JPH0454941B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. In terms of stability, stability over time, and durability, each individual property has been improved, but the reality is that there is still room for further improvement in terms of overall property improvement. be. For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use, and this type of photoconductive member When used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon in which an afterimage occurs. When the photoconductive layer is made of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In some cases, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, or ,
For example, there may be image defects commonly called "white spots" on images transferred to transfer paper, which are thought to be caused by localized discharge breakdown phenomena, or defects that may be caused by rubbing when a blade is used for cleaning, for example. A so-called image defect called "white stripe" may occur. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. You can win by causing phenomena such as ``happening''. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] "a-Si(H,X)" is used as a generic notation for The photoconductive material produced by this method not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, and is particularly effective as a photoconductive material for electrophotography. This is based on the discovery that it has excellent properties. The electrical, optical, and photoconductive properties of the present invention are virtually always stable regardless of the environment in which it is used, and it is extremely resistant to light fatigue and does not deteriorate even after repeated use, making it durable. The main object of the present invention is to provide a photoconductive member that has excellent moisture resistance and has no or almost no residual potential observed. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. Still another object of the present invention is to provide high density images without any image defects or blurring during long-term use.
An object of the present invention is to provide a photoconductive member for electrophotography in which it is possible to easily obtain high-quality images with clear halftones and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics and high voltage resistance. The photoconductive member of the present invention is a photoconductive member that has a support for the photoconductive member and a first amorphous layer that is made of an amorphous material containing silicon atoms as a matrix and exhibits photoconductivity. a first layer region in which the first amorphous layer contains oxygen atoms as constituent atoms;
a second layer region containing atoms belonging to Group Group of the Periodic Table as constituent atoms, and the first layer region and the second layer region are provided in contact with the support body and are at least mutually The layer thickness of the second layer region is _tB , and the difference between the layer thickness of the first amorphous layer and the layer thickness _tB of the second layer region is T. Then, the relationship t _B /(T + t _B )≦0.4 is established, and the first amorphous layer is made of an amorphous material containing silicon atoms, carbon atoms, and halogen atoms as constituent atoms. It is characterized by having a second amorphous layer. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is tough and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 has a-Si (H,
an amorphous layer ( ) 102 consisting of
and a second amorphous layer ( ) 1 formed of an amorphous material having silicon atoms, carbon atoms, and hydrogen atoms as constituent atoms, provided on the amorphous layer ( ) 102
07. The amorphous layer ( ) 102 includes a first layer region (O) 103 containing oxygen atoms as constituent atoms, and a second layer region (V) containing atoms belonging to group group of the periodic table (group atoms). ) 104, and a layer region 106 on the second layer region (V) 104 that does not contain oxygen atoms or group atoms. Layer region 105 provided between first layer region (O) 103 and layer region 106 contains group group atoms but does not contain oxygen atoms. The oxygen atoms contained in the first layer region (O) 103 or the group group atoms contained in the second layer region (V) 104 are continuously arranged in the layer thickness direction in each layer region. Preferably, it is uniformly distributed, and is continuously and substantially uniformly distributed in a plane substantially parallel to the surface of the support 101. In the photoconductive member of the present invention, such as the example shown in FIG. (corresponds to the surface layer region 106 shown in the figure)
However, a layer region (layer region 105 shown in FIG. 1) that contains group atoms but does not contain oxygen atoms does not necessarily need to be provided. That is, for example, in FIG. 1, the first layer region (O) 103 and the second layer region (V) 104 may be the same layer region, or the first layer region (O) ) 103 may be provided with a second layer region (V) 104. In the photoconductive member of the present invention, the first layer region (O) contains oxygen atoms to provide a high dark resistance and a bond with the support on which the amorphous layer () is directly provided. The focus was placed on improving the adhesion between the layers, and the layer region on the surface side of the amorphous layer () did not contain oxygen atoms, further improving moisture resistance and corona ion resistance and increasing sensitivity. is being focused on. In particular, like the photoconductive member 100 shown in FIG.
The amorphous layer ( ) 102 includes a first layer region (O) 103 containing oxygen atoms, a second layer region (V) 104 containing group group atoms, and a layer region 105 containing no oxygen atoms. , and a layer region 106 containing no oxygen atoms or group atoms,
First layer region (O) 103 and second layer region (V)
Better results are obtained with a layer structure having a layer area shared with 104. In the photoconductive member of the present invention, the amorphous layer ()
The first layer region (O), which constitutes a part of the amorphous layer (O) and contains oxygen atoms, is used for the purpose of improving the adhesion of the amorphous layer (O) with the support. The second layer region (V) that constitutes a part of the amorphous layer () and contains group atoms is, for one thing, amorphous layer ().
Each support is supported as part of the amorphous layer () in order to prevent charges from being injected into the amorphous layer () from the support side when the free surface side of the material is charged. A structure is provided in which the body and the amorphous layer share at least a part of each other as a bonding layer region. In addition, in order to more effectively improve the adhesion between the support of the second layer region (V) or the layer region provided directly on the second layer region (V), The first layer region (O) is provided so as to encompass the second layer region (V) from the contact interface with the support. The first layer region (O) is packed so that the layer structure extends from the contact interface with the support to above the second layer region (V) and includes the second layer region (V). It is preferable to provide it in the amorphous layer ( ). In the present invention, the atoms belonging to group of the periodic table contained in the second layer region (V) constituting the amorphous layer () are P (phosphorus),
These include As (arsenic), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferably used. In the present invention, the content of group atoms contained in the second layer region (V) may be appropriately determined as desired so as to effectively achieve the object of the present invention. Usually 30 to 5 in (V)
×10 ⁴ atomic ppm, preferably 50 to 1 × 10 ⁴
atomic ppm, optimally 100 to 5×10 ³ atomic
It is preferable to set it in ppm. The amount of oxygen atoms contained in the first layer region (O) is also determined as desired depending on the characteristics required of the photoconductive member to be formed, but in normal cases,
0.001~50atomic%, preferably 0.002~
It is desirable that the content be 40 atomic%, most preferably 0.003 to 30 atomic%. In the photoconductive member of the present invention, the layer thickness t _B of the layer region (V) containing group group atoms (the layer thickness of the layer region 104 in FIG. 1), The layer thickness T of the layer region (layer region 106 in Fig. 1) excluding the layer region (V) provided in However, more preferably, the value of the relational expression shown above is 0.35 or less, most preferably 0.3 or less. In the present invention, the layer thickness t _B of the layer region (V) containing group atoms is usually 30 Å to 5 μ, preferably 40 Å to 4 μ, and optimally 50 Å to 3 μ. It is desirable. Further, the sum of the layer thickness T and the layer thickness _tB (T+ _tB ) is usually 1 to 100μ, preferably 1 to 80μ, and most preferably 2 to 50μ. . The layer thickness t _O of the layer region (O) containing oxygen atoms may be determined as appropriate for the desired purpose in relation to the layer thickness t _B of the layer region (V) that shares at least a part of the layer region. Therefore, it is desirable that the That is, if the purpose is to strengthen the adhesion between the layer region (V) and the support that is in direct contact with the layer region (V), the layer region (O) is the support for the layer region (V). Since it is sufficient that it is provided at least in the body side end layer region, the layer thickness t _O of the layer region (O) may be at most the layer thickness t _B of the layer region (V). Moreover, if the aim is to strengthen the adhesion between the layer region (V) and the layer region provided directly on the layer region (V) (corresponding to the layer region 106 in FIG. 1), Since it is sufficient that the layer region (O) is provided at least at the end portion of the layer region (V) opposite to the side where the support is provided, the layer thickness t _O of the layer region (0) is as follows. It is sufficient to have at most the layer thickness t _B of the layer region (V). Furthermore, considering the case where the above two points are satisfied, the layer thickness t _O of the layer region (O) must be at least equal to the layer thickness t _B of the layer region (V), and in this case, It is necessary to have a layer structure in which a layer region (V) is provided in the region (O). In order to more effectively measure the adhesion between the layer region (V) and the layer region provided directly on the layer region (V), place the layer region (O) above the layer region (V) (supporting the layer region (V)). It is preferable that it extends in the direction opposite to the side of the body. In the present invention, a portion containing no oxygen atoms is provided in the end layer region of the amorphous layer () on the side of the amorphous layer (), and a layer region (O) is provided on the support side of the amorphous layer (). When locally unevenly distributed, the layer thickness t _O can be determined as desired while taking into account the above points, but it is usually 10〓 to 10μ, preferably
It is desirable that the thickness be 20〓 to 8μ, optimally 30〓 to 5μ. In the photoconductive member 100 shown in FIG. 1, the second amorphous layer ( ) 107 formed on the first amorphous layer ( ) 102 has a free surface 108 and is primarily moisture resistant. properties, continuous repeated use characteristics, pressure resistance,
This is provided in order to achieve the objectives of the present invention in terms of usage environment characteristics and durability. Further, in the present invention, the first amorphous layer ()
102 and the second amorphous layer ( ) 107 each have a common constituent element of silicon atoms, ensuring chemical stability at the laminated interface. It is fully accomplished. The second amorphous layer ( ) 107 is an amorphous material [a-(Si _x C _1-x ) _y X _1-y , where 0<x,
y<1]. The second amorphous layer () composed of a-( _{Si x} C _1-x ) _y This is done by the beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having the above-mentioned photoconductive member. The glow discharge method or the sputtering method is preferably employed because of the advantages that it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second amorphous layer (2) to be produced. Furthermore, in the present invention, the second amorphous layer ( ) may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the second amorphous layer () by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y X _1-y is mixed with a diluent gas as necessary. The mixture is mixed at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and the gas is already deposited on the support. The first amorphous layer formed ()
It is sufficient to deposit a-(Si _x C _1-x ) _y X _1-y thereon. In the present invention, the raw material gas for forming a-(Si _x C _1-x ) _y X _1-y is a gaseous substance containing at least one of Si, C, and Most gasified substances that can be gasified can be used. When using a raw material gas containing Si as one of Si, C, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing Alternatively, a raw material gas containing Si and a raw material gas containing C and X may be mixed at a desired mixing ratio. or with a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, F, Cl, Br, and I are preferable as the halogen atoms (X) contained in the second amorphous layer ( ), with F and Cl being particularly preferable. In the present invention, the second amorphous layer (a)
-(Si _x C _1-x ) _y X _1-y , but it is possible to further contain a hydrogen atom. The inclusion of hydrogen atoms in the second amorphous layer () is
This is advantageous in terms of production costs because it is possible to share some of the raw material gas types when forming a continuous layer with the first amorphous layer (2). In the present invention, raw material gases that can be effectively used to form the second amorphous layer () include those in a gaseous state at room temperature and pressure, or those that can be easily gasified. Can list substances. Examples of the substance for forming the second amorphous layer include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 3 carbon atoms.
acetylenic hydrocarbons, elemental halogens, hydrogen halides, interhalogen compounds, silicon halides,
Examples include halogen-substituted silicon hydride and silicon hydride. Specifically, saturated hydrocarbons include methane (CH ₄ ), methane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₆ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Acetylene (C ₂ H ₂ ), Methylacetylene (C ₃
H ₄ ), butyne (C ₄ H ₆ ), and halogen alone:
Halogen gases such as fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH, HI, HCl, HBr,
Interhalogen compounds include BrF, ClF, ClF ₃ ,
ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃
Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂
Cl ₂ , SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ ,
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₆ ,
Examples include silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ . In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃
Halogen-substituted paraffinic hydrocarbons such as F, CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Si( Alkyl silicides such as C ₂ H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ can also be mentioned as effective. These second amorphous layer () forming substances contain silicon atoms, carbon atoms, halogen atoms and optionally hydrogen atoms in a predetermined composition ratio in the second amorphous layer () to be formed. It is selected and used as desired when forming the second amorphous layer (2) so that it contains atoms. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiCl can contain halogen atoms. ₄ , SiH ₂ Cl ₂ , or SiH ₃ Cl at a predetermined mixing ratio and introducing it in a gaseous state into the apparatus for forming the second amorphous layer () to generate a glow discharge. −(Si _x
A second amorphous layer ( ) consisting of C _1-x ) _y (Cl+H) _1-y can be formed. To form the second amorphous layer () by the sputtering method, target a single-crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C; These may be performed by sputtering in various gas atmospheres containing halogen atoms and, if necessary, hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing C and The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least halogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. C and X, H as necessary
The material for forming the second amorphous layer shown in the glow discharge example described above can also be used as a material gas for the sputtering method. In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluent gas when forming the second amorphous layer () by a glow discharge method or a sputtering method. It can be mentioned as a suitable one. The second amorphous layer ( ) in the present invention is carefully formed so as to provide the desired properties. In other words, substances whose constituent atoms are Si, C, X, and optionally H can have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrically conductive to semiconducting. In the present invention, a- (Si _x
The preparation conditions are strictly selected according to the desired conditions so that C _1-x ) _y X _1-y is formed. For example _, to provide the second amorphous layer () with the main purpose of improving voltage resistance, a-(Si _x C _1-x ) _y Created as a distinctly amorphous material. In addition, if a second amorphous layer () is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation described above will be relaxed to some extent, and it will be more effective against the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y X _1-y
is created. a−(Si _x C _1-x ) _y on the surface of the first amorphous layer ()
When forming the _second amorphous layer ( ) consisting of In this case, a-(Si _x
It is desirable that the temperature of the support during layer formation be strictly controlled so that C _1-x ) _y X _1-y can be formed as desired. In the present invention, an optimal range is selected as appropriate in accordance with the method of forming the second amorphous layer () in order to effectively achieve the desired purpose, and the second amorphous layer () is formed. formation is performed, but typically 50~
The temperature is desirably 350°C, preferably 100-250°C. In order to form the second amorphous layer (2018), we use a glow method, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. It is advantageous to adopt the discharge method or the sputtering method, but when forming the second amorphous layer () using these layer formation methods, the temperature during layer formation as well as the support temperature described above must be adjusted. The discharge power is one of the important factors that influences the characteristics of a-(Si _x C _1-x ) _y X _1-y created. _The discharge power condition for effectively producing a-(Si _x C _1-x ) _y
300W, preferably 20-200W. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the preferable numerical ranges of the support temperature and discharge power for forming the second amorphous layer ( ) include the values in the above ranges, but these layer forming factors are independent of each other. The desired characteristics a−(Si _x C _1-x ) _y
It is desirable that the optimum value of each layer formation factor be determined based on the mutual organic relationship so that the second amorphous layer ( ) consisting of X _1-y is formed. The amounts of carbon atoms and halogen atoms contained in the second amorphous layer () in the photoconductive member of the present invention are the same as the conditions for producing the second amorphous layer ().
This is an important factor in the formation of the second amorphous layer (), which provides the desired properties to achieve the objectives of the present invention. The amount of carbon atoms contained in the second amorphous layer () in the present invention is usually 1×10 ^-3 to 90 atomic%,
Suitably 1 to 90 atomic%, optimally 10 to 90 atomic%
A desirable value is 80 atomic%.
The content of halogen atoms is usually 1
It is desirable that the halogen atom content be ~20 atomic%, preferably 1-18 atomic%, optimally 2-15 atomic%, and when the halogen atom content is within these ranges,
The produced photoconductive member can be sufficiently applied to practical applications. The content of hydrogen atoms, which may be included as necessary, is usually 19 atomic %, preferably 13 atomic % or less. That is, x, y of the previous a-(Si _x C _1-x ) _y X _1-y
If done by display, x is usually 0.1 to 0.99999, preferably 0.1
~0.99, optimally 0.15~09, y usually 0.8~0.99,
It is preferably 0.82 to 0.99, most preferably 0.85 to 0.98. When both a halogen atom and a hydrogen atom are included, a-(Si _x C _1-x ) _y (H+
If expressed as X) _1-y, the numerical range of x and y in this case is almost the same as the case of a-(Si _x C _1-x ) _y X _1-y . The numerical range of the layer thickness of the second amorphous layer ( ) in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. Also, the layer thickness of the second amorphous layer () is also in relation to the layer thickness of the first layer region (O) 103,
It needs to be appropriately determined as desired based on organic relationships depending on the characteristics required for each layer region. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. In the present invention, the thickness of the second amorphous layer (2) is preferably normally 0.003 to 30μ, preferably 0.004 to 20μ, and most preferably 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a pelt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the present invention, the amorphous layer () composed of a-Si (H, done by. For example, by glow discharge method,
In order to form an amorphous layer ( ) composed of a-Si (H, A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. An amorphous layer () made of a-Si(H,X) may be formed on the surface of the support. In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, if necessary, an amorphous layer ()
Specific examples of the halogen atom (X) contained therein include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
An amorphous layer () made of a-Si containing halogen atoms can be formed on a predetermined support. When forming an amorphous layer ( ) containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar,
Gases such as H ₂ and He are introduced into a deposition chamber where an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. By forming an amorphous layer ( ) on a predetermined support, in order to introduce hydrogen atoms, a silicon compound gas containing hydrogen atoms is added to these gases. A predetermined amount of these materials may also be mixed to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form an amorphous layer () made of a-Si(H,
This is sputtered in a predetermined gas plasma atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam. Law (EB Law)
This can be carried out by heating and evaporating the evaporated material by means of a method such as the above, and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective. It can be mentioned as a starting material for forming an amorphous layer. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the amorphous layer. In the present invention, it is used as a suitable raw material for introducing halogen atoms. In order to structurally introduce hydrogen atoms into the amorphous layer (), in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be achieved by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, an amorphous layer () made of a-Si(H,X) is formed on the support. In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the amorphous layer () of the photoconductive member to be formed is normally 1~
It is desirable that the content be 40 atomic %, preferably 5 to 30 atomic %. Hydrogen atoms (H) contained in the amorphous layer ()
Or/and to control the amount of halogen atoms (X), for example, the support temperature or/and hydrogen atoms (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In order to provide the layer region (V) containing Group Group atoms and the layer region (O) containing oxygen atoms in the amorphous layer (), the amorphous layer () is formed by a glow discharge method, a reactive sputtering method, etc. In the formation of the amorphous layer, a starting material for introducing a group atom and a starting material for introducing an oxygen atom are used together with the starting material for forming an amorphous layer described above, and the amount thereof is determined in the formed layer. This is achieved by controlling and containing the When a glow discharge method is used to form the layer region containing oxygen atoms (O) and the layer region containing group atoms (V), which constitute the amorphous layer (), each layer region is formed. The starting materials to be used as raw material gases are selected as desired from among the starting materials for forming the amorphous layer described above, and the starting materials for introducing oxygen atoms and/or group atoms are added. Starting material for introduction is added. Such starting materials for introducing oxygen atoms or starting materials for introducing group atoms include gaseous substances or gasified substances whose constituent atoms are at least oxygen atoms or group atoms. Most can be used. For example, if a layer region (O) is to be formed, a raw material gas containing silicon atoms (Si) as constituent atoms,
A raw material gas containing oxygen atoms (O) as constituent atoms and a raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as necessary are mixed at a desired mixing ratio and used. Or, a raw material gas containing silicon atoms (Si) and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) are also mixed at a desired mixing ratio. ,
Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si) and oxygen atoms (O)
and a raw material gas containing three hydrogen atoms (H) as constituent atoms can be used in combination. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms. Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monooxide (N ₂ O ), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si) and oxygen atoms (O )
and a hydrogen atom (H) as constituent atoms, for example,
Disiloxane H ₃ SiOSiH ₃ , Trisiloxane H ₃
Examples include lower siloxanes such as SiOSiH ₂ OSiH ₃ and the like. When the layer region (V) is formed using a glow discharge method, starting materials for introducing group group atoms that are effectively used in the present invention include PH ₃ and P ₂ H for introducing phosphorus atoms. Phosphorus hydride such as ₄ , PH ₄ I,
Examples include phosphorus halides such as PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , PI ₃ and the like. In addition, AsH ₃ ,
AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ ,
SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. The content of group atoms introduced into the layer region (V) containing group atoms is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, the support It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. To form the layer region (O) containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or a SiO ₂ wafer, or a Si
This can be carried out by targeting a wafer containing a mixture of SiO 2 and SiO ₂ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. In the photoconductive member of the present invention, a layer region (B) not containing group atoms is provided on the layer region (V) containing group atoms (corresponding to layer region 106 in FIG. 1). The layer region (B) contains a substance that controls conduction properties.
The conduction properties of can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-
P gives P-type conduction characteristics to Si(H,X)
Type impurities, specifically atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium),
Among them, B and Ga are particularly preferably used. In the present invention, the content of the substance that controls the conductive properties contained in the layer region (B) is determined by the conductive properties required for the layer region (B) or the substance that is in direct contact with the layer region (B). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided as well as the characteristics of the contact interface with the other layer regions. In the present invention, the content of the substance controlling conduction properties contained in the layer region (B) is usually 0.001 to 1000 atomic ppm, preferably 0.05 atomic ppm.
~500atomic ppm, optimally 0.1-200atomic
It is preferable to set it in ppm. In order to structurally introduce substances that control the conduction properties in the layer region (B), for example atoms of the group group, the starting material for the introduction of atoms of the group group is introduced in a gaseous state into the deposition chamber in a non-volatile manner during layer formation. It may be introduced together with other starting materials for forming a crystalline layer. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlCl ₃ ,
GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the photoconductive member of the present invention, as explained in the example shown in FIGS. 1 and 2, the layer region (O) constituting the amorphous layer ( ) is ()
A preferred embodiment is a case in which the layer region (O) is locally unevenly distributed toward the support, but the present invention is not limited thereto. An amorphous layer () may be formed as the entire layer region of the layer (). In this case, since the amorphous layer ( ) needs to be made to exhibit photoconductivity, the upper limit of the amount of oxygen atoms contained in the layer region (O) is usually 30 atomic%, preferably It is desirable to set it to 10 atomic%, optimally 5 atomic%. In this case as well, the lower limit is of course set to the above value. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method and a sputtering method will be described. FIG. 2 shows an apparatus for manufacturing photoconductive members using both the glow discharge decomposition method and the sputtering method. In the gas cylinders 211 to 215 in the figure, raw material gases for forming the respective layers of the present invention are sealed.
_SiH4 gas diluted with He (purity 99.999% or less)
Abbreviated as SiH ₄ /He. ) cylinder, 212 is PH ₃ gas diluted with He (purity 99.999%, hereinafter PH ₃ /He)
It is abbreviated as ) cylinder, 213 is Si ₂ diluted with He
H ₆ gas (99.99% purity, hereinafter abbreviated as Si ₂ H ₆ /He)
The cylinders 214 are NO gas cylinders (purity 99.999%), and 215 are Ar gas cylinders. When introducing halogen atoms into the formed layer, SiH ₄
For example, the cylinder may be changed to use SiF ₄ gas instead of Si ₂ H ₆ gas or Si 2 H 6 gas. In order to flow these gases into the reaction chamber 201, the valves 231 to 23 of the gas cylinders 211 to 215 are used.
5. Confirm that the leak valve 206 is closed, and confirm that the inflow valves 221 to 225, the outflow valves 226 to 230, and the auxiliary valve 241 are open, and first open the main valve 210 to drain the reaction chamber. 201, exhaust the inside of the gas pipe. Next, when the reading on the vacuum gauge 242 reaches approximately 5×10 ^-6 torr, the auxiliary valve 241 and the outflow valves 226 to 2
Close 30. Next, an example of forming the first amorphous layer on the support 209 will be described. The shutter 205 is closed and connected to be supplied with high voltage power from a power source 243. From gas cylinder 211
SiH ₄ /He gas, PH ₃ /He from gas cylinder 212
Open the valves 231, 232, and 234 to supply NO gas from the gas and gas cylinders 214, respectively, and set the pressures on the outlet pressure gauges 236, 237, and 239 to 1.
Adjust to Kg/cm ² , inflow valve 221, 222, 2
Gradually open 24 and remove the mass flow controller 21.
6,217,219. Subsequently, the outflow valves 226, 227, 229 and the auxiliary valve 241 are gradually opened to supply each gas to the reaction chamber 201.
to flow into. SiH ₄ /He gas flow rate at this time,
Outlet valves 226 _, 227,
229 and the opening of the main valve 210 while checking the reading on the vacuum gauge 242 so that the pressure inside the reaction chamber 201 reaches the desired value. After confirming that the temperature of the support 209 is set to a desired temperature in the range of 50 to 400°C by the heating heater 208, the power source 243 is set to the desired power to cause a glow discharge in the reaction chamber 201. First, a layer region containing phosphorus and oxygen is formed on the support 209 by causing oxidation. At this time, PH ₃ /He gas,
Alternatively, by blocking the introduction of NO gas into the reaction chamber 201 by closing the valve of each corresponding gas introduction pipe, the layer thickness of the layer region containing phosphorus or the layer region containing oxygen can be reduced. can be arbitrarily controlled as desired. After the layer regions each containing phosphorus and oxygen are formed to the desired thickness as described above, the outflow valve 22
By closing each of No. 7 and 229 and continuing glow discharge for a desired time, layer regions containing no phosphorus and oxygen are formed to a desired thickness on the layer regions containing phosphorus and oxygen, respectively. With this, the formation of the first amorphous layer ( ) is completed. When containing halogen atoms in the first amorphous layer (2), the above gas may contain, for example, SiF ₄ /He.
is further added and fed into the reaction chamber 201. To form the second amorphous layer ( ) on the first amorphous layer ( ), for example, the following procedure is performed. First, open the shutter 205. All gas supply valves are once closed, and the reaction chamber 201 is evacuated by fully opening the main valve 210. A target is provided on the electrode 202 to which high-voltage power is applied, in which a high-purity silicon wafer 204-1 and a high-purity graphite wafer 204-2 are placed in advance at a desired area ratio. SiF ₄ /Ar gas is supplied from the gas cylinder 215 to the reaction chamber 201.
into the reaction chamber 201, and the internal pressure of the reaction chamber 201 is 0.05 to 1 torr.
Adjust the main valve 210 so that By turning on the high voltage power supply and simultaneously sputtering the target, it is possible to form the second amorphous layer ( ) on the first amorphous layer ( ). Another method for forming the second amorphous layer () is to use, for example, SiH ₄ gas, SiF ₄ gas, C This is accomplished by diluting each of the ₂ H ₄ gases with a diluent gas such as He as necessary and flowing them into the reaction chamber 201 at a desired flow rate ratio to generate glow discharge according to desired conditions. Ru. Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 201. Valve 21
In order to avoid gas remaining in the gas piping leading from 7 to 221 into the reaction chamber 201, the outflow valve 21
7 to 221 are closed, the auxiliary valves 232 and 233 are opened, and the main valve 234 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. Example 1 Layers were formed on an aluminum substrate using the manufacturing apparatus shown in FIG. 2 under the following conditions. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 2 A layer was formed on an Al substrate under the following conditions using the manufacturing apparatus shown in FIG. Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the process over 100,000 times.

[Table] Example 3 Using the apparatus shown in FIG. 2, a layer was formed on an Al substrate under the following conditions. Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging, exposure and developing device, corona discharge was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image with extremely high density on the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 4 When forming the second amorphous layer (), the area ratio of the silicon wafer and graphite was changed to determine the content ratio of silicon atoms and carbon atoms in the second amorphous layer (). An image forming member was produced in exactly the same manner as in Example 1, except that . The image forming member thus obtained was subjected to the image forming, developing and cleaning steps as described in Example 1 about 50,000 times and then subjected to image evaluation, and the results shown in Table 4 were obtained.

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Example that causes image defects 5 Exactly the same as Example 1 except for changing the layer thickness of the second amorphous layer () An imaging member was prepared by the method. The steps of image formation, development, and cleaning as described in Example 1 were repeated to obtain the following results.

[Table] Example 6 An image forming member was prepared in the same manner as in Example 1, except that the method for forming the first amorphous layer () was changed as shown in the table below, and evaluated in the same manner as in Example 1. Good results were obtained.

[Table] Example 7 An image forming member was prepared in the same manner as in Example 1, except that the method for forming the first amorphous layer () was changed as shown in the table below, and evaluated in the same manner as in Example 1. When conducted, good results were obtained.

[Table] Example 8 Except that the second amorphous layer () was created by the sputtering method under the following conditions,
An image forming member was prepared in the same manner as in Example 3 and evaluated in the same manner as in Example 3, and good results were obtained.

[Table] Example 9 The conditions and procedures shown in Example 2 were followed except that the layer creation conditions in the second and third layer creation stages of Example 2 were as shown in Table 9 below. When electrophotographic image forming members were prepared and evaluated in the same manner as in Example 1, good results were obtained for each of them, particularly in terms of image quality and durability.

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram schematically showing the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG. 2 is an apparatus for manufacturing the photoconductive member of the present invention. It is a typical explanatory view showing an example. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 103...First layer region (O), 104...Second layer region (V),
107...Second amorphous layer ().

Claims (1)

[Scope of Claims] 1. A photoconductive member comprising a support for the photoconductive member and a first amorphous layer that is made of an amorphous material containing silicon atoms as a matrix and exhibits photoconductivity. hand,
The first amorphous layer has a first layer region containing oxygen atoms as constituent atoms, and a second layer region containing atoms belonging to Group Group of the Periodic Table as constituent atoms, and The first layer region and the second layer region are provided in contact with the support and share at least a part of each other, and the layer thickness of the second layer region is _tB , and the first layer region is If the difference between the layer thickness of the amorphous layer and the layer thickness _tB of the second layer region is T, then the relationship _tB /(T+ _tB )≦0.4 is established, and the first amorphous layer A photoconductive member characterized in that it has a second amorphous layer made of an amorphous material containing silicon atoms, carbon atoms, and halogen atoms as constituent atoms thereon.