographic light-receiving member according to the present invention. Electrophotographic photoreceptive member 100 shown in FIG.
Is provided with a light receiving layer 102 on a support 101 for a light receiving member. The light receiving layer 102 is aS
i: a photoconductive layer 103 composed of H and X and having photoconductivity
And an amorphous silicon-based surface layer 104 and an amorphous silicon-based charge injection blocking layer 105.

FIG. 1D is a schematic constitutional view for explaining still another layer constitution of the electrophotographic light-receiving member according to the present invention. An electrophotographic light-receiving member 100 shown in FIG. 1D is formed on a support 101 for a light-receiving member,
A light receiving layer 102 is provided. The light-receiving layer 102 is composed of a charge-generating layer 106 and charge-transporting layer 107 made of a-Si: H, X, which constitutes the photoconductive layer 103, and an amorphous silicon-based surface layer 104.

(Support) The support used in the electrophotographic light-receiving member of the present invention may be either electrically conductive or electrically insulating. As the conductive support, A
1, Cr, Mo, Au, In, Nb, Te, V, Ti,
Examples include metals such as Pt, Pd, Fe, and alloys thereof, such as stainless steel. In addition, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene,
It is also possible to use a support in which the surface of at least the light-receiving layer-forming side of an electrically insulating support such as a film or sheet of a synthetic resin such as polyamide, glass, or ceramics is subjected to a conductive treatment.

The shape of the support 101 can be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness of the support 101 is as desired.
0 is formed appropriately, but when flexibility as the electrophotographic light-receiving member 100 is required, it is made as thin as possible within a range in which the function as the support 101 can be sufficiently exerted. be able to. However, the support 1
01 is usually 10 μm or more in view of manufacturing and handling, mechanical strength and the like.

In particular, when image recording is carried out using coherent light such as laser light, the surface of the support 101 is used in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. You may provide unevenness in.
The unevenness provided on the surface of the support 101 is described in JP-A-60-
168156, 60-178457, 60-225854 and the like, which are known methods.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the support 101 is provided with a concavo-convex shape by a plurality of spherical trace dents. It may be provided. That is, the support 1
The surface of No. 01 has unevenness smaller than the resolving power required for the electrophotographic light-receiving member 100, and the unevenness is due to a plurality of spherical trace depressions. The unevenness due to a plurality of spherical trace depressions provided on the surface of the support 101 is formed by a known method described in JP-A-61-231561.

(Photoconductive Layer) In the light receiving member for electrophotography according to the present invention, it is formed on the support 101 and constitutes a part of the light receiving layer 102 in order to effectively achieve its purpose. The photoconductive layer 103 is formed by the vacuum deposition film forming method.
The numerical conditions of the film forming parameters are appropriately set so that desired characteristics can be obtained. Specifically, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, alternating-current discharge CVD method such as microwave CVD method, or direct-current discharge CVD method), sputtering method, vacuum deposition method, ion plating method, It can be formed by various thin film deposition methods such as a photo CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be prepared. The glow discharge method, particularly the high frequency glow discharge method using a power supply frequency in the RF band or the VHF band, is preferable because it is relatively easy to control the conditions for manufacturing the electrophotographic light-receiving member having the characteristics.

To form the photoconductive layer 103 by the glow discharge method, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a gas for supplying H, which can supply hydrogen atoms (H). Of the raw material gas and / or the raw material gas for supplying X, which can supply the halogen atom (X), is introduced in a desired gas state into a reaction vessel in which the inside can be decompressed, and a glow discharge is generated in the reaction vessel. Then, a-Si: is formed on a predetermined support 101 which is installed at a predetermined position in advance.
A layer made of H and X may be formed.

Further, in the electrophotographic light-receiving member according to the present invention, the photoconductive layer 103 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality. This is because it is required in order to improve the photoconductive property, especially the photoconductivity and the charge retention property.
Therefore, the content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. Is desirable.

The substances that can be used as the Si supply gas include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si _4.
Silicon hydrides (silanes) in a gas state such as H ₁₀ or capable of being gasified are mentioned as being effectively used,
Further, SiH ₄ and Si ₂ H ₆ are preferable as they are easy to handle when forming a layer and have good Si supply efficiency.

Then, hydrogen atoms are structurally introduced into the photoconductive layer 103 to be formed so that the introduction ratio of hydrogen atoms can be controlled more easily to obtain film characteristics that achieve the object of the present invention. Therefore, it is necessary to further mix these gases with a desired amount of H ₂ and / or He or a silicon compound gas containing a hydrogen atom to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

Further, effective source gases for supplying halogen atoms are, for example, halogen gas, halides,
Gaseous or gasifiable halogen compounds such as halogen-containing interhalogen compounds and halogen-substituted silane derivatives are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound which can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, ClF and C.
_{lF 3, BrF 3, BrF 5} , may be mentioned IF _3, IF ₇ or the like interhalogen compounds of. Specific examples of the silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom include SiF ₄ and S.
Silicon fluoride such as i ₂ F ₆ can be mentioned as a preferable example.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 103, for example, the temperature of the support 101, the raw material used for containing hydrogen atoms and / or halogen atoms. The amount of the substance introduced into the reaction container, the discharge power, etc. may be controlled.

In the photoreceptive member for electrophotography according to the present invention, it is preferable that the photoconductive layer 103 contains an atom for controlling conductivity, if necessary. Atoms that control conductivity may be contained in the photoconductive layer 103 in a uniformly distributed state, or may be contained in a nonuniformly distributed state in the layer thickness direction. Good.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field,
Atoms belonging to Group IIIb of the periodic table giving p-type conduction characteristics (hereinafter abbreviated as “Group IIIb atoms”) or atoms belonging to Group Vb of the periodic table giving n-type conduction characteristics (hereinafter “Group Vb atoms”). It is abbreviated as ")" can be used.

Specific examples of the group IIIb atom are:
Boron (B), Aluminum (Al), Gallium (G
a), indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Specific examples of the Vb group atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, and particularly P and As.
Is preferred.

Control the conductivity contained in the photoconductive layer 103
The content of atoms contained is preferably 1 × 10^-2~ 1
× 10³Atomic ppm, more preferably 5 × 10^-2~ 5x
10 ²Atomic ppm, optimally 1 x 10^-1~ 1 × 10²original
It is desirable that the content be ppm.

Atoms that control conductivity, eg, III
To structurally introduce a group b atom or a group Vb atom, a raw material for introducing a group IIIb atom or a raw material for introducing a group Vb atom in a gas state is introduced into a reaction vessel during layer formation. It may be introduced together with another gas for forming the photoconductive layer 103. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified under at least a layer forming condition is adopted. Is desirable.

Raw materials for introducing such group IIIb atoms
Specifically, as a substance, for introducing a boron atom, B is used.₂
H₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆
H₁₂, B₆H₁₄Borohydride, BF, etc.₃, BCl₃, B
Br₃And the like. Besides this, A
lCl₃, GaCl₃, Ga (CH₃)₃, InC
l ₃, TlCl₃Etc. can also be mentioned.

Effectively used as a raw material for introducing a group Vb atom is PH ₃ , P for introducing a phosphorus atom.
Phosphorus hydride such as ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC
Examples thereof include phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF
₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group Vb atom.

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

Further, the photoconductive layer 103 contains carbon atoms and / or
Alternatively, it is also effective to contain an oxygen atom and / or a nitrogen atom. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms.
10 atomic%, more preferably 1 × 10 ⁻⁴ to 8 atomic%, optimally 1 × 10 ^{−3 to} 5 atomic%. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer, or may be non-uniformly distributed so that the content varies in the layer thickness direction of the photoconductive layer. There may be a part that has.

The layer thickness of the photoconductive layer 103 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 20 to 50 μm, more preferably 23 to 45 μm, and most preferably. Is preferably 25 to 40 μm. When the layer thickness is less than 20 μm,
Electrophotographic characteristics such as charging ability and sensitivity become practically insufficient,
When the thickness is more than 50 μm, the production time of the photoconductive layer becomes long and the production cost becomes high.

In order to achieve the object of the present invention and form the photoconductive layer 103 having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and It is necessary to set the support temperature appropriately.

The flow rate of H ₂ and / or He used as the diluent gas is appropriately selected in accordance with the layer design, but H ₂ and / or He is usually added to the Si supply gas in the range of 3 to 5. 20 times, preferably 4 to 15
It is desirable to control in the range of double, optimally 5 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, and an optimum range is selected.
0 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr
r, optimally 1 × 10 ^{−3 to} 1 Torr is preferable.

Similarly, the discharge power is appropriately selected in the optimum range according to the layer design, but the ratio of the discharge power to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 to. It is desirable to set the range of 6 times, optimally 3 to 5 times.

Further, the temperature of the support 101 is appropriately selected according to the layer design, but in the usual case, it is 2
It is desirable that the temperature is 00 to 350 ° C, preferably 230 to 330 ° C, and most preferably 250 to 310 ° C.

In the electrophotographic light-receiving member according to the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature and gas pressure of the support for forming the photoconductive layer, but the conditions are usually independent. It is not individually determined, but it is desirable to determine an optimum value based on mutual and organic relationships so as to form a light receiving member having desired characteristics.

(Surface Layer) In the electrophotographic light-receiving member of the present invention, an amorphous silicon-based surface layer 104 is further formed on the photoconductive layer 103 formed on the support 101 as described above. It is preferably formed. This surface layer 104 has a free surface 106, which is mainly moisture resistant,
Continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics,
It is provided to achieve the object of the present invention in durability.

Further, since each of the amorphous materials forming the photoconductive layer 103 and the surface layer 104 constituting the light receiving layer 102 has a common constituent element of silicon atom,
Chemical stability is sufficiently ensured at the stacking interface.

The surface layer 104 can be made of any material as long as it is an amorphous silicon type material. For example, the surface layer 104 contains hydrogen atoms (H) and / or halogen atoms (X), and further contains carbon atoms. Amorphous silicon (hereinafter referred to as "a-SiC: H, X"), hydrogen atom (H) and / or halogen atom (X), and further amorphous silicon containing oxygen atom (hereinafter referred to as "a-
SiO: H, X "), hydrogen atom (H) and /
Alternatively, amorphous silicon containing a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-SiN: H,
X "), a hydrogen atom (H) and / or a halogen atom (X), and further contains at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as" a-SiCON: H "). , X ”) and the like are preferably used.

In order to effectively achieve the object of the present invention,
The surface layer 104 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, a glow discharge method (low frequency CVD method, high frequency CVD method or microwave C
AC discharge CVD method such as VD method, or DC discharge CVD method
Method), a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, a thermal CVD method, and various thin film deposition methods. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light receiving member to be produced. It is preferable to use the same deposition method as that for the photoconductive layer in terms of productivity of the member.

For example, a-Si is formed by the glow discharge method.
In order to form the surface layer 104 of C: H, X, basically, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying C that can supply carbon atoms (C) are used. A raw material gas and a raw material gas for supplying H, which can supply hydrogen atoms (H), and / or a raw material gas for supplying X, which can supply halogen atoms (X), are placed in a desired reactor in a reaction vessel. A-SiC: X, Y is introduced on the support 101 on which the photoconductive layer 103 formed in advance is introduced by introducing in a gas state to cause glow discharge in the reaction vessel.
It is sufficient to form a layer consisting of.

The material of the surface layer may be any amorphous material containing silicon, such as carbon, nitrogen,
A compound with a silicon atom containing at least one element selected from oxygen is preferable, and a compound containing a-SiC as a main component is particularly preferable.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.

Further, in the surface layer 104, hydrogen atoms or /
And it is necessary that halogen atoms are contained, which compensates dangling bonds of silicon atoms and improves the layer quality.
In particular, it is indispensable for improving the photoconductive property and the charge retention property. The hydrogen content is usually 30 to 70 atom%, preferably 35 to 70 atom% with respect to the total amount of the constituent atoms.
It is desirable that the content is 65 atom%, and optimally 40 to 60 atom%. Further, the content of fluorine atoms is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.

The light receiving member formed within the range of the hydrogen and / or fluorine content can be sufficiently applied as a remarkably excellent one which has not been heretofore in practical use. That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as the electrophotographic light-receiving member. For example, the deterioration of the charging characteristics due to the injection of electric charges from the free surface, the fluctuation of the charging characteristics due to the change of the surface structure under the usage environment, for example, high humidity. This adverse effect is caused by the injection of charges and the trapping of the charges in the defects in the surface layer, resulting in the occurrence of an afterimage phenomenon during repeated use.

However, if the hydrogen content in the surface layer is 30
By controlling the content to be atomic% or more, the defects in the surface layer are significantly reduced, and as a result, the electrical characteristics and the high-speed continuous usability can be dramatically improved as compared with the conventional one.

On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer is lowered, and it cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer to be within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are remarkably excellent. The hydrogen content in the surface layer can be controlled by the flow rate (ratio) of the raw material gas, the support temperature, the discharge power, the gas pressure and the like.

Further, by controlling the fluorine content in the surface layer to be in the range of 0.01 atomic% or more, it is possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Become. Further, as a function of fluorine atoms in the surface layer, it is possible to effectively prevent the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona.

On the other hand, the fluorine content in the surface layer is 15 atom%.
When it exceeds, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breakage of the bond between the silicon atom and the carbon atom due to damage such as corona are hardly recognized. Further, since excess fluorine atoms impede the mobility of carriers in the surface layer, the residual potential and image memory are noticeable. Therefore, controlling the fluorine content in the surface layer within the above range is one of the important factors in obtaining desired electrophotographic characteristics. The fluorine content in the surface layer is the same as the hydrogen content in the flow rate (ratio) of the source gas,
It can be controlled by the support temperature, discharge power, gas pressure and the like.

Silicon used in forming the surface layer
(Si) As a substance that can be a supply gas, Si
H_Four, Si₂H₆, Si₃H₈, Si_FourH_TenGaseous, etc.
Silicon hydrides (silanes) that are
It is listed as a material that is used for the effect of the
SiH is easy to handle and has good Si supply efficiency._Four, S
i ₂H₆Are preferred. Also this
If necessary, the raw material gas for supplying Si may be H₂, He,
It may be diluted with a gas such as Ar or Ne before use.

As a substance which can be a gas for supplying carbon,
CH _4, the _{C 2 H 2, C 2 H} 6, C 3 H 8, C 4 gaseous state of H ₁₀ and the like, or a hydrocarbon which can be gasified are exemplified as being effectively used, further layers when creating CH ₄ , C ₂ H ₂ and C are easy to handle and have good Si supply efficiency.
₂ H ₆ is mentioned as a preferable one. In addition, these raw material gases for supplying C may be added with H ₂ , He and A as needed.
It may be diluted with a gas such as r or Ne before use.

Examples of substances that can be used as a gas for supplying nitrogen or oxygen include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ and C.
Compounds in a gas state such as O, CO ₂ and N ₂ or compounds that can be gasified are mentioned as being effectively used. Further, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

Further, in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 104 to be formed, hydrogen gas or a silicon compound gas containing hydrogen atoms is added to these gases. It is also preferable to mix a desired amount to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

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

To control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 104, for example, the temperature of the support 101, the raw material used for containing hydrogen atoms and / or halogen atoms The amount to be introduced into the reaction container, the discharge power, and the like may be controlled.

The carbon atom and / or the oxygen atom and / or the nitrogen atom may be uniformly contained in the surface layer, or may be nonuniform such that the content varies in the layer thickness direction of the surface layer. There may be a portion with a distribution.

Further, it is preferable that the surface layer 104 contains atoms for controlling the conductivity, if necessary. Atoms that control conductivity may be contained in the surface layer 104 in a state where they are evenly distributed, or even in a portion where they are contained in an uneven distribution in the layer thickness direction. Good.

As the atom for controlling the conductivity, a so-called impurity in the field of semiconductors can be mentioned, and an atom belonging to Group IIIb of the periodic table (hereinafter referred to as “Group IIIb atom”) which gives a p-type conduction characteristic. Or an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that imparts n-type conductivity can be used.

Specific examples of the group IIIb atom are:
Boron (B), Aluminum (Al), Gallium (G
a), indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Specific examples of the Vb group atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, and particularly P and As.
Is preferred.

The conductivity contained in the surface layer 104 is controlled.
The content of atoms is preferably 1 × 10^-3~ 1x
10³Atomic ppm, more preferably 1 × 10^-2~ 5 x 1
0²Atomic ppm, optimally 1 x 10^-1~ 1 × 10²atom
It is desirable to set it to ppm. Atoms that control conductivity,
For example, a group IIIb atom or a group Vb atom may be used.
To introduce artificially, a group IIIb atom must be added during layer formation.
Raw material for introduction or raw material for introduction of Group Vb atom
Forming a surface layer 104 in a reaction container in a gas state with a quality
It may be introduced together with other gas for. No. III
Raw material for introducing group b atoms or for introducing group Vb atoms
The material that can be used as a raw material is
Or can be easily gasified under at least layering conditions
It is desirable that one is adopted. Such a III
As a raw material for introducing a group b atom, specifically, a boron atom
For introduction, B₂H₆, B_FourH_Ten, B_FiveH₉, B_Five
H ₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Boron hydride, such as
BF₃, BCl₃, BBr ₃Such as boron halides
You can In addition, AlCl₃, GaCl₃, Ga (C
H₃)₃, InCl₃, TlCl₃And so on.
Wear.

As a raw material for introducing a group Vb atom,
For the purpose of introducing phosphorus atoms, PH is effectively used.₃,
P₂H_FourPhosphorus hydride, PH, etc._FourI, PF₃, PF_Five, P
Cl ₃, PCl_Five, PBr₃, PBr_Five, PI₃Etc.
Phosphorus phosphide can be mentioned. Besides this, AsH₃, As
F₃, AsCl₃, AsBr₃, AsF_Five, SbH₃,
SbF₃, SbF_Five, SbCl₃, SbCl_Five, BiH
₃, BiCl₃, BiBr ₃Etc. for introducing a Group Vb atom
It can be mentioned as a valid starting material.

Further, these raw materials for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

The thickness of the surface layer 104 is usually 0.0
1 to 3 μm, preferably 0.05 to 2 μm, most preferably 0.
It is desirable that the thickness is 1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion or the like during use of the light receiving member, and if it exceeds 3 μm, the electrophotographic characteristics such as increase in residual potential are deteriorated.

The surface layer 104 is carefully formed to provide the desired properties as desired. That is,
A substance having Si, C and / or N and / or O, H and / or X as a structural element may have a structure from crystalline to amorphous depending on its forming condition, and may have electrical property from conductivity to semiconductor. Properties and properties between insulating properties and photoconductive properties to non-photoconductive properties, respectively, so that a compound having desired properties depending on the purpose is formed, The choice of forming conditions is made strictly as desired.

For example, in order to provide the surface layer 104 mainly for the purpose of improving the pressure resistance, the surface layer 104 is formed as a non-single-crystal material having a remarkable electric insulating behavior in the use environment.

Further, when the surface layer 104 is provided mainly for the purpose of improving the continuous repeated use characteristics and the use environment characteristics, the above-mentioned degree of electrical insulation is relaxed to some extent.
It is formed as a non-single crystal material that has some sensitivity to the light it illuminates.

In order to form the surface layer 104 having the characteristics capable of achieving the object of the present invention, it is necessary to properly set the temperature of the support 101 and the gas pressure in the reaction vessel as desired.

The optimum temperature range (Ts) of the support 101 is selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable that the temperature is 330 ° C., optimally 250 to 310 ° C.

The gas pressure in the reaction vessel was also designed to be a layer.
Therefore, the optimum range is appropriately selected, but in the normal case, it is preferable.
It is 1 × 10^-Four10 Torr, more preferably 5 ×
10 ^-Four~ 5 Torr, optimally 1 x 10^-3~ 1 Torr
Is preferred.

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

Further, by providing a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms and nitrogen atoms is smaller than that of the surface layer between the photoconductive layer and the surface layer, characteristics such as charging ability can be further improved. It is effective for improving.

Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer 103 may be provided between the surface layer 104 and the photoconductive layer 103. good. This can improve the adhesion between the surface layer and the photoconductive layer, and further reduce the influence of interference due to the reflection of light at the interface. (Charge Injection Blocking Layer) In the electrophotographic light-receiving member according to the present invention, a charge injection blocking layer having a function of blocking injection of charges from the conductive support side between the conductive support and the photoconductive layer. It is even more effective to provide layers. That is, the charge injection blocking layer has a function of blocking the injection of charges from the support side to the photoconductive layer side when the photoreceptive layer receives a charge treatment of a constant polarity on its free surface. Such a function will not be exhibited when subjected to the charging treatment of
It has so-called polarity dependence. In order to impart such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.

The conductivity-controlling atoms contained in the layer may be evenly distributed in the layer, or they may be distributed evenly in the layer thickness direction. There may be a portion that contains it in a uniformly distributed state. When the distribution concentration is non-uniform, it is preferable that the content is so distributed as to be distributed more on the support side.

However, in any case, it is necessary that the particles are uniformly distributed in the in-plane direction parallel to the surface of the support in order to make the characteristics uniform in the in-plane direction. .

The atoms contained in the charge injection blocking layer for controlling the conductivity include so-called impurities in the field of semiconductors, and the atoms belonging to Group IIIb of the periodic table (hereinafter referred to as “III”) which give p-type conduction characteristics. Group IIIb atom "
Abbreviated) or the periodic table V which gives n-type conduction characteristics
Atoms belonging to group b (hereinafter abbreviated as "Vb group atoms")
Can be used.

Specific examples of the group IIIb atom are:
There are B (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), etc., and B, Al, and Ga are particularly preferable. Specific examples of the group Vb atom include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth), etc., especially P,
As is preferred.

The content of atoms for controlling the conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved.
Preferably 10 to 1 × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm, most preferably 1 × 10 ^{2 to} 3
It is desirable that the concentration be × 10 ³ atomic ppm.

Further, in the charge injection blocking layer, carbon atoms,
By containing at least one of a nitrogen atom and an oxygen atom, it is possible to further improve the adhesion with another layer provided in direct contact with the charge injection blocking layer.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be evenly distributed in the layer or may be contained evenly in the layer thickness direction. There may be a portion containing the non-uniformly distributed state. However, in any case, it is necessary that the content be evenly distributed in the in-plane direction parallel to the surface of the support in order to obtain uniform properties in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer is appropriately determined so that the object of the present invention can be effectively achieved. In the case of one kind, as the amount thereof, in the case of two or more kinds, as the sum thereof, preferably 1 × 10 ⁻³ to 50
Atomic%, more preferably 5 × 10 ⁻³ to 30 at%, optimally 1 × 10 ⁻² to 10 at%.

Further, hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer compensate for dangling bonds existing in the layer and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1 to 50 atom%,
It is more preferably 5 to 40 atom%, and most preferably 10 to 30 atom%.

The layer thickness of the charge injection blocking layer is preferably 0.1 to 5 μm, more preferably 0.3 to 4 μm, and most preferably 0 from the viewpoint of obtaining desired electrophotographic characteristics and economical effects. It is desirable to be set to 0.5 to 3 μm. When the layer thickness is less than 0.1 μm, the ability to prevent injection of charges from the support becomes insufficient, and sufficient charging ability cannot be obtained,
Even if the thickness is more than 5 μm, the electrophotographic characteristics are not improved, and the production cost is increased due to the extension of the production time.

To form the charge injection blocking layer, a vacuum deposition method similar to the method for forming the photoconductive layer described above is adopted.

To form the charge injection blocking layer 105, similarly to the photoconductive layer 103, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the temperature of the support 101. Need to be set appropriately.

The flow rate of the diluting gas H ₂ and / or He is appropriately selected in accordance with the layer design, but H ₂ and / or He is added to the Si supply gas.
In the usual case, it is desirable to control in the range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the usual case, it is 1 × 1.
0 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr
r, optimally 1 × 10 ^{−3 to} 1 Torr is preferable.

Similarly, the discharge power is appropriately selected in accordance with the layer design, but the ratio of the discharge power to the flow rate of the gas for supplying Si is usually 1 to 7, preferably 2 to 6, It is desirable to set in the range of 3 to 5.

Further, the temperature of the support 101 is appropriately selected in accordance with the layer design, but in the usual case, it is 2
It is desirable that the temperature is 00 to 350 ° C, preferably 230 to 330 ° C, and most preferably 250 to 310 ° C.

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

In addition, in the electrophotographic light-receiving member according to the present invention, the support 10 of the light-receiving layer 102 is used.
On one side, at least aluminum atoms, silicon atoms,
It is desirable to have a layer region containing hydrogen atoms and / or halogen atoms in a non-uniform distribution state in the layer thickness direction.

For the purpose of further improving the adhesion between the support 101 and the photoconductive layer 103 or the charge injection blocking layer 105, for example, Si ₃ N ₄ , SiO ₂ , Si
O or silicon atom as a base, hydrogen atom and /
Alternatively, an adhesion layer formed of an amorphous material containing a halogen atom and a carbon atom and / or an oxygen atom and / or a nitrogen atom may be provided. Further, a light absorption layer may be provided to prevent the occurrence of an interference pattern due to the reflected light from the support.

Next, the apparatus and film forming method for forming the light receiving layer of the light receiving member for electrophotography according to the present invention will be described in detail.

FIG. 2 is a schematic diagram showing an example of an apparatus for manufacturing an electrophotographic light-receiving member by a high frequency plasma CVD method (hereinafter abbreviated as "RF-PCVD") using a frequency in the RF band. The structure of the manufacturing apparatus shown in FIG. 2 is as follows.

This apparatus is roughly classified into a deposition apparatus (210
0), a source gas supply device (2200), a reaction vessel (2)
111) is composed of an exhaust device (not shown) for reducing the pressure. A cylindrical support (2112), a support heating heater (2113), a source gas introduction pipe (211) are provided in a reaction vessel (2111) in the deposition apparatus (2100).
4) is installed, and a high frequency matching box (21
15) is connected.

The source gas supply device (2200) is made of SiH.
₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other source gas cylinders (2212-1226) and valves (22)
31-2236, 2241-2246, 2251-22
56) and a mass flow controller (2211-2)
216), and the cylinder of each source gas is connected to the gas introduction pipe (2114) in the reaction vessel (2111) via the valve (2260).

The deposited film can be formed using this apparatus, for example, as follows.

First, a cylindrical support (2112) is installed in the reaction vessel (2111), and the inside of the reaction vessel (2111) is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the cylindrical support (2112) is raised to 200 ° C. to 350 ° C. by the heater (2113) for heating the support.
Control to a predetermined temperature of ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel (21
11), the gas cylinder valve (223
1 to 2236), a leak valve (2117) of the reaction container
Make sure that the inlet valve (22
41 to 2246), the outflow valve (2251 to 225)
6) After confirming that the auxiliary valve (2260) is open, first, the main valve (2118) is opened to exhaust the reaction vessel (2111) and the gas pipe (2116).

Next, the reading of the vacuum gauge (2119) is about 5 × 1.
Auxiliary valve (2260) at 0 ^-6 Torr,
Close the outflow valves (2251-2256).

After that, the gas cylinders (2221-222)
From (6), each gas is introduced by opening the valves (2231-2236), and the pressure of each gas is adjusted to ² kg / cm ² by the pressure adjuster (2261-2266). Next, the inflow valves (2241-2246) are gradually opened to introduce the respective gases into the mass flow controllers (2211-2216).

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

When the cylindrical support (2112) reaches a predetermined temperature, necessary ones of the outflow valves (2251 to 2256) and the auxiliary valve (2260) are gradually opened, and the gas cylinders (2211 to 2226) are connected to predetermined positions. Of the gas of the reaction vessel (211) via the gas introduction pipe (2114)
1) Introduce. Next, the mass flow controller (2
211 to 2216) so that each raw material gas is adjusted to have a predetermined flow rate. At that time, the opening of the main valve (2118) is adjusted while observing the vacuum gauge (2119) so that the pressure in the reaction vessel (2111) becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable, frequency 1
An RF power source (not shown) of 3.56 MHz is set to a desired power, and RF power is introduced into the reaction vessel (2111) through the high frequency matching box (2115) to cause glow discharge. The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support (2112). After the desired film thickness is formed, the supply of RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

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

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel (211).
1) In order to avoid remaining in the pipe from the outflow valve (2251 to 2256) to the reaction vessel (2111), the outflow valve (2251 to 2256) is closed, the auxiliary valve (2260) is opened, and the main valve is further opened. Valve (21
If necessary, the operation of 18) is fully opened and the system is once evacuated to a high vacuum.

Further, in order to make the film formation uniform, it is effective to rotate the support (2112) at a predetermined speed by a driving device (not shown) during the layer formation.

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

Next, high frequency plasma CVD using a frequency in the VHF band (hereinafter abbreviated as "VHF-PCVD").
A method of manufacturing the electrophotographic light-receiving member formed by the method will be described.

RF-PC in the manufacturing apparatus shown in FIG.
The deposition apparatus (2100) by the VD method is replaced with the deposition apparatus (3100) shown in FIG.
0), it is possible to obtain a photoreceptive member manufacturing apparatus for electrophotography by the VHF-PCVD method.

This apparatus is roughly classified into a reaction vessel (3111) having a vacuum airtight structure and capable of reducing pressure, a source gas supply apparatus (2200), and an exhaust apparatus (not shown) for reducing the pressure in the reaction vessel. ). A cylindrical support (3112), a heater for heating the support (3113), a source gas introduction pipe (not shown), and an electrode (3115) are installed in the reaction vessel (3111), and a high-frequency matching box ( 3116) is connected.
The inside of the reaction vessel (3111) is connected to a diffusion pump (not shown) through an exhaust pipe (3121).

The source gas supply device (2200) is made of SiH.
₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH _{3 and} other source gas cylinders (2212-1226) and valves (22)
31-2236, 2241-2246, 2251-22
56) and a mass flow controller (2211-2)
216), and a cylinder of each source gas is connected to a gas introduction pipe (not shown) in the reaction container (3111) via a valve (2260). Further, the space (3130) surrounded by the cylindrical support (3112) forms a discharge space.

Formation of a deposited film in this apparatus by the VHF-PCVD method can be performed as follows.

First, a cylindrical support (3112) is installed in a reaction vessel (3111), the support (3112) is rotated by a driving device (3120), and a reaction is performed by an exhaust device (not shown) (for example, a diffusion pump). The inside of the vessel (3111) is evacuated through the exhaust pipe (3121), and the reaction vessel (311)
1) Adjust the pressure inside to 1 × 10 ⁻⁷ Torr or less. Subsequently, the temperature of the cylindrical support (3112) is heated and maintained at a predetermined temperature of 200 ° C. to 350 ° C. by the support heating heater (3113).

The source gas for forming the deposited film is supplied to the reaction vessel (31
11), the gas cylinder valve (223
1 to 2236), confirm that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valve (224
1-2246), outflow valves (2251-2256),
After confirming that the auxiliary valve (2260) is open, first open the main valve (not shown) to open the reaction vessel (3
111) and the gas pipe are exhausted.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10.
At the time of ^-6 Torr, the auxiliary valve (2260) and the outflow valve (2251-2256) are closed.

After that, a gas cylinder (2221-222)
From (6), each gas is introduced by opening the valves (2231-2236), and the pressure of each gas is adjusted to ² kg / cm ² by the pressure adjuster (2261-2266). Next, the inflow valves (2241-2246) are gradually opened to introduce the respective gases into the mass flow controllers (2211-2216).

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support (3112) as follows.

When the cylindrical support (3112) reaches a predetermined temperature, the necessary ones of the outflow valves (2251-2256) and the auxiliary valve (2260) are gradually opened, and the gas cylinders (2212-1226) are brought to a predetermined position. Of the gas of the reaction vessel (311) through a gas introduction pipe (not shown).
It is introduced into the discharge space (3130) in 1). Next, the mass flow controllers (2211 to 2216) are adjusted so that each raw material gas has a predetermined flow rate. that time,
The opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the pressure in the discharge space (3130) becomes a predetermined pressure of 1 Torr or less.

When the pressure becomes stable, for example, frequency 5
A VHF power supply (not shown) of 00 MHz is set to a desired power, and VHF power is introduced into the discharge space (3130) through the matching box (3116) to cause glow discharge. Thus, in the discharge space (3130) surrounded by the support (3112), the introduced source gas is excited by the discharge energy and dissociated, and a predetermined deposited film is formed on the support (3112). This time,
In order to make the layer formation uniform, a support rotation motor (31
20) to rotate at a desired rotation speed.

After the desired film thickness is formed, the supply of VHF electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

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

Needless to say, all the outflow valves other than the necessary gas were closed when forming the respective layers, and the respective gases were used in the reaction vessel (311).
1) In order to avoid remaining in the piping from the outflow valve (2251 to 2256) to the reaction vessel (3111), the outflow valve (2251 to 2256) is closed, the auxiliary valve (2260) is opened, and the main valve is further opened. If necessary, the valve (not shown) is fully opened and the system is once evacuated to a high vacuum.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

In either method, the temperature of the support during the formation of the deposited film is preferably 200 ° C. or higher and 350 ° C. or lower,
More preferably 230 ° C or higher and 330 ° C or lower, optimally 2
It is desirable to set the temperature to 50 ° C or higher and 300 ° C or lower.

Any method of heating the support may be used as long as it is a heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, an infrared ray. Examples include a heat-radiating lamp heating element such as a lamp, and a heating element by a heat exchange means using a liquid, a gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used.

In addition to the above, a method may be used in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the support is conveyed into the reaction container in a vacuum.

The pressure in the discharge space in the VHF-PCVD method is preferably 1 mTorr or more and 50 or more.
0 mTorr or less, more preferably 3 mTorr or more 3
It is desirable to set it to 00 mTorr or less, most preferably to 5 mTorr or more and 100 mTorr or less.

In the VHF-PCVD method, the size and shape of the electrode provided in the discharge space may be any as long as the discharge is not disturbed, but in practice, the diameter is 1 mm or more and 1 mm or more.
A cylindrical shape of 0 cm or less is preferable. At this time, the length of the electrodes can be arbitrarily set as long as the electric field is uniformly applied to the support.

Any material may be used as the material of the electrode as long as it has a conductive surface. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te, V,
Metals such as Ti, Pt, Pb, and Fe, alloys thereof, glass whose surface is electrically conductive, and ceramics are usually used.

Next, the image forming process and the image forming apparatus according to the present invention will be described.

FIG. 4 is a schematic view showing an example in which a corona charger is used as the main charger in the image forming process of the image forming apparatus. The main charger 402, the electrostatic latent image forming unit 403, and the developing device 4 are provided around the light receiving member 401 that rotates in the direction of arrow X.
04, transfer paper supply system 405, transfer charger 406 (a),
Separation charger 406 (b), cleaner 407, conveyance system 40
8, a static elimination light source 409 and the like are provided. Further, a drum heater 423 for controlling the temperature of the light receiving member is included on the inner surface of the light receiving member.

The light receiving member 401 is uniformly charged by the main charger 402 to which a high voltage of +6 to 8 kV is applied, and an electrostatic latent image projected and formed by the electrostatic latent image forming portion is formed on this. Negative polarity toner is supplied to the latent image from the developing device 404 to form a toner image. On the other hand, the transfer material P supplied in the direction of the light receiving member through the transfer paper supply system 405 is +7 to 8
In the gap between the transfer charger 406 (a) to which a high voltage of kV is applied and the light receiving member 401, a positive electric field having a polarity opposite to that of the toner is applied from the back surface, whereby the negative polarity toner image on the surface of the light receiving member is transferred. Transferred to the material P. 12-14
The transfer material P reaches the fixing device (not shown) through the transfer paper conveying system 408 by the separation charging device 406 (b) to which a high AC voltage of 300 to 600 Hz is applied, and the toner image is fixed. It is discharged to the outside of the device.

FIG. 5 is a schematic view showing an example in which a roller charger is used as the main charger in the image forming process of the image forming apparatus. The main charger 502, the electrostatic latent image forming unit 503, and the developing device 5 are provided around the light receiving member 501 that rotates in the X direction.
04, a transfer paper supply system 505, a transfer charger 506, a cleaner 507, a conveyance system 508, a charge removal light source 509, and the like.

Further, in this example, the drum heater for controlling the temperature of the light receiving member as shown in FIG. 4 is omitted, and the heater 523 is arranged around the light receiving member 501. Then, before starting the image forming process, the light receiving member 50
By heating 1 with the heater 523 while rotating 1, the ozone products and the like adhering to the surface of the light receiving member 501 during the rest at night are removed.

The light receiving member 501 is uniformly charged by the main charger 502 to which a voltage of +0.6 to 2 kV is applied, on which an electrostatic latent image projected by the electrostatic latent image forming portion is formed, Negative polarity toner is supplied from the developing device 504 to this latent image to form a toner image.

On the other hand, the transfer material P supplied in the direction of the light receiving member through the transfer paper supply system 505 is the roller transfer charger 506 to which a high voltage of +0.6 to 2 kV is applied and the light receiving member 5.
In the gap 01, a positive electric field having a polarity opposite to that of the toner is applied from the back surface, whereby the negative polarity toner image on the surface of the light receiving member is transferred to the transfer material P. The transfer material P reaches a fixing device (not shown) through a transfer paper conveying system 508, and the toner image is fixed and discharged to the outside of the device.

When the heating step is provided before the start of the image forming step in the image forming method of the present invention, the light receiving member may be heated by the drum heater contained in the light receiving member as shown in FIG. Alternatively, the heating may be performed by an auxiliary heater arranged around the light receiving member as shown in FIG.

In the image forming method of the present invention, the temperature in the vicinity of the light receiving member is preferably 0 to 50 ° C., and most preferably 20 to 40 ° C. If it deviates from the above range, the density unevenness of the halftone image, so-called shakyness becomes noticeable.

(Experimental Example) Hereinafter, the present invention will be specifically described with reference to an experimental example.

(Experimental Example 1) An outer diameter of 8 was used by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
On a 0 mm mirror-finished aluminum cylinder (support), a light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 1. Further, by changing the flow rate of SiH _{4 in the} photoconductive layer, the flow rate ratio of SiH ₄ and H ₂ , the discharge power, the temperature of the support, etc., photoreceptive members having various temperature characteristics were prepared. An electrophotographic apparatus having the structure shown in FIG. 4 (NP-6 manufactured by Canon Inc.)
060 was modified for experiments), and potential characteristics and image characteristics were evaluated under various temperature environments.

A probe of a surface electrometer (TREK Model 344) was set at the position of the developing device (404) of the electrophotographic apparatus, the process speed was 380 mm / sec, the pre-exposure (wavelength 565 nm) was 4 lux · sec, and the primary charger (402). )
Under the condition of the current value of 1000 μA, the surface potential of the light receiving member at the position of the developing device (404) was measured and it was defined as the charging ability. Moreover, the temperature is 1 ° C when the charging ability is measured under the same conditions by changing the temperature from room temperature (about 20 ° C) to 50 ° C.
The change in the charging ability per hit was taken as the temperature characteristic.

Regarding the image characteristics, an image was formed by setting the charging conditions such that the surface potential of each light receiving member was constant at room temperature (25 ° C.), and then the temperature in the vicinity of the light receiving member was set to 50 ° C. To form an image. The difference between the image densities of the images obtained by the respective light receiving members at room temperature and at high temperature was judged, and 1: very good, 2: good, 3:
There is no problem in practical use, 4: Rank is classified into four stages, which is somewhat difficult in practical use. As a result, Ranks 1 and 2 were judged to be acceptable.

FIG. 6 shows the relationship between the temperature characteristic and the image density difference at this time. As is clear from FIG. 6, the temperature characteristic is −
It was found that a good image can be obtained regardless of the surrounding environment by using the light receiving member of 2 to 2 V / deg.

[0173]

[Table 1] (Experimental Example 2) A light-receiving member was produced under the production conditions shown in Table 1 in the same manner as in Experimental Example 1, and was set in the electrophotographic apparatus having the configuration shown in FIG. Temperature is −
An image was formed at 20 ° C to 80 ° C and evaluated.

The temperature characteristic of the electrophotographic light-receiving member of this example was 1.3 V / deg.

Regarding the image characteristics, a halftone image (A3 paper) was formed at each temperature, and density unevenness (roughness) in the same image was evaluated by ranking it in four steps as in Experimental Example 1. . As a result, Rank 1 and Rank 2 were judged to be acceptable.

FIG. 7 shows the relationship between the temperature in the vicinity of the light receiving member and the roughness at this time. As is clear from FIG. 7, even when a light receiving member having a temperature characteristic of −2 to 2 V / deg is used, the temperature in the vicinity of the light receiving member is set to 0 to 50 ° C., more preferably 20 to 40 ° C. Have been found necessary to obtain good image characteristics.

(Experimental Example 3) A light-receiving member was produced under the production conditions shown in Table 1 in the same manner as in Experimental Example 1, and the same FIG.
The image density was evaluated by setting the electrophotographic apparatus having the configuration shown in (1) to form 10,000 images continuously without adjusting the temperature of the light receiving member by the drum heater. Based on the density difference from the image density at the start of image formation, rank ranking was performed in the same four steps as in Experimental Example 1.

In this example, the temperature in the vicinity of the light receiving member at the start of image formation was 20 ° C., and it was 46 ° C. after 10,000 sheets had passed. FIG. 8 shows the relationship between the number of formed images, the temperature near the light receiving member, and the image density difference at this time. As is clear from FIG. 8, good electrophotographic characteristics were obtained even if the temperature in the vicinity of the light receiving member was gradually increased.

That is, the temperature characteristic is -2 to 2 V / deg.
It was found that an excellent image can be obtained regardless of the surrounding environment by the image forming method using the light receiving member.

(Experimental Example 4) A light-receiving member was produced under the production conditions shown in Table 1 in the same manner as in Experimental Example 1, set in the electrophotographic apparatus having the configuration shown in FIG. Formed and left for 10 hours. Then, the light receiving member was heated for 3 minutes by the heater 523 while rotating, and then the heater was turned off to continuously form 1000 sheets of images. Resuming image formation for the obtained image 1st sheet, 100th sheet, 100th sheet
When the difference in the image density of the 0th sheet was evaluated, there was almost no difference in the image density, and good results were obtained.

That is, the temperature characteristic is -2 to 2 V / deg.
It was found that a good image can be obtained by using the above-mentioned light receiving member and providing a heating step before the start of the image forming step after being left at rest.

[0182]

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

(Example 1) An outer diameter of 8 was obtained by using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG.
A light receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared on an aluminum cylinder (support) having a mirror surface of 0 mm. Table 2 shows the production conditions of the electrophotographic light-receiving member at this time.

With the electrophotographic light-receiving member of this example, a temperature characteristic of 1.2 V / deg was obtained. The prepared light receiving member was set in the electrophotographic apparatus having the structure shown in FIG. 4, and 10,000 images were continuously formed without adjusting the temperature of the light receiving member by the drum heater. All images were good. It showed a good result.

That is, the temperature characteristic is -2 to 2 V / deg.
It was found that a good image can be obtained regardless of the surrounding environment by using the light receiving member.

[0186]

[Table 2] (Example 2) In this example, instead of the surface layer of Example 1, a surface layer was provided in which the content of silicon atoms and carbon atoms in the surface layer was unevenly distributed in the layer thickness direction. Table 3 shows the manufacturing conditions of the light receiving member for electrophotography at this time.

With the electrophotographic light-receiving member of this example, a temperature characteristic of 0.6 V / deg was obtained. In addition, the produced electrophotographic light-receiving member was processed in the same manner as in Example 1.
When the electrophotographic apparatus having the structure shown in FIG. 1 was set and 10,000 images were continuously formed without controlling the temperature of the light receiving member by the drum heater, good electrophotographic characteristics were obtained as in Example 1. was gotten.

That is, even when the surface layer is provided in which the content of silicon atoms and carbon atoms in the surface layer is non-uniformly distributed in the layer thickness direction, the temperature characteristic is -2 to 2 V /
It was found that a good image can be obtained regardless of the surrounding environment by using the light receiving member of deg.

[0189]

[Table 3] (Example 3) In this example, an intermediate layer (upper blocking layer) containing a carbon atom content lower than that of the surface layer and containing an atom for controlling conductivity was provided between the photoconductive layer and the surface layer. . Table 4 shows the production conditions of the electrophotographic light-receiving member at this time.

With the electrophotographic light-receiving member of this example, a temperature characteristic of 1.8 V / deg was obtained. Further, the produced electrophotographic light-receiving member was set in the electrophotographic apparatus having the configuration shown in FIG. 5, and the image forming process was repeated, followed by leaving for 10 hours (pause). After that, while rotating the light receiving member, the light receiving member was heated for 3 minutes by an external heater and then the heater was turned off to perform image formation, and good results were obtained as in Example 1.

That is, it is found that even when the intermediate layer (upper blocking layer) is provided, a good image can be obtained regardless of the surrounding environment by using the light receiving member having a temperature characteristic of −2 to 2 V / deg. It was

[0192]

[Table 4] (Example 4) In this example, an IR absorption layer was provided between the support and the charge injection blocking layer as a light absorption layer for preventing the occurrence of an interference pattern due to the reflected light from the support. In Table 5,
The conditions for producing the electrophotographic light-receiving member at this time are shown below.

The other points were the same as in Example 1. The temperature characteristic of the electrophotographic light-receiving member of this example is 1.7 V / deg.
The result was obtained. When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained as in Example 1.

That is, it was found that even when the IR absorbing layer was provided, a good image could be obtained regardless of the surrounding environment by using the light receiving member having a temperature characteristic of −2 to 2 V / deg.

[0195]

[Table 5] (Example 5) In this example, instead of the RF-PCVD method of Example 1, a manufacturing apparatus for an electrophotographic light-receiving member by the VHF-PCVD method shown in FIG. A light-receiving member including a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared on an aluminum cylinder (support) that had been subjected to mirror surface processing. Table 6 shows the production conditions of the electrophotographic light-receiving member at this time.

With the electrophotographic light-receiving member of this example, a temperature characteristic of -1.2 V / deg was obtained. Also,
When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained as in Example 1.

That is, even when the manufacturing method of the light receiving member for electrophotography is changed, the temperature characteristic is -2 to 2 V / d.
It was found that a good image can be obtained by using the light receiving member of eg, regardless of the surrounding environment.

[0198]

[Table 6] (Example 6) In this example, as the atoms constituting the surface layer,
The surface layer was provided with nitrogen atoms instead of carbon atoms. Table 7 shows the production conditions of the electrophotographic light-receiving member at this time. The other points were the same as in Example 5.

With the electrophotographic light-receiving member of this example, a temperature characteristic of 1.0 V / deg was obtained. When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained as in Example 1.

That is, as the atoms constituting the surface layer,
Even when the surface layer contains nitrogen atoms instead of carbon atoms, a good image can be obtained regardless of the surrounding environment by using the light receiving member having a temperature characteristic of −2 to 2 V / deg. all right.

[0201]

[Table 7] (Embodiment 7) In the present embodiment, the charge injection blocking layer is deleted, and the photoconductive layer does not substantially contain carbon atoms in the first layer region containing carbon atoms in a non-uniform distribution state in the layer thickness direction. Second
Was formed continuously with the layer region. Table 8 shows the production conditions of the electrophotographic light-receiving member at this time. The other points were the same as in Example 5.

With the electrophotographic light-receiving member of this example, a temperature characteristic of -1.9 V / deg was obtained. Also,
When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained as in Example 1.

That is, the charge injection blocking layer is removed, and the first layer region containing carbon atoms as a photoconductive layer in a non-uniform distribution state in the layer thickness direction and the second layer containing substantially no carbon atoms.
It was found that even when the light receiving member having a temperature characteristic of −2 to 2 V / deg is used, a good image can be obtained even when it is formed continuously with the layer region.

[0204]

[Table 8] Example 8 In this example, an intermediate layer (lower surface layer) having a carbon atom content lower than that of the surface layer is provided between the photoconductive layer and the surface layer, and at the same time, the photoconductive layer is functionally separated. Turn into
The charge transport layer and the charge generation layer were provided in two layers. Table 9
The manufacturing conditions of the electrophotographic light-receiving member at this time are shown in FIG. The other points were the same as in Example 5.

With the electrophotographic light-receiving member of this example, a temperature characteristic of 1.9 V / deg was obtained. When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good electrophotographic characteristics were obtained as in Example 1.

That is, an intermediate layer (lower surface layer) having a carbon atom content lower than that of the surface layer is provided between the photoconductive layer and the surface layer, and at the same time, the photoconductive layer is functionally separated,
It was found that even when the charge transport layer and the charge generating layer are provided in two layers, a good image can be obtained by using a light receiving member having a temperature characteristic of −2 to 2 V / deg regardless of the surrounding environment. It was

[0207]

[Table 9]

[0208]

According to the image forming method of the present invention, a-S
It is possible to solve all the problems in the image forming method using the conventional electrophotographic light receiving member composed of i, and particularly excellent electrical characteristics, optical characteristics, photoconductive characteristics, image characteristics, durability Properties and environmental characteristics of use.

In particular, in the present invention, by using a light receiving member having a photoconductive layer composed of a non-single crystal such as a-Si, the temperature characteristic of which is remarkably reduced as compared with the conventional one, the fluctuation of the ambient environment can be achieved. It has a characteristic that the change of the surface potential and the change of the image density with respect to the above are suppressed and that it has extremely excellent electric characteristics and image characteristics.

In other words, the feature is that a good image can always be obtained without using a heating and holding means such as a drum heater.

Further, by providing a heating means for removing moisture and ozone products adhering to the surface of the light receiving member while the image forming apparatus is at rest, and by providing the heating step before restarting the image forming step, It is characterized in that the influence of the adsorbed matter on the surface of the receiving member on the image characteristics is substantially negligible.

Therefore, the drum heater, which has been conventionally required, can be omitted, or the heating by the drum heater at night can be omitted, so that the power saving design can be realized.

[Brief description of drawings]

FIG. 1 is a schematic layer structure diagram for explaining a layer structure of a preferred embodiment of an electrophotographic light-receiving member according to the present invention.

FIG. 2 is an example of an apparatus for forming a light-receiving layer of an electrophotographic light-receiving member according to the present invention, which is a schematic diagram of an apparatus for manufacturing an electrophotographic light-receiving member by a glow discharge method using RF high frequencies. FIG.

FIG. 3 is an example of an apparatus for forming a light-receiving layer of an electrophotographic light-receiving member according to the present invention, which is a schematic diagram of an apparatus for manufacturing an electrophotographic light-receiving member by a glow discharge method using a VHF band high frequency. FIG.

FIG. 4 is a schematic explanatory view of an image forming apparatus using a light receiving member according to the present invention, which uses a corona charger as a main charger in an image forming process.

FIG. 5 is an example of an image forming apparatus using a light receiving member according to the present invention, in which the roller charger is used as a main charger of the image forming process and a drum heater is provided around the light receiving member. It is a schematic explanatory view.

FIG. 6 is a diagram showing a relationship between temperature characteristics and image density ranks in the image forming method of the present invention.

FIG. 7 is a diagram showing the relationship between the environmental temperature and the rough rank in the image forming method of the present invention.

FIG. 8 is a diagram showing the relationship among the number of image formed sheets, the temperature in the vicinity of the light receiving member, and the image density rank in the image forming method of the present invention.

[Explanation of symbols]

 100 Photoreceptive Member 101 Conductive Support 102 Photoreceptive Layer 103 Photoconductive Layer 104 Surface Layer 105 Charge Injection Blocking Layer 106 Charge Generation Layer 107 Charge Transport Layer 110 Free Surface 2100, 3100 Deposition Device 2111, 3111 Reaction Vessel 2112, 3112 Cylinder Support 2113, 3113 support heating heater 2114 source gas introduction pipe 2115, 3116 matching box 2116 source gas pipe 2117 reaction vessel leak valve 2118 main exhaust valve 2119 vacuum gauge 2200 source gas supply device 2211-2216 mass flow controller 2221-2226 Source gas cylinder 2231 to 2236 Source gas cylinder valve 2241 to 2246 Gas inflow valve 2251 to 2256 Gas outflow valve 2261 to 2266 Pressure regulator 3115 Electrode 3120 Support rotating motor 3121 Exhaust pipe 3130 Discharge space 401, 501 Electrophotographic light receiving member 402, 502 Main charger 403, 503 Electrostatic latent image forming part 404, 504 Developer 405, 505 Transfer paper supply system 406, 506 Transfer / separation charger 407, 507 Cleaner 408, 508 Conveying system 409, 509 Eliminating light source 423, 523 Drum heater

Claims (4)

[Claims] 1. An electrophotographic image forming method using an image forming step including at least a charging step, an exposing step, a developing step, and a cleaning step, wherein a conductive support and a hydrogen atom and / or a halogen atom having a silicon atom as a matrix. And a photoreceptive layer having a photoconductive layer having photoconductivity, the photoreceptive member having a photoconductive layer formed of a non-single-crystal material containing at least −2 V / deg. An image forming method, characterized in that the image forming step is performed using a light receiving member of 2 V / deg or less. 2. The image forming method according to claim 1, wherein the light receiving member is used and the image forming step is performed at a temperature in the vicinity of the light receiving member in the range of 0 to 50 ° C. 3. An electrophotographic image forming method using an image forming step including at least a charging step, an exposing step, a developing step and a cleaning step, wherein a conductive support and a hydrogen atom and / or a halogen atom having a silicon atom as a base material. And a photoreceptive layer having a photoconductive layer having photoconductivity, which is composed of a non-single-crystal material containing, and has a charging characteristic temperature characteristic of −2 V / deg or more and 2 V / de or more.
An image forming method, wherein the image forming step is performed using a light receiving member having a weight of g or less, and a heating step for heating the light receiving member is provided before the start of the image forming step. 4. The image forming method according to claim 3, wherein the light receiving member is used and the image forming step is performed at a temperature in the vicinity of the light receiving member in the range of 0 to 50 ° C.