JPH08262770A - Electrophotographic photoreceptive member - Google Patents

Abstract

PURPOSE: To provide a photoreceptive member which have electrical, optical and photoconductive characteristics stable at all times and have excellent photofatigue resistance, durability and moisture resistance and good image quality by forming a substantially uniform metallic layer contg. metal bonds on a photoreceptive layer. CONSTITUTION: This electrophotographic photoreceptive member has at least a substrate 101 and the photoreceptive layer 102 consisting of a nonconductive layer 103 which is composed of a non-single crystalline material mainly composed of silicon atoms on this substrate and exhibit non-electrical conductivity. The metallic layer 106 having the metal bonds is formed on the surface of the photoreceptive layer 102. Namely, the photoreceptive layer 102 is composed of the photoconductive layer 103 which consists of A-Si:H, X and has photoconductivity. The metallic layer 106 which is formed on the surface of the photoconductive layer 103 and has the metal bonds is formed by properly setting a forming method and unmerical conditions of film forming parameters in such a manner that the desired characteristics are obtd. More specifically, a plasma CVD method, sputtering method, etc., are used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is 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 a light receiving member for electrophotography.

[0002]

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. In particular, 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 to the human body at the time of use is an important point. Amorphous silicon (hereinafter referred to as "A-Si") is a photoconductive material exhibiting excellent properties in this respect. For example, JP-A-54-86341 discloses a photoreceptive member for electrophotography. The application of is described.

2 (a), 2 (b) and 2 (c),
FIG. 3 is a cross-sectional view schematically showing a layer structure of a conventional electrophotographic light-receiving member 200, in which 201 is a conductive support, 202 is a photoconductive layer 203 made of A-Si, a surface layer 204, a charge injection blocking layer. The light receiving layer is made of 205 or the like. Such a photoreceptive member for electrophotography generally comprises heating the conductive support 201 to 50 ° C. to 400 ° C. and subjecting the support to a vacuum deposition method, a sputtering method, an ion plating method,
The light receiving layer 202 made of A-Si is formed by a film forming method such as a thermal CVD method, a photo CVD method, or a plasma CVD method. Among them, the plasma CVD method, that is, the method of decomposing the raw material 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.

JP-A-56-83746 discloses an electrically conductive support and an AS containing a halogen atom as a constituent element.
A photoreceptive member for electrophotography, which comprises a photoconductive layer of i (hereinafter, referred to as “A-Si: X”) has been proposed. In the publication, by containing 1 to 40 atomic% of halogen atoms in A-Si, the dangling bond is compensated to reduce the local level density in the energy gap, and the light of the light receiving member for electrophotography is reduced. It is said that the electrical and optical characteristics suitable for the conductive layer can be obtained. Further, Japanese Patent Application Laid-Open No. 57-11556 discloses a photoconductive member having a photoconductive layer composed of an A-Si deposited film, which has electrical and optical properties such as dark resistance, photosensitivity and photoresponsiveness. In order to improve use environment characteristics such as photoconductive characteristics and moisture resistance, and further stability over time, a photoconductive layer made of an amorphous material containing silicon atoms as a matrix contains silicon atoms and carbon atoms. Techniques for providing a surface barrier layer composed of a non-photoconductive amorphous material are described.

Japanese Unexamined Patent Publication No. 60-67951 discloses a technique relating to a photosensitive member having a translucent insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine, and is disclosed in Japanese Unexamined Patent Publication No. Sho 62-62. In JP-A-168161, silicon atoms, carbon atoms, 41 to 7 are used as a surface layer.
A technique using an amorphous material containing 0 atomic% of hydrogen atoms as a constituent is described. On the other hand, JP-A-59-10
2239, JP-A-59-102240, JP-A-59
In Japanese Patent Laid-Open No. 102246/1992, a surface of an amorphous silicon-based photoconductor is treated with a Friedel-Crafts catalyst, an organometallic compound, or an electron-accepting substance so that specific atoms are adsorbed or bonded to cause surface defects. Techniques for reducing the number of images and image deletion are disclosed. Also,
Japanese Unexamined Patent Publication (Kokai) No. 60-28658 discloses an amorphous silicon-based surface protective layer containing a metal atom and / or a metal ion. Examples of the metal include Group IIIb and Group IVb of the periodic table, Group Vb, Group VIb,
Group VIIb, Group VIII, Group Ib or Group IIb
The transition metals belonging to the family and the metals constituting the Friedel-Crafts catalyst are mentioned.

Further, JP-A-59-102248 discloses that a polymer compound film containing at least one of a Friedel-Crafts catalyst, an organometallic compound and an electron accepting substance is provided on the surface as a protective film. Has been done. Further, Japanese Patent Application Laid-Open No. 61-126561 discloses a technique of chemically modifying the surface of a photoreceptor with a hydrophobic group so as to make the surface hydrophobic and reduce image deletion. In Japanese Patent Laid-Open No. 1-246120, a divalent metal element such as magnesium or calcium is contained in an amorphous silicon film to change the bonding structure into a dense and hard bonding structure, thereby reducing the decrease in photoconductivity. It is disclosed. These techniques have improved the electrical, optical, photoconductive properties and use environment properties of the electrophotographic light-receiving member, and have also made it possible to improve the image quality to some extent.

[0007]

However, the conventional photoreceptive member for electrophotography having a photoconductive layer composed of an A-Si-based material has a disadvantage in that it has a dark resistance value, photosensitivity, photoresponsiveness, etc. Although individual improvements have been made in terms of optical characteristics, photoconductive characteristics, use environment characteristics, and stability over time and durability, in order to improve overall characteristics, The reality is that there is room for further improvement.

The high image quality, high speed and high durability of the electrophotographic apparatus are rapidly advancing, and in the electrophotographic light-receiving member, the electrical characteristics and the photoconductive characteristics are further improved, and at the same time, the high charging ability and the high sensitivity are obtained. It is required to significantly improve performance in all environments while maintaining the above. Further, in order to reduce the service cost, it is necessary to improve the reliability of each part and reduce the number of maintenances. Therefore, the light receiving member for electrophotography has been able to be used repeatedly for a long time more than before without being subjected to maintenance by a service person under various environments.

Although the above-mentioned conventional techniques have made it possible to improve the above problems to some extent, it cannot be said that the control of surface defects and the improvement of surface properties are still sufficient. As a practical problem of the amorphous silicon-based photoreceptive member, potential characteristics due to generation of surface defects during continuous repeated use, especially deterioration of charging ability and deterioration of charging uniformity due to deterioration of surface charge injection blocking ability Can be mentioned. Further, as the speed of the electrophotographic apparatus increases, the requirements for toner releasability due to the surface properties of the surface of the electrophotographic light-receiving member and cleaning performance after the end of the transfer process are increasing.

Therefore, while the characteristics of the A-Si material itself are improved, the layer of the electrophotographic light-receiving member is designed so as to solve the above problems when designing the electrophotographic light-receiving member. It is necessary to improve the structure, chemical composition of each layer, and production method from a comprehensive viewpoint.

It is an object of the present invention to solve various problems in the electrophotographic light-receiving member having the conventional light-receiving layer composed of A-Si as described above. That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially stable regardless of the use environment, are excellent in light fatigue resistance, and do not deteriorate during repeated use. A photoreceptive member for electrophotography having a photoreceptive layer composed of a non-single-crystal material having a silicon atom as a base material, which has excellent durability and moisture resistance, hardly any residual potential is observed, and has good image quality. To provide.

[0012]

The light-receiving member for electrophotography of the present invention is composed of at least a support and a non-single-crystal material having silicon atoms on the support as a matrix and exhibits photoconductivity. An electrophotographic light receiving member having a light receiving layer formed of a photoconductive layer, characterized in that a metal layer having a metal bond is formed on the surface of the light receiving layer.

The light-receiving member for electrophotography of the present invention designed to have the above-mentioned constitution can solve all of the above-mentioned problems and is extremely excellent in electrical, optical and photoconductive properties. The characteristics, image quality, durability and environment characteristics of use are shown.

In order to solve the above-mentioned problems, the present inventors have focused on the behavior of the outermost surface of the light-receiving layer, have a method of reducing the defects on the outermost surface, and improving the surface property of the light-receiving member. As a result of intensive studies, it was found that the above object can be achieved by forming an extremely thin metal layer on the surface of the light receiving member. In particular, it is important in the present invention that the metal atom of the metal layer has a metal bond, and further, the metal atom in the metal layer and the outermost surface atom of the photoreceptive layer are bonded to each other to further enhance the effect. It became clear that it would be done.

The inventors believe that the formation of a metal layer on the surface of the light-receiving layer improves the surface charge injection blocking ability and the surface layer, as follows.
That is, the film thickness of the A-Si based photoreceptor is approximately 20 to
Although it is necessary to set the thickness to about 30 μm, such a thick film may cause structural defects such as minute cracks and pinholes on the surface due to the stress. Bond defects such as dangling bonds and voids occur due to deformation. Further, the atoms on the surface of the light-receiving layer are more energetically unstable than the inside thereof, and therefore, they form a bond different from the inside to have a different atomic arrangement. Furthermore, the atoms adsorbed on the surface generate energy levels localized on the surface, and the non-uniformity of the surface state appears remarkably. As a result, a portion having a low charge blocking ability is partially generated, and from there, the charge imparted to the surface of the light receiving layer at the time of charging is injected into the light receiving layer, and the charge ability is lowered. .

However, by forming a metal layer on the surface that is energetically uniform and has a stable metal bond, the defects generated by the metal atoms on the surface of the photoreceptive layer are effectively compensated, and the surface potential is uniform. Is promoted,
It is considered that the charging ability is improved by improving the charge injection blocking ability and the charging uniformity is improved. Further, by forming a metal layer having a metal bond or an intermetallic compound layer on the surface of the light-receiving layer, a dense, thermally, electrically, and chemically stable film with little change over time is formed on the surface. Therefore, it is considered that the slipperiness of the surface is further improved and the releasing property and cleaning property of the toner are improved. Furthermore, it is presumed that a kind of silicide-like compound is formed by the combination of the metal atom in the metal layer and the silicon atom in the light receiving layer, and the mechanical strength and the injection blocking ability are further improved.

The light receiving member of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a schematic explanatory view for explaining the layer structure of the electrophotographic light-receiving member of the present invention. The light receiving member 100 for electrophotography shown in FIG.
A light receiving layer 102 is provided on a support 101 for a light receiving member. The light receiving layer 102 is made of A-Si: H, X.
And a photoconductive layer 103 having photoconductivity. A metal layer 106 having a metal bond is formed on the surface of the photoconductive layer 103. Further, the electrophotographic light-receiving member 100 shown in FIG. 1B is a support 1 for the light-receiving member.
01, the light receiving layer 102 is provided. The light receiving layer 102 is made of A-Si: H, X, and is composed of a photoconductive layer 103 having photoconductivity and an amorphous silicon-based surface layer 104. On the surface of the surface layer 104,
A metal layer 106 having a metal bond is formed. Further, the light receiving member 100 for electrophotography shown in FIG.
A light receiving layer 102 is provided on a support 101 for a light receiving member. The light receiving layer 102 is made of A-Si: H, X.
And a photoconductive layer 103 having photoconductivity, an amorphous silicon-based surface layer 104, and an amorphous silicon-based charge injection blocking layer 105. A metal layer 106 having a metal bond is formed on the surface of the surface layer 104.

[0018]

[Support] As the support used in the present invention,
It may be electrically conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Further, at least the surface of the electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, or the like, on which the light receiving layer is formed, of the electrically insulating support such as glass or ceramic. It is also possible to use a support obtained by conducting a conductive treatment.

The shape of the support 101 used in the present invention can be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface. Also, its thickness is
It can be appropriately determined so that the electrophotographic light-receiving member 100 can be formed as desired, but when flexibility is required as the electrophotographic light-receiving member 100, the function as the support 101 can be sufficiently exerted. It can be made as thin as possible within the range. However, the support 101 is usually 10 μm or more in view of manufacturing and handling, mechanical strength and the like.

In particular, when image recording is performed using coherent light such as laser light, the surface of the support 101 is used 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 of the surface of the support 101 is described in JP-A-60-168156.
No. 60-178457, No. 60-225.
It is created by a known method described in Japanese Patent Publication No. 854.

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 formed 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. Unevenness due to a plurality of spherical trace dents on the surface of the support 101 is disclosed in JP-A-61-231.
It is prepared by a known method described in Japanese Patent No. 561.

[0022]

[Photoconductive layer] In the present invention, a light receiving layer 102 is formed on a support 101 to effectively achieve its purpose.
The photoconductive layer 103 constituting a part of the above 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 CV
AC discharge CVD method such as D method or microwave CVD method,
Or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method, thermal C
It can be formed by various thin film deposition methods such as the VD 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, the sputtering method, and the ion plating method are preferable because it is relatively easy to control the conditions for producing a photoreceptive member having characteristics. These methods may be used together in the same system. For example,
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 source gas for supplying H, which can supply hydrogen atoms (H), and / or an X supply, which can supply halogen atoms (X). A raw material gas for use in the reactor is introduced into the reaction vessel in a desired gas state in a desired gas state, a glow discharge is generated in the reaction vessel, and a predetermined support 101 is installed at a predetermined position in advance. A layer made of A-Si (H, X) may be formed on.

In the present invention, it is necessary that the photoconductive layer 103 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, particularly This is because it is essential for improving photoconductivity and charge retention characteristics. The content of hydrogen atoms or halogen atoms, or the total amount of hydrogen atoms and halogen atoms is 1 to 40 atomic% with respect to the total of silicon atoms and hydrogen atoms and / or halogen atoms, and more preferably 3 to 35%. Atomic%, optimally 5-30
It is preferably set to atomic%.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
Silicon hydrides (silanes) in a gas state such as ₈ and Si ₄ H ₁₀ or which can be gasified are mentioned, and SiH ₄ and Si ₂ are more easily handled at the time of forming a layer and have good Si supply efficiency. H
₆ is mentioned as a preferable one. Also, these S
If necessary, the raw material gas for supplying i may be H ₂ , He, Ar,
It may be diluted with a gas such as Ne before use.

In order to further facilitate the control of the introduction ratio of hydrogen atoms introduced into the formed photoconductive layer 103, hydrogen gas or a silicon compound gas containing hydrogen atoms is desired for these gases. It is preferable to form a layer by mixing the amounts. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio. In order to structurally introduce hydrogen atoms into the photoconductive layer 103, in addition to the above, H ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄
It can also be carried out by causing silicon hydride such as H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the reaction vessel to cause discharge.

The source gas for supplying halogen atoms effectively used in the present invention is, for example, a gaseous or gas such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. Preferred examples thereof include halogen compounds that can be converted. 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 preferably used in the present invention include fluorine gas (F ₂ ), Br
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , IF
An interhalogen compound such as ₇ can be mentioned. As a silicon compound containing a halogen atom, a so-called silane derivative substituted with a halogen atom, specifically, SiF ₄ ,
Silicon fluoride such as Si 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 to contain hydrogen atoms and / or halogen atoms. The amount of the substance introduced into the reaction container, the discharge power, etc. may be controlled.

It is also effective that the photoconductive layer contains carbon atoms and / or germanium atoms and / or tin atoms and / or oxygen atoms and / or nitrogen atoms.
The content of carbon atom and / or germanium atom and / or tin atom and / or oxygen atom / and / or nitrogen atom is preferably based on the sum of silicon atom, carbon atom, germanium atom, tin atom, oxygen atom and nitrogen atom. 0.
00001-50 atomic%, more preferably 0.01-4
0 atomic%, optimally 1 to 30 atomic% is desirable. Carbon atoms and / or germanium atoms and / or tin atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer or may be contained in the photoconductive layer in the thickness direction. There may be a portion having a non-uniform distribution such that the amount changes.

Further, in the present invention, the photoconductive layer 103
It is preferable to contain an atom for controlling conductivity as necessary. Atoms that control conductivity are photoconductive layer 10
3 may be contained in a state of being uniformly distributed evenly in 3, or there may be a portion containing in an uneven distribution state in the layer thickness direction. Examples of the atoms that control the conductivity include so-called impurities in the field of semiconductors, which give p-type conductivity characteristics.
An atom belonging to group b (hereinafter abbreviated as “group IIIb atom”) or an atom belonging to group Vb of the periodic table (hereinafter abbreviated as “group Vb atom”) which gives n-type conductivity can be used. . Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. Is. Specific examples of the Vb group atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like.
s is preferred.

The content of atoms controlling the conductivity contained in the photoconductive layer 103 is preferably 1 × 10 ^{−3 to} 5
× 10 ⁴ atomic ppm, more preferably 1 × 10 ^-2 to 1 ×
It is desirable that the concentration is 10 ⁴ atomic ppm, optimally 1 × 10 ^{−1 to} 5 × 10 ³ atomic ppm. Atoms that control conductivity,
For example, in order to structurally introduce a Group IIIb 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 formed during layer formation. It may be introduced into the reaction container together with another gas for forming the photoconductive layer 103. No. II
As the raw material for introducing the group Ib atom or the raw material for introducing the group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified under at least the layer forming condition is adopted. Is desirable.

Raw materials for introducing such group IIIb atoms
In the present invention as a substance, it is effective to use boron.
For introducing elementary atoms, B₂H₆, B_FourH_Ten, B_FiveH₉, B_Five
H₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Boron hydride such as B
F₃, BCl₃, BBr₃Such as boron halide, etc.
Be done. In addition, AlCl₃, GaCl₃, Ga ( C
H₃)₃, InCl₃, TlCl₃And so on
It The present invention also provides a raw material for introducing a group Vb atom.
Is effectively used in introducing phosphorus atoms
Is PH₃, P₂H_FourPhosphorus hydride, PH, etc._FourI, PF₃, P
F_Five, PCl₃, PCl_Five, PBr₃, PBr_Five, PI₃Etc.
Phosphorus halide may be mentioned. Besides this, AsH₃, As
F₃, AsCl₃, AsBr₃, AsF_Five, SbH₃, Sb
F₃, SbF_Five, SbCl₃, SbCl_Five, BiH₃, Bi
Cl₃, BiBr₃Etc. of the starting material for introducing the group Vb atom
Can be listed as valid. Also these
If necessary, use raw materials for introducing atoms that control conductivity
H₂Dilute with gas such as He, Ar, Ne
May be.

In the present invention, the layer thickness of the photoconductive layer 103 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, but is preferably 3 to 120 μm. Preferably 5-100μ
m, most preferably 10 to 80 μm.

In order to form the photoconductive layer 103 having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 101 and the gas pressure in the reaction vessel as desired. The temperature (Ts) of the support 101 is appropriately selected according to the layer design, but in the usual case, preferably 20 to 500 ° C., more preferably 50 to 450.
It is desirable to set the temperature to 100 ° C, optimally 100 to 400 ° C. Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the normal case, it is preferably 1
× 10 ^{-5 to} 100 Torr, more preferably 5 × 10 ^-5
-30 Torr, optimally 1 * 10 < ^-4 > ^-10 Torr is preferable. Further, in the present invention, the temperature range described above is mentioned as a desirable numerical range of the support temperature for forming the photoconductive layer, and the gas pressure, but the conditions are not usually independently determined separately, and are desired. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having the above characteristics.

[0034]

[Surface Layer] In the present invention, it is possible to further form an amorphous silicon-based surface layer 104 on the photoconductive layer 103 formed on the support 101 as described above. This surface layer 104 has a free surface 106,
Mainly in order to achieve the object of the present invention in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. Further, in the present invention, the light receiving layer 1
Since each of the amorphous materials forming the photoconductive layer 103 and the surface layer 104 forming 02 has a common constituent element of silicon atom, chemical stability is sufficiently ensured at the stacking interface. Has been done.

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”), a hydrogen atom (H) and / or a halogen atom (X), and further an amorphous silicon (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 the present invention, in order to effectively achieve the object, the surface layer 104 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. . 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,
It can be formed by various thin film deposition methods such as an ion plating method, 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 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, in order to form the surface layer 104 of A-SiC: H, X by the glow discharge method, it is basically possible to supply silicon atoms (Si) to Si.
A source gas for supply, a source gas for C supply capable of supplying carbon atoms (C), and a source gas for H supply capable of supplying hydrogen atoms (H) and / or a halogen atom (X) are supplied. The raw material gas for X supply to be obtained is introduced in a desired gas state into a reaction vessel whose inside can be decompressed, a glow discharge is generated in the reaction vessel, and a predetermined support is installed in a predetermined position in advance. A layer made of A-SiC: H, X may be formed on the body 101.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen is preferable, and particularly, S
It is preferable to use iC as a main component. In the case of SiC, the amount of carbon is 30% with respect to the sum of silicon atoms and carbon atoms.
To 90% is preferred.

In the present invention, it is necessary that the surface layer 104 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms,
It is essential for improving layer quality, especially for improving photoconductivity and charge retention properties. The hydrogen atom content is usually 41 to 70 atom%, preferably 45 to 60 atom%, and the fluorine atom content is usually 0 to 15 atom%, relative to the total amount of constituent atoms. Is 0.1
It is desirable to set the content to 10 atomic%, optimally 0.6 to 4 atomic%.

The light-receiving member formed within the range of the hydrogen and / or fluorine content can be sufficiently applied as a remarkably excellent one in the practical view. 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, the hydrogen content in the surface layer should be 4
By controlling the amount to be 1 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 decreases, and the surface layer 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 of H ₂ gas, the temperature of the support, the discharge power, the gas pressure and the like.

Further, by controlling the fluorine content in the surface layer within the range of 0.1 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,
When the fluorine content in the surface layer exceeds 15 atomic%, most of the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona are generated. Will not be 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 hydrogen content in the surface layer can be controlled by the flow rate of H ₂ gas, the temperature of the support, the discharge power, the gas pressure and the like.

In the present invention, the substance that can be used as the gas for supplying silicon (Si) used for forming the surface layer is a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H _10. , Or silicon hydrides (silanes) that can be gasified are used effectively, and SiH ₄ , SiH ₄ , in terms of ease of handling during layer formation, good Si supply efficiency, and the like.
Si ₂ H ₆ is mentioned as a preferable one. In addition, if necessary, the source gas for supplying Si may be H ₂ , He,
It may be diluted with a gas such as Ar or Ne before use.

Gas for supplying carbon used in the present invention
Possible substances are CH_Four, C₂H ₆, C₃H₈, C_Four
H_TenHydrocarbons in a gaseous state such as
It is listed as a material that is used for the effect of the
CH in terms of ease of handling and good Si supply efficiency_Four, C₂H
₆Are preferred. Also, these C
The raw material gas for supply is H if necessary.₂, He, Ar, N
It may be diluted with a gas such as e before use.

The substances that can be used as the gas for supplying nitrogen or oxygen used in the present invention include NH ₃ , NO and N _2.
The compounds in a gas state such as O, NO ₂ , H ₂ O, O ₂ , CO, CO ₂ , N ₂ or the like which 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 more easily 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.
In order to structurally introduce hydrogen atoms into the surface layer 104, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
It can also be carried out by causing silicon hydride such as Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the reaction vessel to cause discharge.

As the raw material gas for supplying the halogen atom used in the present invention, for example, a halogen gas, a halide, an interhalogen compound containing halogen,
Preference is given to gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives. 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 and Cl.
Interhalogen compounds such as F, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. Specific examples of the silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom include, for example, SiF ₄ ,
Silicon fluoride such as Si 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 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, in the present invention, it is preferable that the surface layer 104 contains atoms for controlling the conductivity, if necessary. Atoms for controlling conductivity may be contained in the surface layer 104 in a state of being uniformly distributed.
Alternatively, there may be a portion containing a non-uniform distribution in the layer thickness direction. Examples of the atom that controls the conductivity include so-called impurities in the semiconductor field, and an atom that belongs to Group IIIb of the periodic table that gives a p-type conductivity (hereinafter abbreviated as “Group IIIb atom”).
Alternatively, an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) which imparts n-type conductivity can be used. Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. As the group Vb atom,
Specifically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable.

The content of atoms controlling the conductivity contained in the surface layer 104 is preferably 1 × 10 ^{−3 to} 5 ×.
10 ⁴ atomic ppm, more preferably 1 × 10 ^-2 to 1 × 1
0 ⁴ atom ppm, optimally 1 × 10 ^{−1 to} 5 × 10 ³ atom p
It is preferably set to pm. In order to structurally introduce a conductivity controlling atom, for example, a group IIIb atom or a group Vb atom, a raw material for introducing a group IIIb atom or a group Vb atom for introducing a group IIIb atom during layer formation is used. The raw material may be introduced into the reaction vessel in a gas state together with another gas for forming the surface layer 104. 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.

As a raw material for introducing such a group IIIb atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ and B ₅ H ₁₁ are effectively used for introducing a boron atom. , B ₆ H ₁₀ ,
B ₆ H _12, B ₆ borohydride of H _14, etc., BF _3, BCl _3, B
Examples thereof include boron halides such as Br ₃ . Besides this, A
lCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , T
lCl _{3 and the} like can also be mentioned. What is effectively used in the present invention as a raw material for introducing a Group Vb atom is phosphorus hydride such as PH ₃ , P ₂ H ₄ or the like, PH ₄ I, PF ₃ , PF ₅ for introducing a phosphorus atom. , PCl ₃ , PCl ₅ , PB
Examples thereof include phosphorus halides such as r ₃ , PBr ₅ , and PI ₃ .
In _{addition, AsH 3, AsF 3, AsCl} 3, AsBr 3, A
sF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , Sb
Cl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group Vb atom. Further, these raw material substances 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 in the present invention is usually 20Å to 10 μm, preferably 100Å to 5 μm.
m, most preferably 500Å to 2 μm. If the layer thickness is less than 20Å, the surface layer will be lost due to wear or the like during use of the light receiving member.
If it exceeds μm, the electrophotographic properties are deteriorated such as the increase of residual potential.

The surface layer 104 according to the present invention is carefully formed to provide its required properties as desired. That is, Si, C and / or N and / or O,
A substance having H and / or X as a constituent element structurally takes a form from crystalline to amorphous depending on its formation condition, and has an electrical property that is a property from conductive to semiconducting to insulating. , Each showing a property from a photoconductive property to a non-photoconductive property, so that in the present invention, the formation conditions are selected as desired so that a compound having desired properties according to the purpose is formed. Is done strictly. 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 continuous repeated use characteristics and use environment characteristics, the degree of electrical insulation described above is relaxed to some extent, and the surface layer 104 has some sensitivity to irradiation light. It is formed as a non-single crystal material.

In order to form the surface layer 104 having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 101 and the gas pressure in the reaction vessel as desired. The temperature (Ts) of the support 101 is appropriately selected according to the layer design, but in the usual case, preferably 20 to 500 ° C., more preferably 50 to 450.
It is desirable to set the temperature to 100 ° C, optimally 100 to 400 ° C. Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the normal case, it is preferably 1
× 10 ^{-5 to} 100 Torr, more preferably 5 × 10 ^-5
-30 Torr, optimally 1 * 10 < ^-4 > ^-10 Torr is preferable. In the present invention, the temperature range described above is mentioned as a desirable numerical range of the support temperature and gas pressure for forming the surface layer, but the conditions are not usually independently determined separately, It is desirable to determine the optimum value based on the mutual and organic relationships to form a characteristic light-receiving member.

Further, in the present invention, it is also possible to provide 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. It is effective for further improving the characteristics of. 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. This can further reduce the influence of interference due to the reflected light at the interface between the surface layer and the photoconductive layer.

In the electrophotographic light-receiving member of the present invention, at least an aluminum atom, a silicon atom, a hydrogen atom or /
It is also desirable to have a layer region in which halogen atoms are contained in a non-uniform distribution state in the layer thickness direction.

Further, in the electrophotographic light-receiving member of the present invention, for the purpose of further improving the adhesion between the support 101 and the photoconductive layer 103, for example, Si ₃ N ₄ , SiO 2 is used.
₂ , an adhesion layer composed of an amorphous material containing SiO, or a silicon atom as a matrix and containing a hydrogen atom and / or a halogen atom, a carbon atom and / or an oxygen atom and / or a nitrogen atom, or the like may be provided. good. A charge injection blocking layer may be provided for the purpose of blocking the injection of charges from the support. Further, a light absorption layer may be provided in order to prevent the occurrence of an interference pattern due to the reflected light from the support.

[0058]

[Metal Layer] In the present invention, a metal layer having a metal bond is formed on the outermost surface of the light-receiving member thus produced. In the present invention, the metal atom contained in the metal layer may be an alkali metal element of Group Ia of the Periodic Table, or Group IIa.
Group Alkaline Earth Metals, Group IIIa, IVa
Group, Va group, VIa group, VIIa group, VIII group
At least one element selected from the group I, the group Ib, and the group IIb transition metal element can be mentioned.

Specific examples of the group Ia atom include lithium (Li), sodium (Na) and potassium (K), and examples of the group IIa atom include beryllium (Be) and magnesium (K). Mg), calcium (C
a), strontium (Sr), barium (Ba), etc. can be mentioned. Specific examples of the group IIIa atom include scandium (Sc) and yttrium (Y). Specific examples of the group IVa atom include titanium (Ti) and zirconium (Zr), and specific examples of the group VIa atom include:
Chromium (Cr), molybdenum (Mo), tungsten (W), etc. can be mentioned. Specific examples of the Group VIIa atom include manganese (Mn) and the like, and specific examples of the Group VIII atom include iron (Fe), cobalt (Co), nickel (Ni), and the like. . Specific examples of the group Ib atom include copper (Cu),
Silver (Ag), gold (Au), etc. may be mentioned.
As the b-group atom, zinc (Zn), cadmium (C
d), mercury (Hg) and the like.

In the present invention, the effect of the present invention can be obtained even with the above-mentioned single metal layer, but the effect of the present invention is further improved by using an alloy of at least two kinds of metals. In particular, it is preferable to contain at least one of Na, Ti, Fe, Co, Ni and Zn. Further, in order to achieve the object of the present invention, it is necessary that the metal atom forming the metal layer has a metal bond. Furthermore, the effect of the present invention can be effectively exhibited in a structure in which the metal atoms forming the metal layer are bonded to the atoms located substantially on the surface of the light receiving layer.

Further, in the present invention, the effect of increasing the strength of the metal layer is recognized by including at least one of carbon atom, oxygen atom and nitrogen atom in the metal layer. The content of carbon, oxygen and nitrogen is preferably 0.01 atom%.
-30 atom%, more preferably 0.05 atom% -20 atom%, optimally 0.1 atom% -10 atom% is desirable.
In addition to the above-mentioned atoms, any other atom can be contained as long as it is in a trace amount (1 atom% or less). However, in any case, it is necessary for the metal atom to have a metal bond in order to obtain the effects of the present invention.

The numerical range of the thickness of the metal layer is 20Å
It is preferably set to 100Å. When the film thickness of the metal layer is out of the above range, the effect of the present invention is significantly reduced. That is, when the thickness is less than 20 Å, the bonding between metal atoms is not sufficient, and when the thickness is more than 100 Å, the amount of light incident on the light receiving layer due to the difference in the refractive index between the metal layer and the light receiving layer and the light absorption of the metal layer itself. Decrease and decrease in sensitivity,
Due to the resistance of the metal layer, adverse effects such as image deletion may occur. When the metal layer is composed of a plurality of metals, the component ratio may change in the layer thickness direction.

In the present invention, the metal layer formed on the surface of the light receiving member in order to effectively achieve the object is prepared by appropriately setting the numerical method of the forming method and film forming parameters so as to obtain desired characteristics. Created. Specifically, a plasma CVD method, a sputtering method, a vacuum deposition method, an ion plating method, a cluster ion beam method, a coating method, an immersion method, etc. are usually used. These thin film deposition methods are based on manufacturing conditions, load level under capital investment, manufacturing scale,
It is appropriately selected and adopted depending on factors such as desired characteristics of the electrophotographic light-receiving member to be produced. For example, in order to form the metal layer 105 by the plasma CVD method, basically, a raw material gas for supplying metal capable of supplying metal atoms is introduced in a desired gas state into a reaction vessel whose inside can be depressurized. A glow discharge may be generated in the reaction vessel, and a metal layer may be formed on a support having a light-receiving layer formed in advance at a predetermined position.

In order to form the metal layer 105 by the sputtering method, an inert gas such as Ar or He, or a gas containing these gases as a base, and if necessary mixed with a gas for supplying a raw material, is introduced into the deposition chamber, By forming a plasma atmosphere of a desired gas by high-frequency discharge and sputtering the target, a metal layer is formed on the support placed at a predetermined position. Further, in order to form the metal layer 105 by the ion plating method, the metal is evaporated by the evaporation source arranged in the reaction vessel whose inside can be decompressed, and the high-frequency oscillation coil arranged so as to cover the evaporated particles causes discharge. Then, the evaporated particles are ionized, and the metal particles are transported by the electric field applied between the support and the evaporation source installed at a predetermined position to form a layer on the support.

In the present invention, as a starting material for forming the metal layer, a simple metal, an alloy, an intermetallic compound, a metal oxide, a gas for supplying a metal atom, etc. are appropriately used. As the substance that can serve as the metal atom supply gas, it is desirable to employ a substance that is gaseous at room temperature and atmospheric pressure or that can be easily gasified under at least the layer forming conditions. For example, sodium amine (N
An organic metal containing aNH ₃ ) or a sodium atom (Na) can be effectively used, and sodium amine is particularly preferable in view of easiness of handling during layer formation and good Na introduction efficiency.

As a substance that can be a gas for introducing Mg,
Organic metals containing magnesium atoms (Mg) are mentioned as being effectively used, and in particular, bis (cyclopentadienyl) magnesium Mg (C ₅ H) in terms of ease of handling during layer formation and good Mg introduction efficiency. ₅ ) ₂ is preferred. As a substance that can serve as a Y introduction gas, an organic metal containing an yttrium atom (Y) can be cited as a substance that can be effectively used. Particularly, triisopropanol yttrium is easy to handle during layer formation and has good Y introduction efficiency. Y (Oi-C
₃ H ₇ ) ₃ is preferred. As a substance that can be used as a gas for introducing Ti, an organic metal containing a titanium atom (Ti) can be mentioned as being effectively used. Pentadienyl) titanium (II) [Ti (C ₅ H ₅ ) ₂ ] ₂ is preferred. As a substance which can be used as a gas for introducing Cr, an organic metal containing a chromium atom (Cr) is mentioned as being effectively used, and hexacarbonyl chromium is particularly preferable in view of ease of handling during layer formation and good efficiency of introducing Cr. Cr (CO) ₆ is preferred. As a substance that can be used as a gas for introducing Mn, an organic metal containing a manganese atom (Mn) can be cited as a substance that can be effectively used.
Monomethylpentacarbonylmanganese Mn (CH ₃ ) (CO) ₅ is mentioned as a preferable one in terms of good introduction efficiency. As a substance that can be used as the Fe introduction gas, an organic metal containing an iron atom (Fe) can be mentioned as being effectively used, and in particular, it is easy to handle at the time of forming a layer and has good Fe introduction efficiency. Pentadienyl) iron (II)
Fe (C ₅ H ₅ ) ₂ is preferred. As a substance that can be used as a gas for introducing Co, an organic metal containing a cobalt atom (Co) can be effectively used, and in particular, hexacarbonyl (in terms of ease of handling during layer formation and good Co introduction efficiency) Acetylene) dicobalt Co ₂ (CO) ₆ (C
₂ H ₂ ) is preferred. As a substance that can be used as a gas for introducing Ni, an organic metal containing a nickel atom (Ni) can be mentioned as being effectively used. Glyoximato) nickel (II) Ni (C ₄ H ₇ N ₂ O ₂ ) ₂ is preferred. As a substance that can be used as a gas for introducing Cu, an organic metal containing a copper atom (Cu) can be mentioned as being effectively used. Oxymat copper Cu (C ₄
H ₇ N ₂ O ₂ ) ₂ is preferred. As a substance that can be used as a gas for introducing Zn, an organic metal containing a zinc atom (Zn) can be cited as a substance that can be effectively used. Particularly, in terms of ease of handling during layer formation and good Zn introduction efficiency, diethyl zinc Zn (C
₂ H ₅ ) ₂ is preferred.

[0067] Also, H ₂ in accordance with these metal atoms source gas for supplying necessary, He, Ar, may be diluted with a gas Ne or the like. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

A plurality of metal atoms forming the metal layer,
In order to form a layer having a desired state of distribution in the layer thickness direction by changing the distribution concentration of carbon atoms, oxygen atoms, and nitrogen atoms contained as necessary in the layer thickness direction, in the case of plasma CVD method Is performed by introducing the atom supply gas, whose distribution concentration is to be changed, into the deposition chamber by appropriately changing the gas flow rate according to the desired rate-of-change curve.
For example, the flow rate setting of the mass flow controller that controls the gas flow rate is appropriately changed by a commonly used method such as using a manual or programmable controller.

In the case of the sputtering method, first, in addition to the metal target, a raw material for introducing atoms is used in a gas state in the same manner as in the case of the plasma CVD method, and the gas flow rate is appropriately changed according to a desired change rate curve. And is introduced into the deposition chamber. Secondly, the mixing ratio of metal atoms forming the sputtering target is appropriately changed in the layer thickness direction in advance. Further, in the case of the ion plating method, the raw material for introducing the raw material atoms is used in a gas state in combination with the evaporation source in the same manner as in the case of the plasma CVD method, and the gas flow rate is appropriately changed according to the desired rate of change curve. , By introducing it into the deposition chamber.

In order to form the metal layer 105 having the characteristics capable of achieving the object of the present invention, the temperature of the support, the gas pressure, etc. are important factors that influence the characteristics of the metal layer. The optimum range of the support temperature is appropriately selected, but in the usual case, it is preferably 20 to 500 ° C., more preferably 50 to 450.
It is desirable to set the temperature to 100 ° C, optimally 100 to 400 ° C. The gas pressure in the deposition chamber is also selected as appropriate, but is preferably 1 × 10 ^{−5 to} 100 Torr, more preferably 5 ×.
10 ^{−5 to} 30 Torr, optimally 1 × 10 ^{−4 to} 10 Tor
It is desirable to set it as rr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature of the support and the internal pressure for forming the metal layer, but these layer forming factors are not usually independently determined. Instead, it is desirable to determine the optimum value of the layer formation factor based on mutual and organic relationships to form a metal layer with the desired properties.

In the present invention, the composition of the metal layer is appropriately selected so as to satisfy the required mechanical strength and environment resistance, but in any case, it is substantially transparent to the image exposure wavelength. And need not have photosensitivity to the pre-exposure and image exposure wavelengths.

Next, the apparatus and method for forming the light receiving layer and the metal layer will be described in detail. First, high frequency plasma CVD method and microwave plasma CVD
An apparatus and a forming method for forming a deposited film or a metal layer forming the light receiving layer by the method will be described in detail.
FIG. 3 shows high frequency plasma CVD (hereinafter referred to as "RF-PCVD").
(Hereinafter referred to as a “) method, a schematic explanatory view showing an example of an apparatus for manufacturing an electrophotographic light-receiving member, FIG. 4A shows a microwave plasma CVD (hereinafter referred to as“ μW-PCVD ”).
FIG. 4B is a schematic explanatory view showing an example of a deposited film forming apparatus for forming a deposited film for an electrophotographic light receiving member by the method, and FIG. 4B is a manufacturing process of the electrophotographic light receiving member by μW-PCVD It is an explanatory view of a device.

The structure of the apparatus for producing a deposited film by the RF-PCVD method shown in FIG. 3 is as follows. This apparatus is roughly classified into a deposition apparatus 3100 and a source gas supply apparatus 320.
0, an exhaust device (not shown) for reducing the pressure inside the reaction container 3111. A cylindrical support 3112, a support heating heater 3113, and a source gas introduction pipe 3114 are installed in a reaction vessel 3111 in the deposition apparatus 3100, and a high frequency matching box 3115 is further connected. Further, the source gas supply device 3200 is
A cylinder 3221 of a raw material gas such as iH ₄ , GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ and PH ₃ and an inert gas such as He and Ar.
~ 3227 and organometallic compound sealed container 3228
And valves 3231 to 237, 3241 to 347, 3
251 to 257 and mass flow controller 32
Each of the source gas cylinders is connected to a gas introduction pipe 3114 in the reaction vessel 3111 via a valve 3260.

The deposited film can be formed using this apparatus, for example, as follows. First, the reaction container 311
1, a cylindrical support 3112 is installed, and the inside of the reaction vessel 3111 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the cylindrical support 3112 is controlled to a predetermined temperature of 20 ° C. to 500 ° C. by the support heating heater 3113.

A source gas for forming a deposited film is supplied to the reaction vessel 311.
In order to make the gas flow into No. 1, the gas cylinder valves 3231-3
237, make sure that the leak valve 3117 of the reaction vessel is closed, and check the inflow valves 3241 to 324.
7, outflow valves 3251 to 3257, auxiliary valve 326
Make sure 0 is open, then first open main valve 3
118 is opened and the reaction container 3111 and the gas pipe 31 are opened.
Evacuate 16. Next, the reading of vacuum gauge 3119 is about 5 x 1
When the pressure reaches 0 ^-6 Torr, the auxiliary valve 3260 and the outflow valves 3251 to 3257 are closed. Then, each gas is supplied from the gas cylinders 3221 to 3227 to the valves 3231 to 332.
237 is opened and introduced, and pressure regulators 3261 to 3267
Each gas pressure is adjusted to ² kg / cm ² by. Next, the inflow valves 3241 to 3247 are gradually opened to introduce the respective gases into the mass flow controllers 3211 to 317.

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support 3112. First, when the cylindrical support 3112 reaches a predetermined temperature, the required ones of the outflow valves 3251 to 3257 and the auxiliary valve 3260 are gradually opened to open the gas cylinder 32.
A predetermined gas is introduced from 21 to 227 into the reaction container 3111 via the gas introduction pipe 3114. Next, the mass flow controllers 3211 to 217 are adjusted so that each raw material gas has a predetermined flow rate. At that time, the main valve 3118 is observed while observing the vacuum gauge 3119 so that the pressure inside the reaction vessel 3111 becomes a predetermined pressure of 1 Torr or less.
Adjust the opening of. When the internal pressure is stable, the RF power source (not shown) is set to a desired power, and the RF is fed into the reaction vessel 3111 through the high frequency matching box 3115.
Electric power is introduced to cause RF 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 3112. 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. Then, by repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

Needless to say, all of the outflow valves other than the necessary gas are closed when forming the respective layers, and the respective gases are supplied to the reaction vessel 3111.
From the outflow valves 3251 to 3257 to the reaction vessel 311
In order to avoid remaining in the piping reaching 1, the outflow valves 3251 to 3257 are closed, the auxiliary valve 3260 is opened, and the main valve 3118 is fully opened to temporarily exhaust the system to a high vacuum. Do it. Also,
In order to make the film formation uniform, the support 3112 is rotated at a predetermined speed by a driving device (not shown) during the film formation. Needless to say, the above-mentioned gas species and valve operation may be changed according to the preparation conditions of each layer.

The support temperature at the time of forming the deposited film is effective at any temperature, but particularly 20 ° C to 500 ° C, preferably 50 ° C to 450 ° C, more preferably 100 ° C to 400 ° C are preferable. It is preferable because it is shown.

Any method of heating the support may be used as long as it is a heating element having a vacuum specification, and more specifically, electric resistance heating elements 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 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 is used.

Next, a method for manufacturing the electrophotographic light-receiving member formed by the microwave plasma CVD method will be described. RF-PCV in the manufacturing apparatus shown in FIG.
By replacing the deposition apparatus 3100 by the D method with the deposition apparatus 4100 shown in FIG. 4A and connecting it with the source gas supply apparatus 3200, the μW plasma CVD shown in FIG. 4B is obtained.
An electrophotographic light-receiving member manufacturing apparatus having the following configuration can be obtained by the method.

This apparatus comprises a reaction vessel 4111 having a vacuum airtight structure and capable of reducing the pressure, and a source gas supply apparatus 320.
0, and an exhaust device (not shown) for reducing the pressure inside the reaction container. Microwave power is efficiently transmitted into the reaction vessel 4111, and
Materials that can maintain vacuum tightness (eg quartz glass,
A microwave waveguide connected to a microwave power source (not shown) via a microwave introduction window 4112 made of alumina ceramics, a stub tuner (not shown) and an isolator (not shown). 4113,
A cylindrical support 4115 on which a deposited film is to be formed, a support heating heater 4116, a source gas introduction pipe 4117, and an electrode 4118 for applying an external electric bias for controlling the plasma potential are installed, and a reaction vessel 4111. The inside is connected to a diffusion pump (not shown) through an exhaust pipe 4121.

The source gas supply device 3200 is composed of SiH ₄ ,
Cylinders 3221 to 322 of source gas such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ and PH ₃ and inert gas such as He and Ar
7 and an organometallic compound sealed container 3228 and valves 3231 to 237, 3241 to 347, 3251
3257 and mass flow controller 3211-3
217, and each source gas cylinder has a valve 32.
Gas introduction pipe 4117 in the reaction vessel 4111 through 60
It is connected to the. A space 4130 surrounded by the cylindrical support 4115 forms a discharge space.

The formation of the deposited film by this apparatus by the μW plasma CVD method can be performed as follows. First, the cylindrical support 4115 is installed in the reaction container 4111, the support 4115 is rotated by the driving device 4120, and the reaction container 4111 is exhausted through the exhaust pipe 4121 by an exhaust device (not shown) (for example, a vacuum pump). Then, the pressure in the reaction vessel 4111 is adjusted to 1 × 10 ⁻⁷ Torr or less. Then, the temperature of the cylindrical support 4115 is heated and maintained at a predetermined temperature of 20 ° C. to 500 ° C. by the support heating heater 4116.

A raw material gas for forming a deposited film is supplied to the reaction vessel 411.
In order to make the gas flow into No. 1, the gas cylinder valves 3231-3
237, make sure that the leak valve (not shown) of the reaction vessel is closed, and inflow valves 3241 to 3241
247, outflow valves 3251 to 3257, auxiliary valve 3
After confirming that 260 is open, first, a main valve (not shown) is opened to evacuate the inside of the reaction vessel 4111 and the gas pipe 4122. Next, when the reading of the vacuum gauge (not shown) reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve 3
260 and the outflow valves 3251 to 3257 are closed. After that, each gas is introduced from the gas cylinders 3221 to 327 by opening the valves 3231 to 237 and the pressure regulator 326.
Each gas pressure is adjusted to ² Kg / cm <2> by 1-3267. Next, the inflow valves 3241 to 3247 are gradually opened, and each gas is supplied to the mass flow controllers 3211 to 32.
Introduced in 17.

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support 4115. First, when the cylindrical support 4115 reaches a predetermined temperature, the necessary ones of the outflow valves 3251 to 3257 and the auxiliary valve 3260 are gradually opened, and the gas cylinder 32 is opened.
A predetermined gas from 21 to 227 is introduced into the discharge space 4130 in the reaction container 4111 via the gas introduction pipe 4117. Next, mass flow controllers 3211 to 317
Is adjusted so that each source gas has a predetermined flow rate. At 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 4130 becomes a predetermined pressure of 1 Torr or less. After the pressure has stabilized, a microwave power source (not shown) generates microwaves having a frequency of 500 MHz or more, preferably 2.45 GHz, and the microwave power source (not shown) is set to a desired power to guide the waves. ΜW energy is introduced into the discharge space 4130 through the tube 4113 and the microwave introduction window 4112 to cause μW glow discharge. Simultaneously with this, an electric bias such as direct current is applied from the power source 4119 to the electrode 4118. Thus, in the discharge space 4130 surrounded by the support body 4115, the introduced source gas is excited by the energy of microwaves and dissociated, so that a predetermined deposited film is formed on the cylindrical support body 4115. At this time, in order to make the layer formation uniform, the support rotation motor 4120 rotates the support at a desired rotation speed.

After the desired film thickness is formed, the supply of μW 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 4111.
From the outflow valves 3251 to 3257 to the reaction vessel 411
In order to avoid remaining in the pipe up to 1, the outflow valves 3251 to 257 are closed, the auxiliary valve 3260 is opened, and the main valve (not shown) is fully opened to temporarily exhaust the system to a high vacuum. Do as needed. Needless to say, the above-mentioned gas species and valve operation may be changed according to the preparation conditions of each layer.

The support temperature at the time of forming the deposited film is effective at any temperature, but particularly 20 ° C. to 500 ° C., preferably 50 ° C. to 450 ° C., more preferably 100 ° C. to 400 ° C. are preferable. It is preferable because it is shown.

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 liquid, 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 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 is used.

In the μW-PCVD method, the pressure in the discharge space is preferably 1 mTorr or more and 100 m or more.
Torr or less, more preferably 3 m Torr or more and 50 m
Torr or less, most preferably 5 m torr or more and 30 m
It is desirable to set it to less than Torr. The pressure outside the discharge space may be lower than the pressure inside the discharge space. However, when the pressure inside the discharge space is 100 mTorr or less, or particularly significantly below 50 mTorr, the pressure inside the discharge space is outside the discharge space. 3 times or more, the effect of improving the characteristics of the deposited film is particularly large.

As a method for introducing microwaves to the reaction furnace, a method using a waveguide can be mentioned. For introduction into the reaction furnace,
One method is to introduce through one or more dielectric windows. At this time, as materials for the microwave introduction window into the furnace, alumina (Al ₂ O ₃ ) and aluminum nitride (Al
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene, and other materials with low microwave loss are usually used. .

The electric field generated between the electrode and the support is preferably a direct current electric field, and the direction of the electric field is more preferably directed from the electrode to the support. The average magnitude of the DC voltage applied to the electrodes to generate the electric field is 15 V or more and 300
V or less, preferably 30 V or more and 200 V or less is suitable.
The DC voltage waveform is not particularly limited, and various waveforms are effective in the present invention. In other words, it does not matter in which case the direction of the voltage does not change with time. For example, not only the constant voltage whose magnitude does not change with time, but also the pulsed voltage and the magnitude rectified by the rectifier A pulsating voltage that changes is also effective. It is also effective to apply an AC voltage. There is no problem with the frequency of the alternating current, practically 50 Hz or 60 Hz for low frequencies and 13.56 for high frequencies.
MHz is suitable. The AC waveform may be a sine wave, a rectangular wave, or any other waveform, but a sine wave is practically suitable. However, the voltage at this time means an effective value in any case.

The size and shape of the electrode may be any as long as they do not disturb the discharge, but in practice, a cylindrical shape having a diameter of 1 mm or more and 5 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. The material of the electrode may be any as long as it has a conductive surface, for example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te,
Metals such as V, Ti, Pt, Pb, and Fe, alloys of these, or glass, ceramics, plastics whose surface is subjected to a conductive treatment are usually used.

Next, a device and a method for forming the metal layer 105 by the sputtering method and the ion plating method will be described in detail. First, an apparatus for forming a metal layer by a sputtering method and a film forming method will be described in detail. FIG. 5 shows high frequency sputtering (hereinafter, referred to as “bias-
It is a schematic explanatory drawing which shows an example of the manufacturing apparatus of the light receiving member for electrophotography by the method (it describes with SP).

The structure of the deposited film manufacturing apparatus by the bias-SP method shown in FIG. 5 is as follows. This apparatus is roughly classified into a deposition apparatus 5100, a gas supply apparatus 5200,
It is composed of an exhaust device (not shown) for reducing the pressure inside the deposition chamber 5101. In the deposition chamber 5101 in the deposition apparatus 5100, a target 511 that is a raw material for the metal layer is provided.
1, a support 5112, a support heating heater (not shown), and gas introduction pipes 5113 and 5114 are arranged, and a high frequency power source 5116 is connected to the target 5111 via a matching box 5115. Further, the support 5112 has a DC or high frequency bias power supply 511.
7 is connected.

The gas supply device 5200 uses Ar, He, H
Cylinders 5221 to 5227 of sputtering gas or source gas such as ₂ , O ₂ , N ₂ , CH _{4 and the} like, closed container 5228 filled with an organometallic compound, valves 5231 to 5237, 524
1 to 5247, 5251 to 5257 and mass flow controllers 5211 to 5217, and each gas cylinder is connected to gas introduction pipes 5113 and 5114 in the deposition chamber 5101 via auxiliary valves 5260 and 5261.

The film formation using this apparatus can be performed, for example, as follows. First, the support 5112 on which the photoconductive layer has been formed is installed in the deposition chamber 5101, and the inside of the deposition chamber 5101 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the support 5112 is controlled to a predetermined temperature of 20 ° C. to 50 ° C. by a heater (not shown) while rotating the support 5112 with a driving device (not shown) at a predetermined speed.

When the support 5112 reaches a predetermined temperature, the necessary ones of the outflow valves 5251 to 5257 and the auxiliary valves 5260 and 5261 are gradually opened, and the sputtering gas is supplied from the gas cylinders 5221 to 5227 through the gas introduction pipe 5113. Further, the source gas is introduced into the deposition chamber 5101 through the gas introduction pipe 5114. Next, the mass flow controllers 5211 to 5217 are adjusted so that each gas has a predetermined flow rate. At that time, the main valve 5 is observed while observing a vacuum gauge (not shown) so that the pressure in the deposition chamber 5101 becomes a predetermined pressure of 10 Torr or less.
Adjust the aperture of 102. When the internal pressure is stable, the high frequency power supply 5116 is set to a desired power, and the high frequency power is applied to the target 5111 via the matching box 5115 to cause glow discharge. Simultaneously with this, a predetermined RF bias, for example, is applied from the power source 5117 to the support 5112.

Sputtering gas atoms excited by this discharge energy collide with the target, thereby knocking out the target material, and the support 511 arranged oppositely.
This is where a predetermined deposited film is formed on 2. After the desired film thickness is formed, the high-frequency power supply is stopped, the outflow valve is closed to stop the gas from flowing into the deposition chamber, and the film formation is completed.

The support temperature at the time of forming the deposited film is effective at any temperature, but particularly 20 ° C to 500 ° C, preferably 50 ° C to 450 ° C, more preferably 100 ° C to 400 ° C is preferable. It is preferable because it is shown.

Any method of heating the support may be used as long as it is a heating element having a vacuum specification, and more specifically, electric resistance heating elements 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 liquid, 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 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 is used.

Next, an apparatus and a film forming method for forming a metal layer by the ion plating method will be described in detail. FIG. 6 is a schematic explanatory view showing an example of an apparatus for manufacturing a photoreceptive member for electrophotography by a high frequency excitation ion plating (hereinafter referred to as “RF-IP”) method.

The structure of the apparatus for producing a deposited film by the RF-IP method shown in FIG. 6 is as follows. This device is roughly classified into a deposition device 6100, a gas supply device 6200, and an exhaust device (not shown) for reducing the pressure in the deposition chamber 6101.
It consists of Deposition chamber 61 in deposition apparatus 6100
In 01, an electron beam evaporation source 611 which is a raw material of the metal layer is formed.
1. RF oscillation coil 6 placed so as to cover the evaporated particles
112, a support body 6113, a support body heating heater (not shown), and a gas introduction pipe 6114 are arranged.
16 are connected. A DC acceleration power source 6117 is connected to the support.

The gas supply device 6200 is equipped with H ₂ , O ₂ ,
Cylinders 6221 to 6227 of raw material gases such as N ₂ and CH ₄ and inert gases such as He and Ar, and a sealed container 6228 filled with an organometallic compound, valves 6231 to 6237, 62
41 to 6247, 6251 to 6257 and mass flow controllers 6211 to 6217, and a cylinder of each gas is deposited in a deposition chamber 610 via an auxiliary valve 6260.
1 is connected to the gas introduction pipe 6114.

The film formation using this apparatus can be performed, for example, as follows. First, in the deposition chamber 6101, the support 61 on which the photoconductive layer or the surface layer has been formed is finished.
13 is installed and an exhaust device (not shown) (for example, a vacuum pump)
The inside of the deposition chamber 6101 is exhausted by. Then, the support 6
While the 113 is rotated at a predetermined speed by a driving device (not shown), the support 61 is rotated by a heater (not shown).
The temperature of 13 is controlled to a predetermined temperature of 20 ° C to 500 ° C.

When the support 6113 reaches a predetermined temperature, the necessary ones of the outflow valves 6251 to 6257 and the auxiliary valve 6260 are gradually opened, and the gas introduction pipe 6 is opened.
A source gas is introduced into the deposition chamber 6101 through 114. Next, mass flow controllers 6211-6217
Is adjusted so that each gas has a predetermined flow rate. At that time, the opening of the main valve 6102 is adjusted while observing a vacuum gauge (not shown) so that the pressure in the deposition chamber 6101 becomes a predetermined pressure of 10 Torr or less. When the internal pressure is stable, a predetermined DC voltage is applied from the power source 6117 to the support 6113, and the metal of the evaporation source is heated by an electron beam or the like to evaporate the metal particles. Simultaneously with this, the high frequency power supply 6116 is set to a desired power, and high frequency power is applied to the RF coil through the matching box 6115 to cause discharge.

The vapor-deposited particles ionized by this discharge energy are accelerated by the electric field with the support 6113, and a predetermined deposited film is formed on the support 6113 facing each other. After the desired film thickness is formed, the electron beam, the high frequency power and the direct current power are stopped, and the outflow valve is closed to stop the gas from flowing into the deposition chamber.
Finish film formation.

The support temperature at the time of forming the deposited film is effective at any temperature, but particularly 20 ° C to 50 ° C, preferably 50 ° C to 450 ° C, more preferably 100 ° C to 400 ° C is preferable. It is preferable because it is shown.

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 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 is used.

[0111]

[Experimental Example] Hereinafter, the effect of the present invention will be specifically described with reference to an experimental example.

[0112]

[Experimental Example 1] Using the apparatus for manufacturing a photoreceptive member for electrophotography shown in FIG. 3, on an aluminum cylinder having a mirror finish, the manufacturing conditions shown in Table 1 by the RF-PCVD method according to the procedure detailed above. To form a photoreceptive layer, and then, using the manufacturing apparatus by the bias-SP method shown in FIG.
Under the conditions of an electric power of 100 W and an RF bias of 50 W, a thin layer having a layer thickness of 50 Å was formed on the light receiving layer to prepare a light receiving member for electrophotography. At this time, by changing the type of the target, various materials for the thin layer were changed, and several kinds of electrophotographic light-receiving members were produced.

The photoreceptive member for electrophotography manufactured in Experimental Example 1 was installed in an electrophotographic apparatus modified from Canon Copier NP-6150 for an experiment, and images of the initial stage and after accelerated durability equivalent to 2 million sheets were recorded. I checked "Gasatsuki". The results are shown in Table 2. In Table 2, with respect to rustiness, image density at 100 points was measured with a circular region having a diameter of 0.05 mm as one unit, and variations in the image density were evaluated. For each, ◎ is "especially good", ○
Indicates “good”, Δ indicates “no problem in practical use”, and × indicates “problem in practical use”. As shown in Table 2, it has been found that particularly good results are obtained when the material of the metal layer is an alkali metal, an alkaline earth metal or a transition metal.

[0114]

[Experimental Example 2] Using the electrophotographic light-receiving member manufacturing apparatus shown in FIG. After forming the receptive layer, the bias shown in FIG.
-Using a manufacturing apparatus based on the SP method, using He as the sputtering gas
Using an internal pressure of 0.1 Torr, RF power of 300 W, R
Under the condition of F bias of 20 W, a metal layer made of Ti was formed on the light receiving layer to prepare a light receiving member for electrophotography. At this time, various kinds of electrophotographic light-receiving members were produced by changing the thickness of the Ti layer variously.

The electrophotographic light-receiving member thus produced was installed in an electrophotographic apparatus which was a Canon copying machine NP-6150 modified for experiments, and "chargeability", "sensitivity",
"Image deletion" and "image unevenness" were examined. Table 3 shows the results. In Table 3, ⊚ indicates “particularly good”, ◯ indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”. As shown in Table 3, it has been found that particularly good results are obtained when the layer thickness of the metal layer is in the range of 20 to 100Å. Further, when the cleaning blade was observed under a microscope after the durability test, almost no defects were observed in the light receiving member in the above range.

[0116]

EXAMPLES The constitution of the present invention was determined by the above experimental examples. Next, examples and comparative examples of the present invention will be described in more detail, but the present invention is not limited thereto.

[0117]

EXAMPLE 1 Using an apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 3, a mirror-finished aluminum cylinder (support) was formed according to the procedure detailed above. A photoreceptive layer having a photoconductive layer and a surface layer, and a metal layer were formed under the above-mentioned production conditions to prepare a photoreceptive member for electrophotography.

[0118]

Comparative Example An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that the metal layer was not formed on the surface of the light-receiving layer. The electrophotographic light-receiving members produced in Example 1 and Comparative Example were replaced with the Canon copier NP-manufactured in the same manner as in the Experimental Example.
Install the 5060 in the electrophotographic device modified for the experiment,
When the charging ability, sensitivity, image unevenness, rubbing, and cleaning performance were evaluated in the same manner as in the experimental example, all the items in Example 1 were better than the comparative example. In addition, the electrophotographic light-receiving member manufactured in Example 1 was processed by XPS.
As a result of the binding state analysis by (ESCA), the presence of metal bonds was confirmed in the metal layer.

[0119]

Example 2 Using the apparatus for producing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. 3, the photoreceptive layer including the photoconductive layer and the surface layer was prepared in the same manner as in Example 1 under the production conditions shown in Table 5. Then, a metal layer is formed on the surface layer under the manufacturing conditions shown in Table 6 by using the apparatus for manufacturing an electrophotographic light-receiving member by the bias-SP method shown in FIG. A member was produced. When the electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1, the same favorable results as in Example 1 were obtained.

[0120]

[Embodiment 3] Using the apparatus for manufacturing a photoreceptive member for electrophotography by the RF-PCVD method shown in FIG. Then, using the apparatus for manufacturing an electrophotographic light-receiving member by the RF-IP method shown in FIG. 6, a metal layer is formed on the surface layer under the manufacturing conditions shown in Table 8 to form an electrophotographic light-receiving member. It was made. When the electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1, the same favorable results as in Example 1 were obtained.

[0121]

Fourth Embodiment μW− shown in FIGS. 4 (a) and 4 (b)
Using an apparatus for producing a photoreceptive member for electrophotography by the PCVD method, a charge injection blocking layer, a photoconductive layer, and a photoconductive layer were formed on a mirror-finished aluminum cylinder according to the procedure described in detail above according to the procedure described above. A light-receiving layer composed of a surface layer is formed, and subsequently, a metal layer is formed on the surface layer under the manufacturing conditions shown in Table 6 by using the manufacturing apparatus for a light-receiving member for electrophotography by the bias-SP method shown in FIG. Then, a light receiving member for electrophotography was produced. When the electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1, the same favorable results as in Example 1 were obtained. In addition, as a result of analyzing the binding state by XPS of the electrophotographic light-receiving member manufactured in this example, the presence of a metal bond in the metal layer and a bond between the metal and a silicon atom in the surface layer were confirmed.

[0122]

[Embodiment 5] μW− shown in FIGS. 4 (a) and 4 (b)
Using the apparatus for producing a photoreceptive member for electrophotography by the PCVD method, a photoreceptive layer including a charge injection blocking layer, a charge transport layer, a charge generation layer, and a surface layer was formed under the production conditions shown in Table 10, and subsequently, FIG. Using the apparatus for manufacturing a light-receiving member for electrophotography by the RF-IP method shown in, a metal layer was formed on the surface layer under the manufacturing conditions shown in Table 8 to manufacture a light-receiving member for electrophotography.
When the electrophotographic light-receiving member thus obtained was evaluated in the same manner as in Example 1, the same favorable results as in Example 1 were obtained.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

[0130]

[Table 8]

[0131]

[Table 9]

[0132]

[Table 10]

[0133]

EFFECTS OF THE INVENTION The electrophotographic light-receiving member of the present invention having the above-mentioned specific structure can solve all the problems in the conventional electrophotographic light-receiving member made of A-Si. In particular, it exhibits extremely excellent electrical properties, optical properties, photoconductive properties, image properties, durability and use environment properties. Particularly, in the present invention, by forming an extremely thin metal layer on the surface of the light-receiving layer, it is possible to compensate for minute defects on the surface of the light-receiving layer and suppress deterioration of charging ability and non-uniformity of charging due to injection of surface charges. In addition, since a dense metal layer is present on the surface, the toner releasability and cleaning property due to the surface property are improved,
It is characterized by having extremely excellent potential characteristics and image characteristics.

[Brief description of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining a layer configuration of a preferred embodiment of a light receiving member for electrophotography of the present invention.

FIG. 2 is a schematic layer configuration diagram for explaining a layer configuration of a conventional electrophotographic light-receiving member.

FIG. 3 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, which is a schematic view of an apparatus for manufacturing a light-receiving member for electrophotography by a glow discharge method using high frequency (RF). FIG.

FIG. 4 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention, which is a schematic view of an apparatus for manufacturing a light-receiving member for electrophotography by a glow discharge method using microwave (μW). FIG.

FIG. 5 is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography of the present invention, which is a schematic view of an apparatus for manufacturing a light-receiving member for electrophotography by a glow discharge method using microwave (μW). FIG.

FIG. 6 is an example of an apparatus for forming a metal layer of an electrophotographic light-receiving member of the present invention, which is a schematic explanatory view of an apparatus for manufacturing an electrophotographic light-receiving member by a sputtering method using high frequency (RF). Is.

FIG. 7 is another example of an apparatus for forming a metal layer of an electrophotographic light-receiving member of the present invention, which is an apparatus for manufacturing an electrophotographic light-receiving member by an ion plating method using high frequency (RF). It is a schematic explanatory view.

[Explanation of symbols]

 100,200 Photoreceptive member 101,201 Conductive support 102,202 Photoreceptive layer 103,203 Photoconductive layer 104,204 Surface layer 105,205 Charge injection blocking layer 106 Metal layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display area G03G 5/08 336 G03G 5/08 336 (72) Inventor Junichiro Hashizume 3-30 Shimomaruko, Ota-ku, Tokyo No. 2 in Canon Inc. (72) Inventor Tetsuya Takei 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (5)

[Claims] 1. A photoreceptive member for electrophotography, comprising at least a support and a photoreceptive layer comprising a photoconductive layer having photoconductivity and formed of a non-single crystal material having silicon atoms on the support as a matrix. 2. A photoreceptive member for electrophotography, comprising forming a substantially uniform metal layer having a metal bond on the photoreceptive layer. 2. The photoreceptive layer comprises a photoconductive layer made of a non-single-crystal material having silicon atoms as a matrix, and a surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen. It is comprised from 1.
The light-receiving member for electrophotography according to item 1. 3. The photoreceptive layer comprises a photoconductive layer made of a non-single-crystal material having silicon atoms as a matrix, and a surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen. And a charge injection blocking layer made of a non-single-crystal material having silicon atoms as a base and containing at least one of carbon, oxygen and nitrogen and at least one atom selected from Group IIIb or Group Vb of the periodic table. The light-receiving member for electrophotography according to claim 1, wherein the light-receiving member is for electrophotography. 4. The metal film layer has a layer thickness of 20Å to 100.
4. The light-receiving member for electrophotography according to claim 1, wherein the light-receiving member is Å. 5. The photoreceptor for electrophotography according to claim 1, wherein the metal film layer is composed of at least one element selected from alkali metals, alkaline earth metals and transition metals. Element.