JPH047503B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, r-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material 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 and
It must have a high signal-to-noise ratio [photocurrent (I _p )/dark current (I _d )], have absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use, and being able to easily dispose of 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 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 stability over time, and it is necessary to improve overall characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases, etc. 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. However, when the commonly used halogen lamps and fluorescent lamps are used as light sources, there remains room for improvement in that they cannot effectively use light on the long wavelength side. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio 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 larger 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. Alternatively, when the photoconductive layer is composed of a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. In the past, 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 attention of charge from the support side is not sufficiently blocked in dark areas, or ,
There may be image defects commonly called "white spots" on the image transferred to the transfer paper, which are thought to be caused by a local discharge breakdown phenomenon. In some cases, so-called image defects called "white streaks" 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 materials designed and produced under this method not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially when used in electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive member and that it has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, has excellent photosensitivity characteristics on the long wavelength side, and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that does not deteriorate even after repeated use and has no or almost no residual potential 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 maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance. 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,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between laminated layers, a dense and stable structural arrangement, and a quality layer. It is an object of the present invention to provide a photoconductive member with high quality. 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. The photoconductive member of the present invention includes a support for the photoconductive member, a first layer region made of an amorphous material containing silicon atoms and germanium atoms on the support, and a first layer region containing silicon atoms as a matrix. and a first amorphous layer having a layered structure in which a second layer region made of an amorphous material not containing germanium and exhibiting photoconductivity is provided in order from the support side, and silicon atoms and carbon atoms. A second material made of an amorphous material with
an amorphous layer, wherein the distribution concentration of germanium atoms in the first layer region decreases from the support toward the side opposite to the support, and The crystalline substance is characterized by containing oxygen atoms. 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 image forming member for electrophotography, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it is highly sensitive.
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. Further, 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. 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 first amorphous layer ( ) 102 and a second amorphous layer ( ) 105 on a support 101 for the photoconductive member, The amorphous layer ( ) 105 has a free surface 10
6 on one end face. The first amorphous layer ( ) 102 is formed from a-Si(H,X) containing germanium atoms (hereinafter referred to as "a-
The first
layer region (G) 103 and a second layer region (S) 10 composed of a-Si(H,X) and having photoconductivity.
It has a layered structure in which 4 and 4 are laminated in order. The germanium atoms contained in the first layer region (G) 103 are continuous in the thickness direction of the first layer region (G) 103 and on the side where the support 101 is provided. on the opposite side (second amorphous layer 105
It is contained in the first layer region (G) 103 in such a manner that it is more distributed on the side of the support 101 than on the side of the first layer (G). In the photoconductive member of the present invention, the germanium atoms contained in the first layer region (G) have the above-mentioned distribution state in the layer thickness direction, and are parallel to the surface of the support. It is desirable to have a uniform distribution state in the in-plane direction. In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (G), and the first amorphous layer has such a layer structure. By forming a transparent layer (), it is possible to make a photoconductive member that has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. be. In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the second layer region. Since the change decreases toward the layer region (S), there is excellent affinity between the first layer region (G) and the second layer region (S), and as will be described later. By making the distribution concentration C of germanium atoms extremely large at the edge of the support, when a semiconductor laser or the like is used, the second layer region (S) absorbs almost no light on the longer wavelength side. can be substantially completely absorbed in the first layer region (G), and interference due to reflection from the support surface can be prevented. Further, in the photoconductive member of the present invention, each of the amorphous materials constituting the first layer region (G) and the second layer region (S) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the first layer region (G) of the photoconductive member of the present invention in the layer thickness direction. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G), and t _B represents the first layer region (G) on the support side. t _T indicates the position of the end surface of the first layer region (G) on the side opposite to the support side. That is, in the first layer region (G) containing germanium atoms, layers are formed from the t _B side toward the t _T side. FIG. 2 shows the first distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction.
A typical example is shown. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region (G) containing germanium atoms is formed and the surface of the first layer region (G) contact, t ₁ Up to the position, the distribution concentration C of germanium atoms takes a constant value of C ₁ and is contained in the first layer region (G) in which germanium atoms are formed, and from the position t ₁ to the interface position from the concentration C ₂ It is gradually and continuously decreased until t _T. At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. reduced, and at position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased from the concentration C ₃ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
C ₁₀ will be done. Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . 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 germanium atoms contained in the first layer region (G) in the layer thickness direction, in the present invention, On the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface _tT side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. is provided in the layer region (G). The first layer region (G) constituting the first amorphous layer () constituting the photoconductive member in the present invention preferably has a relatively high concentration of germanium atoms on the support side as described above. It is desirable to have a localized region (A) containing a high concentration. In the present invention, the localized region (A) is desirably provided within 5 μm from the interface position _tB , as explained using the signals shown in FIGS. 2 to 10. In the present invention, the localized region (A) 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 A is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. The localized region (A) is a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration C _nax of germanium atoms is usually 1000 atomic ppm or more, optimally, relative to silicon atoms.
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the first layer region (G) containing germanium atoms has the maximum distribution concentration C _nax within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B) . It is preferable that it be formed so that there is. In the present invention, the content of germanium atoms contained in the first layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but usually 1 ~9.5× ¹⁰⁵ atomic
ppm, preferably 100 to 8.0×10 ⁵ atomic ppm, optimally 500 to 7×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region (G) and the second layer region (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the photoconductive member has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is typically 30 Å to 50 μ, preferably 40 Å
The thickness is desirably ~40μ, optimally 50Å~30μ. Further, the layer thickness T of the second layer region (S) is usually 0.5 to 90μ, preferably 1 to 80μ, and optimally 2
It is desirable that the thickness be ~50μ. The sum (T _B +T) of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) is the first amorphous layer having the characteristics required for both layer regions. When designing the layers of the photoconductive member, depending on the organic relationship between the properties and the properties required for the entire layer,
To be determined accordingly. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is usually 1 to 100μ,
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are usually T _B /
When satisfying the relationship T≦1, it is desirable that appropriate numerical values be selected for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (G) is 1×10 ⁵
In the case of atomic ppm or more, the layer thickness T _B of the first layer region (G) is desirably as thin as possible, preferably 30μ or less, more preferably
The thickness is desirably 25μ or less, optimally 20μ or less. In the photoconductive member of the present invention, the distribution state of germanium atoms in the first layer region (G) is as follows:
Germanium atoms are continuously distributed in the entire layer region of the layer region (G), and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the first amorphous layer ().
Since a decreasing change is given toward the free surface side of The crystalline layer ( ) can be realized as desired. For example, the distribution concentration C of germanium in the first layer region (G) should be sufficiently increased on the support side and as low as possible on the free surface side of the first layer region (G). By applying changes in the distribution concentration C to the distribution concentration curve of germanium atoms, photosensitivity can be achieved for light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. It is possible to aim for In addition, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer region (G) on the support side, when a semiconductor laser is used, the laser irradiation surface side The layer region (G) can substantially completely absorb the light on the longer wavelength side that cannot be fully absorbed in the second layer region (S), and the light is reflected from the support surface. Interference can be effectively prevented. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and increasing dark resistance, and further improving the adhesion between the support and the first amorphous layer (),
Oxygen atoms are contained in the first amorphous layer (). The oxygen atoms contained in the first amorphous layer ( ) may be evenly contained in the entire layer area of the first amorphous layer ( ), or the oxygen atoms contained in the first amorphous layer ( It may be contained and unevenly distributed only in a part of the layer region of the layer (). In addition, the distribution state of oxygen atoms is such that the distribution concentration C(O) is
In the layer thickness direction of the first amorphous layer (), even if it is uniform, the distribution concentration C(O) is similar to the distribution state of germanium atoms explained using FIGS. 2 to 10. may be non-uniform in the layer thickness direction. The distribution state of oxygen atoms when the distribution concentration C(O) of oxygen atoms is non-uniform in the layer thickness direction can be explained in the same way as the case of germanium atoms using FIGS. 2 to 10. In the present invention, a layer region (O) containing oxygen atoms provided in the first amorphous layer ()
is provided so as to occupy the entire layer area of the first amorphous layer () when the main purpose is to improve photosensitivity and dark resistance.
When the main purpose is to strengthen the adhesion between the first amorphous layer and the first amorphous layer, it is provided so as to occupy the end layer region of the first amorphous layer on the side of the support. In the former case, the content of oxygen atoms contained in the layer region (O) is kept relatively low in order to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. It is desirable that the amount be relatively large in order to achieve this goal. In addition, in order to achieve both the former and the latter at the same time, a relatively high concentration is distributed on the support side, and a relatively low concentration is distributed on the free surface side of the first amorphous layer (). Or, in the surface layer region on the free surface side of the first amorphous layer (), a distribution state of oxygen atoms is created in the layer region (O) such that oxygen atoms are not actively included. Just form it. In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the first amorphous layer () depends on the characteristics required of the layer region (O) itself or the layer region. When (O) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (O), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in the layer region (O) is
It can be 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%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region (O) occupies the entire area of the first amorphous layer () or even if the layer region (O) does not occupy the entire area of the first amorphous layer (), the layer region (O)
If the proportion of the first amorphous layer () with a layer thickness T ₀ in the layer thickness T is sufficiently large, the upper limit of the content of oxygen atoms contained in the layer region (O) is the above value. It is desirable that the amount be sufficiently reduced. In the case of the present invention, if the ratio of the layer thickness T ₀ of the layer region (O) to the layer thickness T of the amorphous layer is two-fifths or more, The upper limit of the amount of oxygen atoms contained in
30 atomic% or less, preferably 20 atomic% or less,
Optimally, it is desirable to set it to 10 atomic% or less. In the present invention, the layer region (O) containing oxygen atoms constituting the first amorphous layer () contains oxygen atoms at a relatively high concentration toward the support side, as described above. It is desirable to provide the support with localized regions (B), and in this case, the adhesion between the support and the first amorphous layer () can be further improved. The above localized region (B) can be explained using the symbols shown in FIGS. 2 to 10, by 5μ from the interface position _tB .
It is desirable that it be established within 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 is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. The localized region (B) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum value C _nax of the distribution concentration of oxygen atoms is usually 500 atomic ppm or more, preferably 800 atomic ppm or more, most preferably 800 atomic ppm or more.
It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be achieved. That is, in the present invention, the layer region (O) containing oxygen atoms has the maximum distribution concentration within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the formation be such that C _nax is present. In the present invention, if necessary, the first layer region (G) and the second layer region constituting the first amorphous layer () may be
Specifically, the halogen atoms (X) contained in the layer region (S) include fluorine, chlorine, bromine,
Examples include iodine, and particularly preferred are fluorine and chlorine. In the present invention, the first layer region (G) composed of a-SiGe (H, It is done by a deposition method. For example, by glow discharge method, a-SiGe
To form the first layer region (G) composed of (H, Possible raw material gas for supplying Ge and raw material gas for introducing hydrogen atoms (H) as necessary or/
and introducing a raw material gas for introducing halogen atoms (X) into a deposition chamber whose interior can be reduced in pressure at a desired gas pressure to generate a glow discharge within the deposition chamber;
While controlling the distribution concentration of germanium atoms contained on the surface of a predetermined support that has been placed at a predetermined position in advance according to a desired rate of change curve, a-SiGe
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
Using a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or using two targets made of this target and Ge, or , Si and
Using a mixed target of Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He, Ar, etc. as necessary is converted into hydrogen atoms (H).
Or/and a gas for introducing halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and the gas flow rate of the raw material gas for supplying Ge is adjusted to a desired rate of change curve. Therefore, the target may be sputtered while being controlled. 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 the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the above method, 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:
_GeH4 , _{Ge2H6 , Ge3H8 , Ge4H10 , Ge5H12 , Ge6}
Germanium hydride in a gaseous state or which can be gasified, such as H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., can be mentioned as one that can be effectively used, and in particular, it is easy to handle during layer formation work. In terms of Ge supply efficiency, etc.
Preferred examples include GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ . Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be gasified. Further, a silicon hydride 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, CF, CF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , IC, 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 , SiC 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. The first layer region (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically:
For example, silicon halide, which will be the raw material gas for supplying Si, germanium hydride, which will be the raw material gas for Ge supply, and gases such as Ar, H ₂ , He, etc., are mixed at a predetermined mixing ratio and gas flow rate. A first layer region (G) is deposited on the desired support by introducing a layer region (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the ratio of hydrogen atoms introduced, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. It may be formed. 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, such as 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 gaseous plasma atmosphere. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms, but in addition, HF, HC,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such as I ₂ , SiH ₂ C ₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ , GeH _{2
F2 , GeH3F} , _GeHC3 , _GeH2C2 , _GeH3C
, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ ,
Hydrogenated germanium halides such as GeH ₂ I ₂ and GeH ₃ I, halogen compounds containing hydrogen atoms as one of their constituent elements, GeF ₄ , GeC ₄ , GeBr ₄ , GeI ₄ ,
Germanium halides such as GeF ₂ , GeC ₂ , GeBr ₂ , GeI ₂ and the like, gaseous or gasifiable substances can also be mentioned as useful starting materials for forming the first layer region (G). The halides containing hydrogen atoms in these substances introduce halogen atoms into the layer when forming the first layer region (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Since it will be introduced,
In the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H ₂ , SiH ₄ , Si ₂
Silicon hydride such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge _Five
Silicon or a silicon compound for supplying germanium hydride, such as H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., coexists in the deposition chamber to generate a discharge. It can also be done by letting someone do it. In a preferred example of the present invention, the first layer region (G) constituting the first amorphous layer () to be formed
The amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained therein, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X), is usually 0.01 to 40 atomic%,
Suitably 0.05~30atomic% Optimally 0.1~
It is desirable to set it to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer region (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms What is necessary is to control the amount of the starting material used to incorporate X into the deposition system, the discharge power, etc. In the present invention, in order to form the second layer region (S) composed of a-Si(H,X), the starting material () for forming the first layer region (G) described above is The first layer region (G) is formed using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying G from the inside. It can be carried out according to the same method and conditions as in the case of That is, in the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the second layer region (S) composed of a-Si (H, It is made by a vacuum deposition method. For example, in order to form the second layer region (S) composed of a-Si (H, A source gas for introducing hydrogen atoms (H) and/or a source gas for introducing halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow is generated in the deposition chamber. A discharge is generated to deposit a-Si(H,
What is necessary is to form a layer consisting of X). In addition, when forming by sputtering method, for example, Ar, He
When sputtering a target composed of Si in an atmosphere of an inert gas such as or a mixed gas based on these gases, hydrogen atoms (H) or /
Also, a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the photoconductive member of the present invention, the second layer region (S) provided on the first layer region (G) containing germanium atoms and not containing germanium atoms has conductive properties. By including a controlling substance, the conductive properties of the layer region (S) can be controlled as desired. Such substances include so-called impurities in the semiconductor field, and in the present invention, a-Si(H,X) constituting the second layer region (S) to be formed. In contrast, examples include a P-type impurity that provides P-type conduction characteristics, and an n-type impurity that provides N-type conduction characteristics. Specifically, the P-type impurity is an atom belonging to a group of the periodic table (group atom), such as B (boron), A (aluminum), Ga (gallium), In
(indium), T (thallium), etc., and B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (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 second layer region (S) depends on the conduction properties required for the layer region (S) or directly on the layer region (S). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided in contact with the layer region and the relationship with the characteristics at the contact interface with the other layer regions. In the present invention, the content of the substance controlling conduction properties contained in the second layer region (S) is usually 0.001 to 1000 atomic ppm, preferably 0.05 to 500 atomic ppm, and optimally is 0.1~
It is desirable that the content be 200 atomic ppm. In order to structurally introduce substances that control the conduction properties into the second layer region (S), for example group atoms or group atoms, starting materials for introducing group atoms or group atoms can be added during layer formation. The starting material for introducing atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the second layer region. 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 such group group atom introduction include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆
Boron hydride such as H ₁₂ , B ₆ H ₁₄ , BF ₃ , BC ₃ ,
Examples include boron halides such as BBr ₃ . In addition, AC ₃ , GaC ₃ , Ga(CH ₃ ) ₃ , InC ₃ ,
TC ₃ etc. 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 PF ₅ , PC ₃ , PC ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, AsH ₃ ,
AsF ₃ , AsC ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ ,
SbF ₅ , SbC ₃ , SbC ₅ , BiH ₃ , BiC ₃ , BiBr ₃
etc. 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 (O) containing oxygen atoms in the first amorphous layer (), it is necessary to prepare a layer region (O) containing oxygen atoms during the formation of the first amorphous layer (). The starting material may be used together with the above-mentioned starting material for forming the first amorphous layer (), and the amount thereof may be controlled and contained in the layer to be formed. When a glow discharge method is used to form the layer region (O), oxygen atoms are introduced into a material selected as desired from among the starting materials for forming the first amorphous layer (O) described above. The starting materials for are added. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas whose constituent atoms are silicon atoms (Si), a raw material gas whose constituent atoms are oxygen atoms O, and a raw material gas whose constituent atoms are hydrogen atoms (H) or halogen atoms (X) as necessary. or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) in a desired mixing ratio. , also by mixing at a desired mixing ratio, or by mixing a raw material gas containing silicon atoms (Si) with three atoms: silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used by mixing with the raw material gas which is the constituent atoms. 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, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), 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), oxygen atoms (O), and hydrogen atoms (H), such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H Examples include lower siloxanes such as ₃ SiOSiH ₂ OSiH ₃ ). To form the first amorphous layer containing oxygen atoms by the sputtering method, single-crystal or polycrystalline Si wafers or SiO ₂ wafers are targeted, and they are placed in various gas atmospheres. This can be done by sputtering. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
Then, the raw material gas for introducing halogen atoms is diluted with a diluent 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, 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, when a layer region (O) containing oxygen atoms is provided when forming the first amorphous layer (), the distribution concentration C( In order to form a layer region (O) having a desired depth profile by changing O) in the layer thickness direction, the distribution concentration C(O) is changed in the case of glow discharge. This is accomplished by introducing a gas as a starting material for introduction of oxygen atoms into the deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve. For example, the opening of a predetermined needled valve provided in the middle of the gas flow path system may be gradually changed using any commonly used method such as manual operation or 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 may be used to control the flow rate according to a pre-designed rate curve to obtain a desired content rate curve. When the layer region (O) is formed by a sputtering method, the distribution concentration C of oxygen atoms in the layer thickness direction
In order to change (O) in the layer thickness direction and form a desired distribution state (depth profile) of oxygen atoms in the layer thickness direction, firstly, as in the glow discharge method, a This is accomplished by using the starting material in a gaseous state and appropriately varying the gas flow rate at which the solution is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be achieved by changing the mixing ratio of Si and SiO ₂ in advance in the direction of the layer thickness of the target. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or hydrogen atoms and halogen atoms contained in the second layer region (S) constituting the amorphous layer to be formed The sum of the amounts (H+X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%,
The optimum value is 5 to 25 atomic%, but it is desirable. In the photoconductive member 100 shown in FIG. 1, the second amorphous layer ( ) 103 formed on the first amorphous layer ( ) 102 has a free surface and is mainly moisture resistant. , in order to achieve the objects of the present invention in terms of continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability. Further, in the present invention, the first amorphous layer ()
102 and the second amorphous layer (103) each have a common constituent element of silicon atoms, ensuring chemical stability at the laminated interface. It is fully accomplished. The second amorphous layer () in the present invention comprises silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
(hereinafter referred to as "a-(Si _x C _1-x ) _y
( _H ,
Consists of. The second amorphous layer ( ) composed of a-(Si _x C _1-x ) _y (H,X) _1-y can be formed by glow discharge method, sputtering method, ion plantation method, ion spray This is done by the Teing method, electron 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 silicon atoms, and it is easy to introduce carbon atoms and rogen atoms into the second amorphous layer (2) to be manufactured. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. 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 (H,X) _1-y is added as necessary. The gas is mixed with a diluted gas 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. What is necessary is to deposit a-(Si _x C _1-x ) _y (H,X) _1-y on the first amorphous layer ( ) already formed on the support. In the present invention, a-(Si _x C _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Most of gaseous substances or gasified substances having at least one constituent atom among carbon atoms (C), hydrogen atoms (H), and halogen atoms (X) can be used. . When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as necessary. Depending on the situation, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si and C and H may be used. The raw material gas containing constituent atoms and/or the raw material gas containing C and and H as constituent atoms, or a raw material gas containing Si, C, and X as constituent atoms can be mixed and used. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. Raw material gases serving as constituent atoms may be mixed and used. In the present invention, F, C, Br, and I are preferable as the halogen atoms (X) contained in the second amorphous layer ( ), with F and C being particularly preferable. 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. In the present invention, Si and H are effectively used as raw material gases for forming the second amorphous layer ().
SiH ₄ , SiH ₂ H ₆ , Si ₃ H ₈ , Si ₄ whose constituent atoms are
Silicon hydride gas such as silanes such as H ₁₀ , whose constituent atoms are C and H, for example, carbon number 1
~4 saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, Examples include silicon hydride. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (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 ), 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. ,
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, HC, HBr,
Interhalogen compounds include BrF, CF, C
F ₃ , CF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , IC,
IBr silicon halides include SiF ₄ , Si ₂ F ₆ , SiC
₄ , SiC ₃ Br, SiC ₂ Br ₂ , SiCBr ₃ , SiC ₃ I,
SiBr ₄ , SiH ₂ as halogen-substituted silicon hydride
F ₂ , SiH ₂ C ₂ , SiHC ₃ , SiH ₃ C, SiH ₃ Br,
SiH ₂ Br ₂ , SiHBr ₃ , as silicon hydride, SiH ₄ ,
Examples include silanes such as Si ₂ H ₈ and Si ₄ H ₁₀ . In addition to these, CF ₄ , CC ₄ CBr ₄ , CHF ₃ ,
CH ₂ F ₂ , CH ₃ F, CH ₃ C, CH ₃ Br, CH ₃ I,
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ C, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si
Alkyl silicides such as (CH ₃ ) ₄ , Si(C ₂ H ₅ ) ₄ and SiC
Silane derivatives with halogen-containing alkyl silicide names such as (CH ₃ ) ₃ , SiC ₂ (CH ₃ ) ₂ and SiC ₃ CH ₃ can also be mentioned as effective. These second amorphous layer () forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary 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 SiHC _{3 and} SiH can contain halogen atoms. _{2C2 , SiC4} ,
Alternatively, _a-
A second amorphous layer ( ) consisting of (Si _x C _1-x ) _y (C+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/or hydrogen atoms as constituent elements, if necessary. For example, if a Si wafer is used as a target, the raw material gas for introducing C and H or/and The Si wafer may be sputtered by forming a gas plasma of the above gas. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as necessary by using Si and C as separate targets or by using a mixed target of Si and C. This is done by sputtering inside.
The material used as the raw material gas for introducing C, H and can be used as In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluting 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 containing Si, C, and optionally H or/and In the present invention, it exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive. a
-(Si _x C _1-x ) _y ( _H , For example, to provide the second amorphous layer () with the main purpose of improving pressure resistance, a-(Si _x C _1-x ) _y
( _H , In addition, when 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 is relaxed to some extent, and it becomes more resistant to the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y
(H,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 _(H, In the present invention, the temperature of the support during layer formation is controlled so that a-(Si _x C _1-x ) _y (H,X) _1-y having the desired properties can be formed as desired. It is desirable to have strict control. In the present invention, an optimal range is appropriately selected according to the method of forming the second amorphous layer () in order to effectively achieve the desired purpose, and the second amorphous layer ( ) formation is performed, but typically 20~
400℃, preferably 50-350℃, optimally 100-300℃
It is desirable that this is the case. 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. A discharge power of a-(Si _x C _1-x ) _y (H,X) ₁ is created.
-It is one of the important factors that influences the characteristics of _y . The discharge power conditions for producing a-(Si _x C _{1-x ) y} (H, usually
10~300W, preferably 20~250W, optimally 50W~
It is desirable that it be 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 above-mentioned 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 (H,X) _1-y is formed. The amount of carbon atoms contained in the second amorphous layer ( ) in the photoconductive member of the present invention achieves the object of the present invention, as do the conditions for forming the second amorphous layer ( ). This is an important factor in the formation of the second amorphous layer () that provides the desired properties. The amount of carbon atoms contained in the second amorphous layer (2) in the present invention can be determined as appropriate depending on the type and characteristics of the amorphous material constituting the second amorphous layer (2). It can be decided according to the That is, the general formula a-(Si _x C _1-x ) _y (H,X) _1-y
The amorphous material represented by can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ", where 0<a<1) , an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C _1-b ) _C H _1-e ". However, 0<b, c<1) , an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as "a-(Si _d C _1-d )")
_e (H,X) _1-e ''. However, 0<d, e<1)
are categorized. In the present invention, the second amorphous layer () is a-
The second amorphous layer () when composed of Si _a C _1-a
The amount of carbon atoms contained in is usually 1×
10 ^-3 to 90 atomic%, preferably 1 to 80 atomic%,
Optimally, it is desirable to set it to 10 to 75 atomic%. That is, if we use the representation of a in a-Si _a C _1-a above, a is usually 0.1 to 0.99999, preferably 0.2
~0.99, optimally 0.25-0.9. In the present invention, the second amorphous layer () is a-
(Si _b C _1-b ) _c H _1-c , the amount of carbon atoms contained in the second amorphous layer () is usually 1×
10 ^-3 ~90 atomic%, preferably 1 ~
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is usually 1 to 40 atomic%, preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%. The photoconductive member thus prepared is of excellent practical application. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is usually 0.1 to 0.99999, preferably 0.1 to 0.99, optimally 0.15 to 0.9, and c is usually 0.6. ~0.99, preferably
It is desirable that it be between 0.65 and 0.98, most preferably between 0.7 and 0.95. The second amorphous layer () is a-(Si _d C _1-d ) _e
When composed of ⁽ _H , It is desirable that the content be 1 to 90 atomic%, optimally 10 to 80 atomic%. The content of halogen atoms is usually 1 to 20 atomic%, preferably 1 to 18 atomic%, and optimally 2 to 15 atomic%.
It is desirable that the halogen atom content falls within these ranges, and photoconductive members formed when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is usually 19 atomic% or less, preferably
It is desirable that the content be 13 atomic% or less. That is, d of the previous a-(Si _d C _1-d ) _e (H,X) _1-e ,
If expressed as e, d is usually 0.1 to 0.99999, preferably 0.1 to 0.99, optimally 0.15 to 0.9, and e is usually
0.8~0.99, preferably 0.82~0.99, optimally 0.85~
A value of 0.98 is desirable. The number 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 determined depending on the amount of carbon atoms contained in the layer () and the layer thickness of the first amorphous layer (). 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 consider economic efficiency by taking into account productivity and mass production. The layer thickness of the second amorphous layer ( ) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ,
The optimum value is 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, A,
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. . 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,
A, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Conductivity can be imparted by providing a thin film made of Pt, 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 ,A,Ag,Pb,Zn,
Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of a metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. 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.
If the photoconductive member 100 shown in the figure is used as an electrophotographic image 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 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, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (purity 99.99%, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is NO gas (purity
99.999%) cylinder, 1106 is C ₂ H ₄ gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 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 the first amorphous layer () on the cylindrical substrate 1137, SiH ₄ /He gas is supplied from the gas cylinder 1102, GeH ₄ /He gas is supplied from the gas cylinder 1103, and the first amorphous layer () is formed from the gas cylinder 11.
From 05, NO gas is supplied to valves 1122, 1123,
Open 1124 and check the outlet pressure gauges 1127, 112
Adjust the pressure of 8, 1129 to 1 Kg/cm ² , gradually open the inflow valves 1112, 1113, 1114, and mass flow controllers 1107, 1108,
1109 respectively. Subsequently, the outflow valves 1117, 1118, 1119 and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 11.
01. The outflow valves 1117 and 11 are adjusted so that the ratio of the SiH ₄ /He gas flow rate, GeH ₄ /He gas flow rate, and NO gas flow rate at this time becomes a desired value
18 and 1119, 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 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the flow rate of GeH ₄ /He gas is controlled manually or by an externally driven motor or other method according to a pre-designed rate of change curve.
The distribution concentration of germanium atoms contained in the formed layer is controlled by performing an operation of gradually changing the apertures 118. In the manner described above, glow discharge is maintained for a desired period of time to form a first layer region (G) on the substrate 1137 to a desired layer thickness. First layer region (G) to desired layer thickness
At the stage where the outflow valve 1118 is formed, the outflow valve 1118
Substantially all germanium atoms are formed on the first layer region (G) by maintaining the glow discharge for the desired time following similar conditions and procedures, except for completely closing the It is possible to form a second layer region (S) which is not contained in the above. In order to contain a substance that controls conductivity in the second layer region (S), a gas such as B ₂ H ₆ or PH ₃ is added to the deposition chamber when forming the second layer region (S). 11
It may be added to the gas introduced into 01. When halogen atoms are contained in the first amorphous layer (2), for example, SiF ₄ gas may be further added to the above gas to generate glow discharge. Furthermore, in the case of containing halogen atoms instead of hydrogen atoms in the first amorphous layer (), instead of the above SiH ₄ /He gas and GeH ₄ /He gas,
SiF ₄ /He gas and GeF ₄ /He gas may be used. In order to form a second amorphous layer () on the first amorphous layer () formed to a desired layer thickness as described above, it is necessary to For example, SiH ₄ gas, C ₂ H ₄
This is accomplished by diluting each of the gases with a diluent gas such as He as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the second amorphous layer (), for example, SiF ₄ gas and C ₂ H ₄ gas, or by adding SiH ₄ gas thereto, form the second amorphous layer in the same manner as above. This is done by forming a layer (). Needless to say, all the 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 1101. Valve 1
In order to avoid gas remaining in the gas piping leading from 117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, and the auxiliary valve 11
32, 1133 and fully open the main valve 1134 to temporarily evacuate the system to high vacuum, as necessary. For example, in the case of glow discharge, the amount of carbon atoms contained in the second amorphous layer ( ) is determined by adjusting the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas introduced into the reaction chamber 1101 as desired. Therefore, when forming a layer by sputtering, the sputtering area ratio of the silicon wafer and the graphite wafer should be changed when forming the target, or the mixing ratio of the silicon powder and the graphite powder should be changed. By molding the target, it can be controlled as desired. The amount of halogen atoms (X) contained in the second amorphous layer (2) is determined when the raw material gas for introducing halogen atoms, for example SiF ₄ gas, is
This is done by adjusting the flow rate when introduced into 101. Further, during layer formation, it is desirable that the base 1137 be 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 production apparatus shown in FIG. 11, GeH ₄ /He was deposited on the cylindrical A substrate under the conditions shown in Table 1 and according to the rate of change curve of the gas flow rate ratio shown in FIG.
The first amorphous layer () was formed by changing the gas flow rate ratio of gas and SiH ₄ /He gas with the elapsed layer formation time, and then the second amorphous layer was formed under the conditions shown in Table 1. An electrophotographic image forming member was obtained. The image-forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0kV for 0.3sets, and a light image was immediately irradiated using a tungsten lamp light source, transmitting a light amount of 2lux.set. It was irradiated through a mold 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 2 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 13 under the conditions shown in Table 2. An electrophotographic image forming member was produced in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 3 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 14 under the conditions shown in Table 3. Electrophotographic image formation was carried out in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. A member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH 4 /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 15 under the conditions shown in Table _4. Electrophotographic image formation was carried out in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. A member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 5 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 16 under the conditions shown in Table 5. Electrophotographic image formation was carried out in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. A member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 6 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 17 under the conditions shown in Table 6. Electrophotographic image formation was carried out in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. A member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 7 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 18 under the conditions shown in Table 7. Electrophotographic image formation was carried out in the same manner as in Example 1, except that the first amorphous layer () was formed by changing the ratio with the elapsed layer formation time and using the other conditions as in Example 1. A member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 8 In the same manner as in Example 1, except that Si ₂ H ₆ /He gas was used instead of SiH ₄ /He gas and the conditions shown in Table 8 were changed, electrons were A photographic imaging member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 9 An electrophotographic image was produced in the same manner as in Example 1 except that SiF ₄ /He gas was used instead of SiH ₄ /He gas and the conditions shown in Table 9 were changed. A forming member was formed. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 10 In Example 1, (SiH ₄ /He + SiF ₄ /He) gas was used instead of SiH ₄ /He gas, and the
An electrophotographic image forming member was formed under the same conditions as in Example 1 except that the conditions shown in Table 10 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 11 In Examples 1 to 10, the conditions for creating the third layer were
Electrophotographic image forming members were formed under the same conditions as shown in each example except that the conditions shown in Table 11 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, the results shown in Table 11A were obtained. Example 12 In Examples 1 to 10, the conditions for creating the third layer were
Each of the electrophotographic image forming members was formed under the same conditions as shown in each Example except that the conditions shown in Table 12 were used. 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 12A were obtained. Example 13 GeH ₄ /He gas, SiH ₄ /He gas,
An electrophotographic image forming member was formed under the same conditions as in Example 1 except that the gas flow rate ratio of NO gas and SiH ₄ /He gas was changed as well as the elapsed time of layer formation. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 14 GeH ₄ /He gas, SiH ₄ /He gas,
An electrophotographic image forming member was formed under the same conditions as in Example 1, except that the gas flow rate ratio of NO gas and SiH ₄ /He gas was varied with the elapsed time of layer formation. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 15 In Examples 1 to 10, the same toner as in Example 1 was used, except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp to form an electrostatic image. When the image quality of the toner transfer images was evaluated for each of the electrophotographic image forming members prepared under the same image forming conditions as in Examples 1 to 10, it was found that the images had excellent resolution and good gradation reproducibility. Clear, high-quality images were obtained. Example 16 An electrophotographic image forming member was prepared according to the same conditions and procedures as in Examples 2 to 10, except that the conditions for creating the amorphous layer () were as shown in Table 15. Huo (Sample No. 12-201~12-208, 12-301~12-
308,..., 72 samples from 12-1001 to 12-1009) were created. Each of the electrophotographic image forming members thus obtained was individually placed in a copying machine, corona charged at 5 kV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux.sec.
The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper.
The transferred image was extremely good. Toner remaining on the electrophotographic imaging member without being transferred was cleaned with a rubber blade.
Even after repeating this process over 100,000 times,
In either case, no image deterioration was observed. Table 15A shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use. Example 17 When forming an amorphous layer (), a sputtering method was adopted and the target area ratio of silicon wafer and graphite was changed to separate silicon atoms and carbon in the amorphous layer (). Each of the image forming members was produced in exactly the same manner as in Example 1 except that the content ratio of atoms was changed. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated about 50,000 times, and then image evaluation was performed, and the results shown in Table 16 were obtained. . Example 18 When forming the amorphous layer (), SiH ₄ gas and C ₂
An image forming member was prepared in the same manner as in Example 1 except that the content ratio of silicon atoms and carbon atoms in the amorphous layer was changed by changing the flow rate ratio of H ₄ gas. I made it. For each of the image forming members thus obtained, the steps up to transfer were repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 17 were obtained. Example 19 When forming the amorphous layer (), SiH ₄ gas,
The method was exactly the same as in Example 1, except that the flow rate ratio of SiF ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the amorphous layer (). Then, each of the image forming members was prepared. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed and the results shown in Table 18 were obtained. Example 20 Each of the image forming members was prepared in exactly the same manner as in Example 1, except that the layer thickness of the amorphous layer (2) was changed. Image formation, development, as described in Example 1
The cleaning process was repeated and the results shown in Table 19 were obtained.

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[Table] ◎: Excellent ○: Good

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[Table] ◎: Excellent ○: Good

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【table】

【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Produces image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Produces image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: Germanium atom (Ge) containing layer... ...approx. 200℃ Germanium atom (Ge) non-containing layer... ...approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 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 each show the distribution state of germanium atoms in the first layer region (G). FIG. 11 is a schematic explanatory diagram of the device used in the present invention, and FIG.
20 are explanatory diagrams showing rate of change curves of the gas flow rate ratio in the embodiments of the present invention, respectively. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 105...Second amorphous layer ().

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, and a first layer region on the support that exhibits photoconductivity and is composed of an amorphous material containing silicon atoms and germanium atoms as a matrix, and silicon. A second material that is composed of an amorphous material containing no germanium atoms and exhibits photoconductivity.
a first amorphous layer having a layer structure in which layer regions are provided in order from the support side, and a second amorphous layer made of an amorphous material having silicon atoms and carbon atoms as a matrix. and the distribution concentration of germanium atoms in the first layer region decreases from the support side toward the side opposite to the support side, and the first amorphous layer A photoconductive member characterized by containing oxygen atoms. 2. The photoconductive member according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms. 3. The photoconductive member according to claim 2, wherein the hydrogen atom content is 0.01 to 40 atomic%. 4. The photoconductive member according to claim 1, wherein at least one of the first layer region and the second layer region contains a halogen atom. 5 The content of the halogen atoms is 0.01 to 40 atomic
% of the photoconductive member according to claim 4. 6. The photoconductive member according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms and halogen atoms. 7 The sum of the contents of hydrogen atoms and halogen atoms is
The photoconductive member according to claim 6, wherein the content is 0.01 to 40 atomic%. 8. The photoconductive member according to claim 4 or 6, wherein the halogen atom is selected from fluorine and chlorine. 9. 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. 10 The content of the germanium atoms is 1×10 ⁵
10. The photoconductive member according to claim 9, wherein the thickness of the first layer region is atomic ppm or more and the layer thickness of the first layer region is 30 μm or less. 11. The photoconductive member according to claim 1, wherein the first layer region has a layer thickness T of 30 Å to 50 μ. 12. The photoconductive member according to claim 1, wherein the second layer region has a layer thickness T _B of 0.5 to 90 μm. 13. The photoconductive member according to claim 1, wherein the sum of layer thicknesses (T+T _B ) of the first layer region and the second layer region is 1 to 100 μ. 14. The photoconductive member according to claim 1, wherein a layer thickness T of the first layer region and a layer thickness T _B of the second layer region satisfy T _B /T≦1. 15. The photoconductive member according to claim 1, wherein the distribution concentration of the oxygen atoms is non-uniformly distributed in the layer thickness direction of the amorphous layer. 16. The photoconductive member according to claim 15, wherein the distribution concentration of the oxygen atoms is higher on the support side. 17 The content of oxygen atoms is 0.001 to 50 atomic
% of the photoconductive member according to claim 1. 18 The maximum value of the distribution concentration of the oxygen atoms is
Claim 1 which is 500 atomic ppm or more
The photoconductive member according to item 6. 19. The photoconductive member according to claim 1, wherein the second amorphous layer has a thickness of 0.003 to 30 μm. 20. The photoconductive member according to claim 1, wherein the second amorphous layer contains hydrogen atoms. 21 The content of hydrogen atoms is 1 to 40 atomic%
The photoconductive member according to claim 20. 22. The photoconductive member according to claim 1, wherein the second amorphous layer contains hydrogen atoms and halogen atoms. 23. The photoconductive member according to claim 22, wherein the hydrogen atom content is 19 atomic %, and the halogen atom content is 1 to 20 atomic %. 24 The content of the carbon atoms is 1×10 ^-3 ~
The photoconductive member according to claim 1, which has a content of 90 atomic %.