JPH0145991B2 - - 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. Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and low signal-to-noise ratio [photocurrent (I _p )/dark current (I _d )]. ] has absorption spectrum characteristics that closely match the spectrum characteristics of the electromagnetic waves being irradiated, has fast photoresponsiveness, has the desired dark resistance value, is non-polluting to the human body during use, and furthermore, solid-state imaging. The device is required to have characteristics such as 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.
German Publication No. 2,855,718 describes a technique for use as an electrophotographic image forming member, and German Publication No. 2,933,411 describes a technique for applying it to a photoelectric conversion/reading device. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics. For example, when applying it to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the response gradually decreases. There were many cases where problems occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. Furthermore, in the case where commonly used halogen lamps and fluorescent lamps are used as light sources, light on the long wavelength side cannot be used effectively, so there is still room for improvement. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the reflectance of the support itself to the light that passes through the photoconductive layer will decrease. When the value is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc. Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for control purposes, or other atoms for the purpose of improving other properties, but how these constituent atoms are contained is determined. Problems may therefore arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of the photocarrier generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side in a dark area may not be sufficiently prevented. There are many cases. Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or cracks may develop over time when the layer is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs particularly 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
As a result of intensive research and study on a-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 Atom (Si) and germanium atom (Ge) are used as base materials, and hydrogen atom
(H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter collectively referred to as these] As a notation, “a-SiGe(H,
A photoconductive member having a photoreceptive layer exhibiting photoconductivity consisting of the following: Such a photoconductive member not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive members in all respects, particularly as a photoconductive member for electrophotography. It was found that it has excellent absorption spectrum characteristics on the long wavelength side. In view of the above findings, the present invention provides electrical, optical,
It is an all-environment type that has stable photoconductive properties at all times and is almost unrestricted by the usage environment.It has excellent photosensitivity characteristics on the long wavelength side and is extremely resistant to light fatigue, and does not deteriorate even with repeated use. The main object of the present invention is to provide a photoconductive member in which no or almost no residual potential is observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. 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, the present invention has a charge retention ability during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively. It is an object of the present invention to provide a photoconductive member having sufficient electrophotographic properties and excellent electrophotographic properties in which the properties hardly deteriorate even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
It is an object of the present invention to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with a support. The photoconductive member of the present invention includes a support for the photoconductive member and a photoreceptive layer showing photoconductivity and made of an amorphous material containing silicon atoms and germanium atoms as a matrix, The receptor layer is characterized in that it contains carbon atoms and has unevenly distributed regions on the support side that contain a substance that controls conductivity. 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, and photoconductive properties. Indicates 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 photoreceptive layer formed on the support in the photoconductive member of the present invention is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used. Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast optical response. 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. A photoconductive member 100 shown in FIG. 1 includes a support 101 for use as a photoconductive member, and a photoreceptive layer having photoconductivity made of a-SiGe (H,X) laminated on the support 101. 102. The germanium atoms contained in the photoreceptive layer 102 are continuously and uniformly distributed in the layer thickness direction of the photoreceptive layer 102 and in the in-plane direction parallel to the surface of the support 101. Contained in layer 102. In the photoconductive member of the present invention, the photoreceptive layer containing germanium atoms is provided with a layer region (PN) containing a substance (C) that controls conductivity on the support side. The conduction properties of the region (PN) can be arbitrarily controlled as desired. Such substances (C) include so-called impurities in the semiconductor field, and in the present invention, a-SiGe constituting the photoreceptive layer to be formed is used.
Examples include a p-type impurity that gives p-type conductivity to (H, Specifically, p-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. The n-type impurity is an atom belonging to a group of the periodic table (group atom), such as P (phosphorus), As (arsenic), Sb (antimony), Si (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance that controls the conduction properties contained in the layer region (PN) provided in the photoreceptive layer is determined based on the conduction properties required for the layer region (PN) and the layer region (PN). The organic relationship can be appropriately selected by looking at the relationship with the properties of the contact interface with the support in which the PN) is provided in direct contact with the support. In addition, considering the relationship with the characteristics of other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions, the material for controlling the conduction characteristics is selected. The content is selected appropriately. In the present invention, the content of the substance controlling conduction properties contained in the layer region (PN) is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5×10 ⁴ atomic ppm. , optimally 1-5×
10 ³ atomic ppm. In the present invention, the content of the substance controlling conduction characteristics in the layer region (PN) containing the substance is preferably 30 atomic ppm or more, more preferably 30 atomic ppm or more.
By setting the content to 50 atomic ppm or more, optimally 100 atomic ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, the free surface of the photoreceptive layer is supported when subjected to polar charging treatment. Injection of electrons into the photoreceptive layer from the body side can be effectively prevented. In addition, when the substance to be contained is the n-type impurity described above, when the free surface of the amorphous layer is subjected to polar charging treatment, it is possible to effectively inject holes from the support side into the photoreceptive layer. can be prevented. In the above case, the layer area (PN)
The layer region (Z) excluding the layer region (PN) may contain a substance that governs the conduction characteristics with a polarity different from the polarity of the material that governs the conduction characteristics contained in the layer region (PN), Alternatively, the substance controlling the same polarity conduction characteristics may be contained in an amount much smaller than the actual amount contained in the layer region (PN). In such a case, the content of the substance controlling the conduction characteristics contained in the layer region (Z) may be determined as desired depending on the polarity and content of the substance contained in the layer region (PN). Therefore, it should be determined appropriately, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05-500 atomic ppm, optimally 0.1-200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably 30 atomic Must be less than ppm. In addition to the above-described case, in the present invention, a layer region containing a conductivity-controlling substance having one polarity in the photoreceptive layer and a layer region containing a conductivity-controlling substance having the other polarity are included. It is also possible to provide a so-called depletion layer in the contact region by directly contacting the layer region containing the material. For example, the p-type impurity-containing layer region and the n-type impurity-containing layer region are provided in the photoreceptor layer so as to be in direct contact with each other to form a so-called p-n junction to eliminate depletion. layers can be provided. In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9.5×10 ⁵ atomic ppm,
More preferably 100 to 8.0×10 ⁵ atomic ppm, optimally 500 to 7×10 ⁵ atomic ppm. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the photoreceptive layer, the photoreceptor layer contains Contains carbon atoms. The carbon atoms contained in the photoreceptive layer may be uniformly contained in the entire layer area of the photoreceptive layer, or may be contained in only some layer areas of the photoreceptive layer and unevenly distributed. . Further, the distribution state of carbon atoms may be such that the distribution concentration C (C) is uniform or non-uniform in the thickness direction of the photoreceptive layer. In the present invention, when the main purpose of the layer region (C) containing carbon atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is When the main purpose is to strengthen the adhesion between the support and the light-receiving layer, the light-receiving layer is provided so as to occupy the support-side end layer region of the light-receiving layer. The content of carbon atoms contained in the layer region (C) is
In the former case, it is desirable to use a relatively small amount in order to maintain high photosensitivity, and in the latter case, it is desirable to use a relatively large amount in order to reliably strengthen the adhesion to the support. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute the concentration at a relatively high concentration on the support side and to distribute at a relatively high concentration on the free surface side of the photoreceptive layer, or It is sufficient to form a carbon atom distribution state in the layer region (C) such that carbon atoms are not actively contained in the surface layer region on the free surface side of the photoreceptive layer. In the present invention, the layer region (C) provided in the photoreceptive layer
The content of carbon atoms contained in the layer region (C) depends on the characteristics required for the layer region (C) itself, or when the layer region (C) is provided in direct contact with the support, the content of carbon atoms in It can be selected as appropriate based on the organic relationship, considering the relationship with the properties at the contact interface. In addition, when another layer region is provided in direct contact with the layer region (C), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The carbon atom content is appropriately selected with consideration given to the carbon atom content. The amount of carbon atoms contained in the layer region (C) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001.
~50atomic%, more preferably 0.002~40atomic
%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region (C) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is equal to the layer thickness To of the layer region (C). When the proportion of carbon atoms in the layer region (C) is sufficiently large, it is desirable that the upper limit of the content of carbon atoms contained in the layer region (C) is sufficiently smaller than the above value. In the case of the present invention, if the ratio of the layer thickness To of the layer region (C) to the layer thickness T of the photoreceptive layer is two-fifths or more, The upper limit of the amount of carbon atoms contained is preferably:
30 atomic% or less, more preferably 20 atomic%
Hereinafter, the optimum value is 10 atomic% or less. 2 to 10 show typical examples of the distribution state of carbon atoms contained in the layer region (C) of the photoconductive member of the present invention in the layer thickness direction. In Figures 2 to 10, the horizontal axis represents the carbon atom distribution concentration C (C), the vertical axis represents the layer thickness of the layer region (C), and t _B represents the layer region (C) on the support side. The position of the end face is t _T
indicates the position of the end surface of the layer region (C) on the side opposite to the support side. That is, the layer region (C) containing carbon atoms is
Layer formation occurs from the _tB side toward the _tT side. FIG. 2 shows a first typical example of the distribution state of carbon atoms contained in the layer region (C) in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B to the position t ₁ where the surface where the layer region (C) containing carbon atoms is formed and the surface of the layer region (C) are in contact, the carbon While the distribution concentration of atoms C (C) takes a constant value of C ₁ , carbon atoms are contained in the layer region (C) where they are formed, and gradually increase from the position t ₁ to the concentration C ₂ to the interface position t _T. has been continuously decreased. At the interface position _tT , the distribution concentration C(C) of carbon atoms is assumed to be _C3 . In the example shown in FIG. 3, the distribution concentration C of the contained carbon atoms gradually and continuously decreases from the concentration C ₄ from the position t _B to the position t _T , and reaches the concentration C ₅ at the position t _T. It forms a distribution state like this. In the case of Fig. 4, the distribution concentration C(C) of carbon atoms is assumed to be a constant value of concentration _C6 from position _tB to position _t2 ,
The distribution concentration C(C) is gradually and continuously decreased between the position _t2 and the position _tT , and at the position _tT , the distribution concentration C(C) is substantially zero (here, substantially zero is defined as the detection (if the amount is less than the limit amount). In the case of Fig. 5, the distribution concentration C(C) of carbon atoms gradually decreases continuously from the concentration _C8 from position _tB to position _tT , and becomes substantially zero at position _tT . has been done. In the example shown in FIG. 6, the distribution concentration C of carbon atoms is a constant value of concentration C ₉ between position t _B and position t ₃ , and is set to a concentration C ₁₀ at position t _T. Between position _t3 and position _tT , the distribution concentration C(C) is linearly decreased from position _t3 to position _tT . In the example shown in FIG. 7, the distribution concentration C(C)
takes a constant value of concentration C ₁₁ from position t _B to position t ₄ , and from position t ₄ to position t _T the concentration is C ₁₂ to C ₁₃
It is said that the distribution state decreases linearly until In the example shown in FIG. 8, from position t _B to position t _T
Until , the distribution concentration C(C) of carbon atoms is the concentration C ₁₄
It decreases in a linear function so as to substantially reach zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C(C) of carbon atoms decreases linearly from the concentration C ₁₅ to the concentration C ₁₆ , and from position t ₅ to position t _T
An example is shown in which the concentration C ₁₆ is set to a constant value. In the example shown in FIG. 10, the distribution concentration C(C) of carbon atoms is the concentration C ₁₇ at position t _B ;
Until reaching position t ₆ , the concentration C ₁₇ is slowly decreased at first, and near the position t ₆ , it is rapidly decreased to the concentration C ₁₈ at position t ₆ . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of carbon atoms contained in the layer region (C) in the layer thickness direction, in the present invention, on the support side , distribution concentration of carbon atoms C(C)
The layer region (C) is provided with a carbon atom distribution state in which the distribution concentration C is considerably lower on the interface _tT side than on the support side. preferable. In the present invention, the layer region (C) containing carbon atoms constituting the photoreceptive layer is the localized region (B) containing carbon atoms at a relatively high concentration on the support side as described above. It is desirable that the support be provided as having the following properties, and in this case, the adhesion between the support and the light-receiving layer can be further improved. The localized region (B) is desirably provided within 5 μm from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region (B) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region (B) is a part or all of the layer region (L _T ) is appropriately determined depending on the characteristics required of the photoreceptive layer to be formed. The localized region (B) has a carbon atom distribution concentration C (C) as the distribution state of the carbon atoms contained therein in the layer thickness direction.
The layers are formed so that a distribution state can be obtained in which the maximum value Cmax is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more. That is, in the present invention, the layer region (C) containing carbon atoms has a layer thickness of 5 μm or less from the support side (t _B
The maximum value of the distribution concentration C (C) in the layer region with a thickness of 5μ from
It is desirable that the structure be formed so that Cmax exists. In the present invention, specific examples of the halogen atom (X) contained in the light-receiving layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as. In the present invention, the photoreceptive layer composed of a-SiGe (H, will be accomplished. For example, by the glow discharge method, a
- To form a photoreceptive layer composed of SiGe (H, The raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) are kept in a desired gas pressure state in a deposition chamber whose interior can be reduced in pressure. It is sufficient to introduce the a-SiGe (H, In addition, when forming by sputtering method, for example, a target composed of Si or a target composed of Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using two targets composed of Ge,
Alternatively, using a mixed target of Si and Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He or Ar as necessary is converted into hydrogen atoms (H) or / A gas for introducing halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and the
The target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. In the case of the ion plating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and these evaporation sources are used by resistance heating method or electron beam method. This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by (EB method) or the like and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. 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 Furthermore, silicon hydride compounds containing silicon atoms and halogen atoms in a gaseous state or containing gasifiable halogen atoms can also be mentioned as effective 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 using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. A light-receiving layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically silicon halide, which is a raw material gas for supplying Si, germanium hydride, and Ar, which are raw material gases for supplying Ge, are manufactured using the glow discharge method. ，
Gases such as H ₂ and He are introduced into a deposition chamber where a photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. A light-receiving layer can be formed on a desired support by using these gases, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of a silicon compound gas containing . 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. 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 form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. 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 ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
Halogen compounds containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenation halides such as GeHI 3 , GeH ₂ I ₂ , GeH ₃ I, GeF _{4 ,} GeCl ₄ , GeBr ₄ ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as effective starting materials for forming the photoreceptor layer. In the case of halogen compounds containing hydrogen atoms in these substances, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the photoreceptive layer. In the invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
It is also possible to cause a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in the deposition chamber. I can do it. In a preferred example of 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) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%
30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the photoreceptive layer, for example, the support temperature or /hydrogen atoms (H) or halogen atoms (X) can be controlled. For this purpose, the amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled. In order to structurally introduce a substance that controls conduction properties, such as a group atom or a group atom, into the layer region (PN) constituting the photoreceptive layer, it is necessary to introduce a substance for introducing a group atom during layer formation. The starting material or the starting material for introducing the group atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the photoreceptive 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 ₄ H ₁₀ , B ₅ H ₉ ,
Boron hydride such as B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ ,
Examples include 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 can also be mentioned. In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _PI3 . 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. In the present invention, in order to provide the layer region (C) containing carbon atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing carbon atoms is added to the above-mentioned starting material for forming the photoreceptive layer. It may be used together with the starting material and incorporated in the formed layer in a controlled amount. When a glow discharge method is used to form the layer region (C), a starting material for introducing carbon atoms is added to the starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for introducing carbon atoms, most of the gaseous substances containing at least carbon atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (C), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and a raw material gas containing carbon atoms (C) and hydrogen atoms (H) are used. are also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) are mixed. It can be used by mixing with a raw material gas having constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
A raw material gas containing carbon atoms (C) as constituent atoms may be mixed with a raw material gas containing carbon atoms (C) as constituent atoms. Examples of those having C and H as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
Propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylenic hydrocarbons include: Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), and butylene (C ₄ H ₆ ). In addition to these, alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ can be cited as raw material gases containing Si, C, and H as constituent atoms. In the present invention, the layer region (C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effect obtained by nitrogen atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (C) include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO),
Nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), trinitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) Examples include lower siloxanes such as. Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) used when forming the layer region (C) include those containing N as a constituent atom or those containing N and H. _{Constituent atoms , such as gaseous or} Mention may be made of nitrogen compounds that can be gasified, such as nitrogen, nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Mention may be made of halogenated nitrogen compounds. To form a layer region (C) containing carbon atoms by sputtering, a single crystal or polycrystalline
This can be carried out by sputtering a Si wafer, a C wafer, or a wafer containing a mixture of Si and C in various gas atmospheres. For example, if a Si wafer is used as a target, carbon 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 sputtering deposition chamber, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, by using Si and C as separate targets or as a single mixed target of Si and C, it is possible to generate at least hydrogen atoms in an atmosphere of a diluent gas as a sputtering gas. This is accomplished by sputtering in a gas atmosphere containing (H) or/and halogen atoms (X) as constituent atoms. As the raw material gas for carbon atom introduction, the raw material gas for carbon atom introduction 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, when a layer region (C) containing carbon atoms is provided when forming a photoreceptive layer, the layer region (C)
In order to form a layer region (C) having a desired distribution state (depth profile) in the layer thickness direction by changing the distribution concentration C (C) of carbon atoms contained in (C) in the layer thickness direction, it is necessary to In the case of discharge, a starting material gas for introducing carbon atoms whose distribution concentration C(C) is to be changed is introduced into the deposition chamber while the gas flow rate is appropriately changed according to a desired rate of change curve. It is accomplished by doing so. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time,
The rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a pre-designed rate-of-change curve to obtain a desired content rate curve. When forming the layer region (C) by the sputtering method, the distribution concentration C (C) of carbon atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth) of carbon atoms in the layer thickness direction. First, as in the glow discharge method, the starting material for introducing carbon atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is controlled. This can be done by appropriately changing it as desired. Second, when using a target for sputtering, for example, a target containing a mixture of Si and C, it is necessary to change the mixing ratio of Si and C in advance in the direction of the layer thickness of the target. It will be done. The layer thickness of the photoreceptive layer in the photoconductive member of the present invention is appropriately determined as desired so that photocarriers generated in the photoreceptor layer are efficiently transported, and is preferably 1 to 100 μm. Preferably 1 to 80μ,
The optimal thickness is 2 to 50μ. 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. . It is preferable that at least one surface of these electrically insulating supports is conductively treated, and another layer is 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 belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that the 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 a case, the thickness is preferably 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, and one example is 1102
1103 is a SiH ₄ gas diluted with He (purity 99.999%, hereinafter referred to as SiH 4 /He), and 1103 is a He diluted GeH ₄ gas (purity 99.999%, hereinafter referred to as SiH ₄ /He) cylinder.
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is B ₂ H ₆ gas diluted with He (purity 99.99%, hereinafter referred to as B ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is C ₂ H ₄ gas (purity 99.999%) cylinder, 1106 is H ₂ gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, the valves 11 of the gas cylinders 1102 to 1106 are
22 to 1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112
~1116, confirming that the outflow valves 1117~1121 and auxiliary valves 1132, 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.
Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH 4 /He gas from gas cylinder 1103, GeH ₄ /He gas from gas cylinder 1104
B ₂ H ₆ /He gas, C ₂ H ₄ from gas cylinder 1105
Valves 1122 to 1125 are opened to adjust the pressures of outlet pressure gauges 1127 to 1130 to 1 Kg/cm ² , and inflow valves 1112 to 1115 are gradually opened to flow into mass flow controllers 1107 to 1110, respectively. Subsequently, the outflow valve 1117
~1120, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valves 1117 to 112 are adjusted so that the ratio of the SiH ₄ /He gas flow rate, the GeH ₄ /He gas flow rate, the B ₂ H ₆ /He gas flow rate, and the NO gas flow rate becomes a desired value.
0, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of approximately 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. , maintaining the glow discharge for a desired time to the base 1137.
A layer region (B, C) containing boron atoms (B) and carbon atoms (C) to a desired thickness and composed of a-SiGe (H, X) is formed thereon. At the stage when the layer regions (B, C) have been formed to the desired layer thickness, the same conditions are applied except that the outflow valves 1119 and 1120 are completely closed, and the discharge conditions are changed as necessary. By maintaining glow discharge for a desired time according to the procedure, the layer region (B, C) is made of a-SiGe (H, X) containing neither boron atoms (B) nor carbon atoms (O). The formation of the photoreceptive layer is completed by forming the upper layer region. When forming the above-mentioned photoreceptive layer, after a desired period of time has elapsed after the start of the layer formation, the deposition chamber is
By stopping the flow of B ₂ H ₆ /He gas or C ₂ H ₄ gas, the layer thicknesses of the layer region containing boron atoms (B) and the layer region containing carbon atoms (C) can be adjusted as desired. can be controlled. Also, the deposition chamber 1101 is adjusted according to a desired rate of change curve.
By controlling the gas flow rate of C ₂ H ₄ gas to the layer region (C), the distribution state of carbon atoms contained in the layer region (C) can be formed as desired. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged voltage of developer (including toner and carrier) across the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0kV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 2 The same procedure as Example 1 was carried out except that the flow rate of B ₂ H ₆ to (SiH ₄ +GeH ₄ ) was changed as shown in Table 2 when creating the first layer. Each of the electrophotographic imaging members was prepared under the following conditions. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 2 were obtained. Example 3 Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the thickness of the first layer was changed as shown in Table 3. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 3 were obtained. Example 4 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Table 4 to obtain an electrophotographic image forming member. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0kV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 5 In Example 4, the conditions were the same as in Example 4, except that the flow rate of PH ₃ to (SiH ₄ +GeH ₄ ) was changed as shown in Table 5 when creating the first layer. Each of the electrophotographic imaging members was prepared. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained. Example 6 Electrophotographic image forming members were prepared in the same manner as in Example 4, except that the thickness of the first layer was changed as shown in Table 6. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 6 were obtained. Example 7 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Tables 7 and 8 to produce an electrophotographic image forming member (sample no.
701, 702) were obtained. For each of the image forming members obtained in this way, a toner image was obtained on a transfer paper using the same method and conditions as in Example 1, and the image was evaluated. A high-density image was obtained. Example 8 Using the manufacturing apparatus shown in FIG. 11, layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Tables 9 to 11 were used to form electrophotographic image forming members ( Sample Nos. 801 to 803) were obtained. For each of the image forming members thus obtained,
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 9 In Example 8, when creating the first layer, the flow rate of B ₂ H ₆ for (SiH ₄ +GeH ₄ ) was shown in Tables 12 to 14.
Each electrophotographic image forming member was produced under the same conditions as in Example 8 except for the changes shown in the table. For each of the image forming members thus obtained,
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, the results shown in Tables 12 to 14 were obtained. Example 10 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image was evaluated using an electrophotographic image forming member prepared under the same conditions as described above, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

【table】

[Table] ◎: Excellent ○: Good

[Table] ◎: Excellent ○: Good △: Adequate for practical use

【table】

[Table] ◎: Excellent ○: Good △: Adequate for practical use

[Table] ◎: Excellent ○: Good △: Adequate for practical use

【table】

【table】

【table】

【table】

【table】

【table】

[Table] ◎: Excellent ○: Good

[Table] ◎: Excellent ○: Good

[Table] ◎: Excellent ○: Good
Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: germanium atom (Ge) containing layer...
…Approx. 200℃ Discharge frequency: 13.56MHz Reaction time Reaction chamber pressure: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of carbon atoms in the layer region (C), respectively. FIG. 11 is a schematic explanatory diagram of the apparatus used to produce the photoconductive member of the present invention in Examples. 100...Photoconductive member, 101...Support, 102
...Photoreceptor layer.

Claims (1)

[Scope of Claims] 1. A photoconductive material comprising a support for a photoconductive member and a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, A photoconductive member characterized in that the layer contains carbon atoms and has unevenly distributed regions on the support side containing a substance that controls conductivity. 2. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms. 3. The photoconductive member according to claim 1, wherein the photoreceptive layer contains halogen atoms. 4. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms and halogen atoms. 5. The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 6. The photoconductive member according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 7 The amount of hydrogen atoms contained in the photoreceptive layer is
The photoconductive member according to claim 2, wherein the content is 0.01 to 40 atomic%. 8. Claim 3, wherein the amount of halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%.
The photoconductive member described in . 9. The photoconductive member according to claim 3, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%. 10. The photoconductive member according to claim 1, wherein the amount of germanium atoms contained in the first layer region is 1 to 9.5×10 ⁵ atomic ppm. 11. The photoconductive member according to claim 1, wherein the photoreceptive layer has a thickness of 1 to 100 μm. 12 The atom belonging to Group 1 of the periodic table is B,
The photoconductive member according to claim 5, which is selected from Ga. 13 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member according to claim 6, which is selected from As. 14 The substance controlling the conductivity is 0.01 to 5×
Claim 1 containing 10 ⁴ atomic ppm
The photoconductive member according to item 1 and item 19. 15 The substance that controls the conductivity is 30 atomic
The photoconductive member according to claim 24, which contains ppm or more. 16. The photoconductive member according to claim 1, wherein the distribution concentration of the carbon atoms decreases from the support side toward the opposite side. 17. The photoconductive member according to claim 1, wherein the distribution concentration of the carbon atoms is uniformly distributed in the layer thickness direction of the photoreceptive layer. 18 The content of the carbon atoms is 0.001 to 50 atomic
% of the photoconductive member according to claim 1. 19 The maximum value of the distribution concentration of the carbon atoms is
Claim 2 which is 500 atomic ppm or more
The photoconductive member according to item 8. 20. The photoconductive member according to claim 28, wherein the distribution concentration of the carbon atoms is higher on the support side. 21. The photoconductive member according to claims 3 and 4, wherein the halogen atom is selected from fluorine and chlorine.