JPH0145984B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and economic stability, and it is necessary to improve the combined 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 has often been observed that residual potential remains during use, and this type of 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 afterimages, or when used repeatedly at high speeds, the response gradually decreases. There were many cases where spots appeared. 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 a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance 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. On the other hand, it has been proposed to provide an amorphous layer made of an amorphous material containing at least germanium atoms on a support in consideration of matching with a semiconductor laser. Adhesion with the crystalline layer and diffusion of impurities from the support into the amorphous layer may pose problems. Alternatively, when the photoconductive layer is composed of an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, 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. Consequently, problems may arise in the electrical or photoconductive properties of the formed layer with respect to voltage resistance. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, or ,
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. A so-called image defect called "white stripe" sometimes occurred. 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. The present invention has been made in view of the above points, and includes a
-As a result of comprehensive and intensive research on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., a- Amorphous materials based on Si, especially silicon atoms, and containing at least either hydrogen atoms (H) or halogen atoms (), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated The layer structure of a photoconductive member that is composed of amorphous silicon (hereinafter referred to as "a-Si(H,X)") and has an amorphous layer exhibiting photoconductivity will be described below. A photoconductive member designed and produced under the specifications described not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive members in every respect. This is based on the discovery that it has particularly excellent properties as a photoconductive member for electrophotography, and that it has excellent absorption spectrum properties on the long wavelength side. The present invention is not easily affected by the material of the support, has always stable electrical, optical, and photoconductive properties, and is applicable to all environments with almost no restrictions on the usage environment. The main object of the present invention is to provide a photoconductive member which has excellent photosensitivity characteristics, is extremely resistant to light fatigue, does not cause deterioration 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. The photoconductive member of the present invention includes a support for the photoconductive member, and a first layer region on the support that is composed of an amorphous material having germanium atoms as a matrix and is at least partially crystallized. , a second layer region made of an amorphous material containing germanium atoms having silicon atoms as a host, and a third layer region exhibiting photoconductivity made of an amorphous material having silicon atoms as a host. a fourth layer region made of an amorphous material containing silicon atoms and carbon atoms as a matrix;
has a light-receiving layer having a layered structure provided in order from the support side, and the distribution concentration of germanium atoms in the second layer region is directed from the support side to the side opposite to the support side. It is characterized by the fact that it has been decreasing in the past. The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, 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. 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 photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG.
The photoreceptive layer 102 has a free surface 105 on one end surface. From the side of the support 101, the photoreceptive layer 102 has germanium atoms as a matrix, or germanium atoms and silicon atoms as a matrix, contains hydrogen atoms or halogen atoms as necessary, and is at least partially crystallized. material (hereinafter referred to as “μc-Ge(Si,
A first layer region (C) 106 composed of "H, X)" and a-
A second layer region (G) 103 made of Si(H,X) (hereinafter abbreviated as "a-SiGe(H,X)"),
-Si, preferably a-Si (H, _x C _1-x ) _y (abbreviated as H,X) _1-y ) are stacked in this order. The germanium atoms contained in the second layer region (G) 103 are continuous in the layer thickness direction of the second layer region (G) 103 and on the side where the support 101 is provided. is contained in the second layer region (G) 103 so that it is more distributed on the support 101 side than on the opposite side (the surface 105 side of the photoreceptive layer 102). Ru. In addition, when the first layer region (C) 106 is made of a material containing silicon atoms in addition to germanium atoms, the germanium atoms contained in the first layer region (C) 106 is preferably the second
As in the case of the layer region (G) 103, it is desirable that the content be in a non-uniform distribution state, with a large amount distributed on the support 101 side. Furthermore, in such a case, the first layer region (C) 106 and the second layer region (G) 1
In 03, the distribution state of germanium atoms is
In the in-plane direction parallel to the surface of the support 101,
It is continuous and uniform, and in the layer thickness direction, the first
It is preferable that the non-uniform distribution is continuous through the layer region (C) 106 and the second layer region (G) 103 and increases toward the support 101 side. In the present invention, germanium atoms are not contained in the third layer region (S) provided on the second layer region (G), and an amorphous layer is not included in such a layer structure. including the visible light region, by forming
The photoconductive member can be made to have excellent photosensitivity to light having wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths. The distribution state of germanium atoms in the first layer region (C) and the second layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction is C. is given a change that decreases from the support side toward the third layer region (S), and the affinity between the first layer region (C) and the second layer region (G) is In addition, as will be described later, by making the distribution concentration C of germanium atoms extremely large at the side edge of the support, almost no germanium atoms are present in the third layer region (S) when a semiconductor laser or the like is used. In the second layer region (G), it is possible to substantially completely absorb light on the long wavelength side that cannot be completely absorbed, 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 second layer region (G) and the third 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 second layer region (G) of the photoconductive member of the present invention in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the second layer region (G), and _tB represents the second layer region on the support side.
(G), and t _T indicates the position of the end surface of the second layer region (G) on the side opposite to the support side. That is, the second layer region (G) containing germanium atoms is smaller than _tB .
t Layer formation occurs toward _{the T} side. FIG. 2 shows a first typical distribution of germanium atoms contained in the second layer region (G) in the layer thickness direction. _tB indicates the interface position between the support and the second layer region (C), and _tT indicates the interface position between the second layer region (G) and the third layer region (S). From _tB to the position _t1 , the distribution concentration C of germanium atoms takes a constant value _C1 , and from the position _t1 , the concentration gradually and continuously decreases from _C2 to the interface position _tT . There is. 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 contained germanium atoms gradually and continuously decreases from the concentration C ₄ from the position t _B to the position t _T , and at the position t _T the concentration C ₅ decreases. The distribution state is formed as follows. 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. At 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 continuously from the concentration C ₈ 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
It is said to be C ₁₀ . 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 , it is first rapidly decreased, and then slowly decreased to C ₁₉ at position t ₇ , and between position t ₇ and position t ₈ . ,
It is gradually reduced very slowly until it reaches 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 distribution states of germanium atoms contained in the second 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 distribution state of germanium atoms contained in the second layer region (G) has been explained above using FIGS. 2 to 10.
In (G), the above explanation also applies when germanium atoms are contained non-uniformly in the layer thickness direction. That is, in the explanation of FIGS. 2 to 10, the layer thickness (t _B t _T ) is the layer thickness of the second layer region (G), but it is the layer thickness of the first layer region (C). If the second layer region (G) contains germanium atoms non-uniformly in the layer thickness direction, the layer thickness (t _B t _T ) is explained as the sum of the layer thicknesses of these two layer regions. In each figure, the interface position t _S between the first layer region (C) and the second layer region (G) is t _B
Any position from t _T to t T is appropriately selected as desired. In the case where the first layer region (C) does not contain silicon atoms, the second layer region (G) constituting the photoreceptive layer of the photoconductive member in the present invention is preferably placed toward the support side. It is desirable to have a localized region (A) containing germanium atoms at a relatively high concentration. In the present invention, the localized region (A) is the first layer region
It is desirable to provide the second layer region (G) within 5 μm from the interface position t _S between the second layer region (G) and the second layer region (C). In the present invention, the localized region (A) may be the entire layer region (L _T ) up to a thickness of 5μ on the side of the second layer region (G) from the interface position t _S ; , may be part of the layer region (L _T ). 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) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration C _nax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 1000 atomic ppm or more with respect to silicon atoms. 5000 atomic ppm or more, optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be achieved. That is, in the present invention, the photoreceptive layer containing germanium atoms is formed in the second layer region (G) from the interface t _s between the first layer region (C) and the second layer region (G). It is preferable to form the layer so that the maximum value C _nax of the distribution concentration exists within a layer thickness of 5 μm from t S (a layer region of 5 μm thickness from t _S ). In the present invention, when the first layer region (C) contains silicon atoms, the localized region (A) has a layer thickness (t _B t _T ) in FIGS. 2 to 10. First layer area (C)
and the layer thickness of the second layer region (G), and the reference for the position of the localized region (A) is t _B (in this case,
The same idea as described above can be applied to the support side end surface of the first layer region (C). In the present invention, hydrogen atoms (H) contained in the third layer region (S) constituting the photoreceptive layer to be formed
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%.
It is desirable that it be 30 atomic %, most preferably 5 to 25 atomic %. In the present invention, when the first layer region (C) is made of germanium atoms and silicon atoms,
The content of germanium atoms contained in the first layer region (C) may be determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to x1. ×10 ⁶ atomic ppm, more preferably 100 to 1 × 10 ⁶ atomic ppm, optimally 500 to
It is preferable to set it to 10 ⁶ atomic ppm. In the present invention, the content of germanium atoms and atoms contained in the second layer region (C) may be appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably is 1~×1×
¹⁰⁶ atomic ppm, more preferably 100-8×
10 ⁵ atomic ppm, optimally 500 to 7×10 ⁵ atomic
It is preferable to set it in ppm. In the present invention, the first layer region (C) and the second layer region
(G) layer thickness is one of the important factors for effectively achieving the object of the present invention. due care must be taken in the design of the In the present invention, the layer thickness of the second layer region (G) and the third layer region (S) is one of the important factors for effectively achieving the object of the present invention, so the formation 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 (C) is preferably 30 Å to 50 μ, more preferably 100 Å to
It is desirable that the thickness be 30μ, optimally 500Å to 20μ. In the present invention, the layer thickness T _B of the second layer region (C) is
Preferably from 30 Å to 50 μ, more preferably from 40 Å
It is desirable that the thickness be 40μ, optimally 50Å to 30μ. Further, the layer thickness T of the third layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. Layer thickness T _B of the second layer region (G) and third layer region (S)
The sum of the layer thicknesses T (T _B +T) of the photoconductive member is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire amorphous layer. It is determined as desired during layer design. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. 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 second layer region (G) is 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the second layer region (G)
It is desirable that the thickness be quite thin, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less. In the present invention, the first layer region (C) and the second layer region
Specific examples of the halogen atom (X) contained in (G) and the third layer region (S) as necessary include fluorine, chlorine, bromine, and iodine, particularly fluorine, Chlorine may be mentioned as suitable. 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 first layer region (C) composed of μc-Ge (Si, H, X). This is accomplished by a vacuum deposition method and a vacuum evaporation method. For example, in order to form the first layer region (C) composed of μc-Ge (Si, H, X) by the glow discharge method, basically Si Can supply raw material gas and germanium atoms (Ge) for supply
Raw material gas for Ge supply and hydrogen atoms if necessary
(H) Introducing the raw material gas for introduction and/or the raw material gas for introducing halogen atoms (X) at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate glow discharge within the deposition chamber. , μC-Ge (Si,
It is sufficient if a layer consisting of H, X) is formed. In addition, when forming by sputtering method, for example, Ar,
One target made of Ge and a target made of Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases,
Alternatively, you can use two pieces of this target and a target composed of Ge, or use a mixed target of Si and Ge, and add He, Ge, etc. as necessary.
A raw material gas for supplying Ge diluted with a diluent gas such as Ar is introduced into a deposition chamber for sputtering, and a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into the deposition chamber for sputtering as necessary. The target may be sputtered by forming a gas plasma atmosphere of . 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 resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and passed through a desired gas plasma atmosphere. Second layer region composed of a-SiGe (H,X)
(G) is formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method.
For example, a-SiGe (H,
To form the first layer region (G) consisting of X), basically silicon atoms (Si) can be supplied.
Raw material gas and germanium atoms (Ge) for Si supply
A raw material gas for Ge supply that can supply Ge, and a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as required, into a deposition chamber whose interior can be reduced in pressure as desired. A glow discharge is generated in the deposition chamber, and a
- It is sufficient to form a layer made of SiGe(H,X). In addition, when forming by sputtering method,
For example, one target made of Ge and a target made of Si, or a combination of the target and Ge in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using two targets, or with Si.
Using a mixed target of Ge, a raw material gas for supplying Ge diluted with a diluent gas such as He or Ar is added as necessary to hydrogen atoms (H) and/or halogen atoms ( X) The target may be sputtered by introducing a gas for introduction into a sputtering deposition chamber to form a desired gas plasma atmosphere. 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 resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and 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 ,
Germanium hydrides in a gaseous state or capable of being gasified, such as Ge ₆ H ₁₄ , Ge ₇ , H ₁₆ , Ge ₈ , H ₁₈ , Ge ₉ H ₂₀ , etc., can be mentioned as being effectively used, especially in layer-forming operations. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling and good Ge supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon 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 preferably used in the present invention include halogen gases such as fluorine, fluorine, chlorine, bromine, and iodine, BrF, ClF,
Examples include interhalogen compounds such as ClF ₃ , 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. The first layer region (C) and the second layer region (G) containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating a first layer region (C) and a second layer region (G) containing halogen atoms according to the glow discharge method, basically silicon halide, which serves as a raw material gas for supplying Si, is used. A first layer region (C) and a second layer region are formed by mixing germanium hydride, which is a raw material gas for supplying Ge, and gases such as Ar, H ₂ , He, etc. at a predetermined mixing ratio and gas flow rate. (G) into a deposition chamber forming a first layer region (C) and a second layer region (C) on the desired support by creating a glow discharge and forming a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or a silicon compound gas containing hydrogen atoms may also be added to these gases. A layer may be formed by mixing desired amounts. 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 crystallize a part of the first layer region (C) using the above formation method, the temperature of the support needs to be 50 to 200°C higher than the temperature of the support that forms the second layer region (G). There is. 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 the above-mentioned silane and/or germanium hydride gases, 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 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,
Hydrogen halogenated germanium atoms such as GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc. are used as one of the constituent elements.
halides, 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 are also effective in the first layer region (C) and the second layer region (C).
It can be mentioned as a starting material for forming the layer region (G). Among these substances, halides containing hydrogen atoms are used to introduce halogen atoms into the layer at the time of forming the first layer region (C) and the second layer region (G). Since hydrogen atoms, which are extremely effective in controlling properties, are also introduced, they are used as a suitable raw material for introducing halogen in the present invention. Hydrogen atoms are separated into the first layer region (C) and the second layer region.
In addition to the above, H ₂ ,
Alternatively, silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is combined with germanium or a germanium compound for supplying Ge, or 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 ,
This can also be achieved by causing germanium hydride such as Ge ₈ H ₁₈ or Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si to coexist in a deposition chamber to generate a discharge. As a preferred example of the present invention, when at least one of hydrogen atoms or halogen atoms is contained in the first layer region (C) of the photoconductive member to be formed, the amount of hydrogen atoms (H) contained or The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.0001 to 40 atomic%,
More preferably 0.005-30atomic%, optimally 0.01
It is desirable that it be ~25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the second layer region (C), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled. In a preferred example of the present invention, hydrogen atoms contained in the second layer region (G) of the photoconductive member to be formed
The amount of (H) or 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 0.005 to 40 atomic%.
It is desirable that it be 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 second layer region (G), for example, the support temperature or/and the hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the third layer region (S) composed of a-Si(H,X), the starting material () for forming the second layer region (G) described above is Form the second layer region (G) using the starting material [starting material for forming the third layer region (S) ()] excluding the starting material that will become the raw material gas for supplying Ge. It can be carried out in the same manner and under the same conditions as in the previous case. 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 third layer region (S) composed of a-Si(H,X). It is made by vacuum deposition method. For example, in order to form the third layer region (S) composed of a-Si (H, Along with the raw material gas for Si supply, if necessary, the gas for introducing hydrogen atoms (H) or/
Then, a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber, so that the material gas is introduced onto the surface of a predetermined support that has been installed at a predetermined position in advance. a-Si(H,X)
What is necessary is to form a layer consisting of. In addition, when forming by a sputtering method, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber. In the present invention, hydrogen atoms (H) contained in the third layer region (S) constituting the photoreceptive layer to be formed
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%.
It is desirable that it be 30 atomic %, most preferably 5 to 25 atomic %. In the present invention, the conductivity of the layer region (PN) containing the substance (D) is improved by containing the substance (D) that controls the conduction characteristics in the first to third layer regions. The characteristics can be controlled as desired. Such a substance (D) may be evenly contained in the entire layer region of the first to third layer regions, or,
It may be locally contained in some layer regions. In the present invention, when the substance (D) that controls conduction properties is contained in the second layer region (G) so as to be ubiquitously distributed in a part of the second layer region (G), The layer region (PN) containing the substance (D) is preferably provided as an end layer region of the second layer region (G). In particular, when the layer region (PN) is provided as the end layer region on the support side of the second layer region (G), the substance (D) contained in the layer region (PN) By appropriately selecting the type and content thereof as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the amorphous layer. In the photoconductive member of the present invention, the substance (D) capable of controlling conduction properties is contained in the second layer region (G) constituting a part of the amorphous layer as described above. It is preferable to contain it evenly throughout the layer region (G) or evenly distributed in the layer thickness direction.
Furthermore, the substance (D) may also be contained in the third layer region (S) provided on the second layer region (G). When the substance (D) is contained in the third layer region (S), the type, amount, and content of the substance (D) contained in the second layer region (G) are determined. Depending on the method, the substance contained in the third layer region (S)
The type of (D), its content, and the manner of its inclusion are determined as appropriate. In the present invention, when the substance (D) is contained in the third layer region (S), preferably the substance (D) is contained in the layer region including at least the contact interface with the second layer region (G). It is desirable to include substance (D). In the present invention, the substance (D) may be evenly contained in the entire layer region of the third layer region (S),
Alternatively, it may be contained uniformly in a part of the layer region. When both the second layer region (G) and the third layer region (S) contain a substance (D) that controls conduction characteristics, the substance (D) in the second layer region (G) It is desirable that the layer region containing the substance (D) and the layer region of the second layer region (S) containing the substance (D) be in contact with each other. Further, when the substance (D) is contained in the first layer region (C), the second layer region (G), and the third layer region (S),
The substance (D) is a first layer region (C) and a second layer region (G).
and the third layer region (S) may be of the same kind or different kinds, and the content may be the same or different in each layer region. However, in the present invention, if the substance (D) contained in each layer region is the same in the three, the content in the second layer region (G) is sufficient. or use different types of substances (D) with different electrical properties.
It is preferable to contain each layer in each desired layer region. In the present invention, by containing the substance (D) that controls the conduction characteristics at least in the second layer region (G) constituting the photoreceptive layer, the layer containing the substance (D) can be improved. The conductive properties of the region (which may be part or all of the second layer region (G)) can be controlled as desired, but such a material (D) Examples of such impurities include so-called impurities in the semiconductor field, and in the present invention, p-type impurities that provide p-type conductivity characteristics and n-type impurities that provide n-type conductivity characteristics can be cited. 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. 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 in the layer region (PN) containing the substance (D) that controls conduction properties is determined by the conduction properties required for the layer region (PN),
Alternatively, when the layer region (PN) is provided in direct contact with the support, organic relationships such as the relationship with the properties at the contact interface with the support,
It can be selected as appropriate. In addition, the characteristics of other layer regions provided in direct contact with the layer region (PN) and the relationship with the characteristics at the contact interface with the other layer regions are also taken into consideration to control the conduction characteristics. The content of the substance is selected appropriately. In the present invention, the content of the substance (D) that controls conduction properties contained in the layer region (PN) is as follows:
Preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to
It is desirable that the content be 5×10 ³ atomic ppm. In the present invention, the content of the substance (D) that controls conduction characteristics in the layer region (PN) containing the substance (D) is preferably 30 atomic ppm or more, more preferably 50 atomic ppm. Above, optimally,
By setting the concentration to 100 atomic ppm or more, for example, when the substance (D) to be contained is the above-mentioned P-type impurity, at least the first phase is removed from the support side when the free surface of the photoreceptive layer is subjected to polar charging treatment. 2nd layer area
Injection of electrons into the third layer region (S) through (G) can be effectively prevented, and when the substance (D) to be contained is the n-type impurity, When the free surface of the photoreceptor layer is subjected to polar charging treatment, holes are effectively injected from the support side through at least the second layer region (G) into the third layer region (S). can be prevented. In the above case, as described above, the layer region (Z) excluding the layer region (PN) has the conductivity type of the substance that controls the conduction characteristics contained in the layer region (PN). The layer region (PN) may contain a substance that controls conduction characteristics with a conduction type different from that of the polarity, or a substance that controls conduction characteristics with a conduction type of the same polarity may be contained in the layer region (PN). It may be contained in an amount much smaller than the above amount. 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 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (D) that controls conductivity, the content in the layer region (Z) is preferably is desirably 30 atomic ppm or less. In the present invention, in the first to third layer regions, there is a layer region containing a substance controlling conductivity having conductivity of one polarity, and a conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance that controls the properties. For example, in the first to third layer regions, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided so as to be in direct contact with each other.
- A depletion layer can be provided by forming an n-junction. A substance (D) that controls conduction properties, for example, group group atoms or group atoms, is structurally introduced into the layer region of the photoreceptive layer to form a layer region (PN) containing the substance (D). During layer formation, a starting material for introducing group atoms or a starting material for introducing group atoms is introduced into a gaseous deposition chamber together with other starting materials for forming the photoreceptive layer. Just do it. 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 , B ₅ H ₁₁ ,
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ , etc. can also be mentioned. As starting materials for introducing group atoms, those effectively used in the present invention for introducing phosphorus 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 , SiH ₃ , SiCl ₃ , SiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. The fourth layer region (M) in the present invention is an amorphous layer containing silicon atoms (Si), carbon atoms (C), and optionally hydrogen atoms (H) and/or halogen atoms (X). quality material (hereinafter referred to as “a-(Si _x C _1-x ) _y (H,X) _1-y
) ”. However, 0<x, y<1). a-(Si _x C _1-x ) _y (H,X) _1-y
The layer region (M) is formed by a glow discharge method, a sputtering method, an electron beam method, or the like. 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 a photoconductive member, it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the fourth layer region (M) to be manufactured, etc. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same equipment system to achieve the fourth
A layer region (M) may be formed. To form the fourth layer region (M) by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y (H,X) _1-y is diluted as necessary. The gas is mixed with a predetermined mixing ratio and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and the gas is already deposited on the support. What is necessary is to deposit a-(Si _x C _1-x ) _y (H,X) _1-y on the first to third layer regions that have been formed. 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 gaseous substances or gasified substances containing at least one of carbon atoms (C), hydrogen atoms (H), and halogen atoms (X) are used. obtain. When using a raw material gas containing Si as one of Si, C, H, and According to or/and a raw material gas containing C and X as constituent atoms, also at a desired mixing ratio, or a raw material gas containing Si as constituent atoms,
A raw material gas containing Si, C, and H as constituent atoms or a raw material gas containing Si, C, and X as constituent atoms can be used in combination. 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, preferred halogen atoms (X) contained in the fourth layer region (M) are F,
Cl, Br, and I, with F and Cl being particularly preferred. In the present invention, raw material gases that can be effectively used to form the fourth layer region (M) include those in a gas state at normal temperature and normal pressure, or substances that can be easily gasified. can be mentioned. In the present invention, SiH 4 , Si 2 H 6 , Si 3 H 8 , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , which are constituent atoms of Si and H, are effectively used as the atomic gas for forming the fourth layer region (M). _{Si4H10 _}
Silicon hydride gas such as silanes, C
and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogen, hydrogen halide, halogen intermediate compound,
Examples include silicon halides, halogen-substituted silicon hydrides, and silicon hydrogen. 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 ₅ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), Isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and simple halogens. Examples include halogen gases such as fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH,
As HI, HCl, HBr, and interhalogen compounds,
BrF, ClF, ClF ₃ , ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ ,
IF ₅ , ICl, IBr, SiF ₄ as silicon halide,
Si ₂ F ₆ , SiCl ₃ Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I,
SiBr ₄ , halogen-substituted silicon hydride,
SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl, SiH ₃ Cl, SiH ₃ Br,
SiH ₂ Br ₂ , SiHBr ₃ , SiH ₄ ,
Silanes such as Si ₂ H ₈ , Si ₃ H ₈ , SiH ₁₀ ,
etc. can be mentioned. In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
CH ₂ F ₂ , CH ₃ F, CH ₃ ClOCH ₃ Br, CH ₃ I,
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ ,
Si(C ₂ H ₅ ) ₄ , isoalkyl silicide and SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These fourth layer region (M) forming substances contain silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the fourth layer region (M) to be formed. is selected and used as desired when forming the fourth layer region (M) so that it contains. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiH can contain halogen atoms. By introducing ₂ Cl ₂ , SiCl ₄ , SiH ₃ Cl, etc. at a predetermined mixing ratio in a gaseous state into the apparatus for forming the fourth layer region (M) and causing a glow discharge, a- (Si _x
C _1-x ) _y (Cl+H) Fourth layer region (M) consisting of _1-y
can be formed. To form the fourth layer region (M) by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted. This may be carried out 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, raw material gases for introducing C, H and/or The Si wafer may be sputtered by forming plasma. 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.
As the 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. are suitable as the diluting gas used when forming the fourth layer region (M) by the glow discharge method or the sputtering method. It can be mentioned as such. The fourth layer region (M) in the present invention is carefully formed so as to provide the required properties as desired. In other words, substances containing Si, C, and optionally H or/and In the present invention, a-(Si _x C1 _-x ) _y
In order to form (H,X) _1-y , the preparation conditions are strictly selected as desired. For example, to provide the fourth layer region (M) with the main purpose of improving voltage resistance, a-(Si _x C _1-x ) _y (H,X) _1-y is electrically insulating in the usage environment. Created as an amorphous material with pronounced sexual behavior. In addition, when the fourth layer region (M) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it resists the irradiated light to a certain extent. As an amorphous material with a sensitivity of 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 third layer region (S)
When forming the _{fourth layer region (M) consisting of (H} ,
In the present invention, a-
It is desirable that the temperature of the support during layer formation be strictly controlled so that (Si _x C _1-x ) _y (H,X) _1-y can be formed as desired. In the present invention, the formation of the fourth layer region (M) is performed by appropriately selecting an optimal range in accordance with the method for forming the fourth layer region (M) in order to effectively achieve the desired purpose. carried out, preferably at 20-400°C,
The temperature is more preferably 50 to 350°C, most preferably 100 to 300°C. The formation of the fourth layer region (M) involves the use of glow technology, which allows microsecond control of the composition ratio of atoms constituting the layer and control of the layer thickness compared to other methods. It is advantageous to adopt the discharge method or the sputtering method, but when forming the fourth layer region (M) using these layer forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. Discharge power is created a-(Si _x C _1-x ) _y (H,X) _1-y
It is one of the important factors that influences the characteristics of As a discharge power condition for effectively producing a-(Si _x C _1-x ) _y (H _, is preferably 10~300W, more preferably 20~
250W, optimally 50-200W is desirable. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr. In the present invention, the values of the support temperature and discharge power for forming the fourth layer region (M) are preferably within the ranges described above, but these layer forming factors are independent of each other. The desired characteristic a-(Si _x C _1-x )
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that a fourth layer region (M) consisting of _y (H,X) _1-y is formed. Similar to the production conditions for the fourth layer region (M), the amount of carbon atoms contained in the fourth layer region (M) in the photoconductive member of the present invention is determined according to the desired amount to achieve the object of the present invention. This is an important factor in the formation of the fourth layer region (M) where the properties are obtained. The amount of carbon atoms contained in the fourth layer region (M) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the fourth layer region (M). It can be determined by That is, the general formula a-(Si _x C _1-x ) _y (H,X) _1-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ". However, 0<a<1 ),
Amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C _1-b ) _c H _1-c ". However, 0<b, c<1) , an amorphous material (hereinafter referred to as "a-(Si _d
C _1-d ) _e (H,X) _1-e ”. However, 0<d, e<
1). In the present invention, the fourth layer region (M) is a-
When composed of Si _a C _1-a , the fourth layer region (M)
The amount of carbon atoms contained in is preferably 1×
10 ^-3 to 90 atomic%, more preferably 1 to 80 atomic%
%, preferably 10 to 75 atomic%. That is, if expressed as a in the above a-Si _a C _1-a , a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25 to 0.9. In the present invention, the fourth layer region (M) is a-
(Si _b C _1-b ) _c H _1-c , the amount of atoms contained in the fourth layer region (M) is preferably 1×
10 ^-3 to 90 atomic%, more preferably 1 to 90 atomic%
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%.
It is desirable that the hydrogen atom content be within this range, and photoconductive members formed with hydrogen atom content within these ranges can be satisfactorily applied in practice. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is preferably 0.1 to 99999, more preferably 0.1.
~0.99, optimally 0.15-0.9, c preferably 0.6
~0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. The fourth layer region (M) is a-(Si _d C _1-d ) _e (H,
X) When composed of _1-e , the content of carbon atoms contained in the fourth layer region (M) is as follows:
Preferably 1×10 ⁻³ to 90 atomic%, more preferably 1 to 90 atomic%, optimally 10 to 80 atomic%
It is desirable that this is the case. The halogen atom content is preferably 1 to 20 atomic%
It is desirable that the halogen atom content be within these ranges, so that photoconductive members produced when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more preferably 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, b is preferably 0.1 to 0.99999,
More preferably 0.1 to 0.99, optimally 0.15 to 0.9, e
is preferably 0.8 to 0.99, more preferably 0.82 to
0.99, optimally 0.85 to 0.98. The number range of the layer thickness of the fourth layer region 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. Further, the layer thickness of the fourth layer region (M) is the same as that of the fourth layer region (M).
The relationship between the amount of carbon atoms contained therein and the layer thickness of the first to third layer regions can be adjusted as desired based on the organic relationship depending on the characteristics required for each layer region. Therefore, it needs to be determined appropriately. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The layer thickness of the fourth layer region (M) in the present invention is preferably 0.003 to 30μ, preferably 0.004 to 30μ.
A desirable value is 20μ, most preferably 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NICr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, polyester, polyethylene,
Films or sheets of synthetic resins such as 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, Al, Cr, Mo, Au, Ir, Nb, Ta,
V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₂ +
Conductivity is imparted by providing a thin film consisting of SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
The surface is made conductive by providing a thin film of metal such as Ti or Pt on the surface 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. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
Usually, it is 100μ or more. 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 He gas (purity
99.999%) cylinder, 1106 is _H2 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 layer region (C) on the cylindrical substrate 1137, SiH 4 /He gas from the gas cylinder 1102 and SiH ₄ /He gas from the gas cylinder 11
03 to GeH ₄ /He gas from valves 1122, 11
23 and adjust the pressure of the outlet pressure gauges 1127 and 1128 to 1Kg/cm ² , and open the inflow valves 1112 and 1.
Gradually open 113 and install mass flow controller 1.
107 and 1108, respectively. Subsequently, the outflow valves 1117 and 1118, and the auxiliary valve 1
132 is gradually opened to supply each gas to the reaction chamber 110.
1. Adjust the outflow valves 1117 and 1118 so that the ratio of the SiH ₄ /He gas flow rate and the GeH ₄ /He gas flow rate at this time becomes a desired value,
Further, the opening of the main valve 1134 is adjusted while checking the reading of the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches a desired value. And basic 113
7 temperature is 400~600 by heating heater 1138
After confirming that the temperature is set in the range of °C, the power supply 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101, and at the same time the GeH _Four /
The distribution concentration of germanium atoms contained in the formed layer is controlled by gradually changing the opening of the valve 1118 by controlling the flow rate of He gas manually or by using an externally driven motor. In the manner described above, the glow discharge is maintained for a desired time to form a first layer region on the substrate 1137 to a desired layer thickness.
Form (C). At the stage when the first layer region (C) has been formed to a desired layer thickness, all outflow valves are closed. To give an example of forming the second layer region (G) on the first layer region (C), from the gas cylinder 1102
SiH ₄ /He gas, from gas cylinder 1103
Open the GeH ₄ /He gas valves 1122 and 1123 to reduce the pressure on the outlet pressure gauges 1127 and 1128 to 1.
Adjust to Kg/cm ² , inflow valve 1112, 1113
Gradually open the mass front roller 1107,
1108 respectively. Subsequently, the outflow valves 1117, 1118 and the auxiliary valve 1123 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
Adjust the outflow valves 1117 and 1118 so that the ratio with the GeH ₄ /He gas flow rate becomes the desired value, and
While checking the reading on the vacuum gauge 1136, adjust the main valve 1 so that the pressure inside the reaction chamber 1101 reaches the desired value.
Adjust the aperture of 134. 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. , and at the same time GeH ₄ /He according to the predesigned rate of change curve.
The distribution concentration of germanium atoms contained in the formed layer is controlled by gradually changing the opening of the valve 1118 by adjusting the gas flow rate manually or by using an externally driven motor. In the manner described above, the glow discharge is maintained for a desired period of time to form the second layer region (G) to a desired layer thickness on the first layer region (C). At the stage where the second layer region (G) has been formed to the desired layer thickness, following the same procedure of conditions, except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary, By maintaining the glow discharge for a desired period of time, a third layer region (S) substantially free of germanium atoms can be formed on the second layer region (G). In order to contain a substance that controls conductivity in an arbitrary layer region of each layer region constituting the photoreceptive layer, a gas such as B ₂ H ₆ or PH ₈ is added to the deposition chamber during layer formation.
Just add it to the gas introduced into 1101. In order to form the fourth layer region (M) in the third layer region (S) formed to the desired layer thickness as described above, a gas line that is not used during the deposition of the fourth layer region (M) is required. is changed to CH ₄ gas, and the third layer region (M)
By the same valve operation as in the formation of e.g.
This is accomplished by diluting each of SiH ₄ gas and C ₂ H ₂ gas with He or the like as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the fourth layer region (M), for example, SiF ₄ gas or
This is done by adding SiH ₄ gas and forming the fourth layer region (M) in the same manner as above. Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 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. The amount of carbon atoms contained in the fourth layer region (M) can be determined, for example, by glow discharge, SiH ₄ gas,
The flow rate ratio of the C ₂ H ₄ gas introduced into the reaction chamber 1101 can be changed as desired, or if the layer is formed by sputtering, sputtering of the silicon wafer and graphite wafer can be used to form the target. It can be controlled as desired by changing the area ratio or by changing the mixing ratio of silicon powder and graphite powder and molding the target. The amount of halogen atoms (X) contained in the fourth layer region (M) can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF ₄ gas, is introduced into the reaction chamber 1101. It is accomplished by doing so. 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 manufacturing apparatus shown in FIG. 11, the following steps were carried out on a cylindrical Al 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. 12.
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas with the elapsed layer formation time. 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 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. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation to obtain an electrophotographic image forming member. 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. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation to obtain an electrophotographic image forming member. 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. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation to obtain an electrophotographic image forming member. 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. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation to obtain an electrophotographic image forming member. 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. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. 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. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation to obtain an electrophotographic image forming member. 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 Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that Si ₂ H ₆ /He gas was used and the conditions shown in Table 8 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 9 In Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that SiF ₄ /He gas was used and the conditions shown in Table 9 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 10 Same conditions as in Example 1 except that (SiH ₄ /He + SiF ₄ /He) gas was used instead of SiH ₄ /He gas and the conditions shown in Table 10 were changed. Layer formation was carried out to obtain an electrophotographic image forming member. 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
Each of the electrophotographic image forming members was produced under the same conditions as shown in each Example except that the conditions shown in Table 11 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 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 produced 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 Toner image formation was performed in the same manner as in Example 1, except that an 810 nm GaAS semiconductor laser (10 mW) was used instead of the tungsten lamp as the light source to form an electrostatic image. When the image quality of the toner transfer image was evaluated on an electrophotographic image forming member prepared under the same conditions as in Example 1, it was found that a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. was gotten. Example 14 An electrophotographic image forming member was produced according to the same conditions and procedures as in Examples 2 to 10, except that the conditions for forming the fourth layer region (M) were as shown in Table 13. (Sample No. 12-201 to 12-208, 12-301 to 12-
308,..., 72 samples from 12−1001 to 12−1009)
It was created. Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine, and
Corona charging was performed for 0.2 seconds and a light image was irradiated. The light source uses a tungsten lamp, and the light intensity is 1.0lux.
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, no image deterioration was observed in any case. Table 14 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 15 When forming the fourth layer region (M), the target area ratio between the silicon wafer and graphite is changed to change the content ratio of carbon atoms to silicon atoms in the fourth layer region (M). Each of the image forming members was produced in exactly the same manner as in Example 1, except for the following steps. For each of the imaging members thus obtained,
After repeating the steps of image formation, development, and cleaning as described in Example 1 about 50,000 times, image evaluation was performed, and the results shown in Table 15 were obtained. Example 16 When forming the layer of the fourth layer region (M), the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas is changed to increase the concentration of silicon atoms and carbon atoms in the fourth layer region (M). Each of the image forming members was produced in exactly the same manner as in Example 1 except that the content ratio was changed. 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 16 were obtained. Example 17 When forming the fourth layer region (M), SiH ₄ gas,
Completely the same method 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 fourth layer region (M). Each of the imaging members was prepared by.
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.
The results shown in Table 17 were obtained. Example 18 Imaging and development were carried out as described in Example 1, in which each of the image forming members was prepared in exactly the same manner as in Example 1, except that the layer thickness of the fourth layer region (M) was changed. , the cleaning process was repeated to obtain the results shown in Table 18. Common layer forming conditions in the above embodiments of the present invention are shown below. Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

【table】

【table】

【table】

【table】

【table】

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【table】

【table】

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【table】

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[Table] ◎: Excellent ○: Good

【table】

[Table] ◎: Excellent ○: Good

【table】

【table】

【table】

【table】

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

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

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

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of germanium atoms in the second layer region, respectively. , and FIG. 11 are schematic illustrations of the apparatus used in the present invention, and FIGS. 12 to 18 are explanatory diagrams showing the rate of change curves of the gas flow rate ratio in the embodiments of the present invention, respectively. It is a diagram. 100...Photoconductive member, 101...Support, 1
02...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, and a first layer region on the support that is made of an amorphous material containing germanium atoms as a matrix and that is at least partially crystallized; A second layer region made of an amorphous material containing germanium atoms having silicon atoms as a host; and a third layer region exhibiting photoconductivity made of an amorphous material having silicon atoms as a host. and a fourth layer region made of an amorphous material having silicon atoms and carbon atoms as a host, the light-receiving layer having a layered structure in which the fourth layer region is provided in order from the support side, and A photoconductive member characterized in that the distribution concentration of germanium atoms in the second layer region decreases from the support side toward the side opposite to the support side. 2. Claim 1, wherein at least one of the first layer region, the second layer region, the third layer region, and the fourth layer region contains hydrogen atoms. The photoconductive member described. 3. According to claim 1, wherein at least one of the first layer region, the second layer region, the third layer region, and the fourth layer region contains a halogen atom. The photoconductive member described. 4 Claims in which at least one of the first layer region, the second layer region, the third layer region, and the fourth layer region contains hydrogen atoms and halogen atoms. The photoconductive member according to item 1. 5. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the first layer region is 0.0011 to 40 atomic%. 6. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the first layer region is 0.0001 to 40 atomic%. 7. The photoconductive member according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the first layer region is 0.0001 to 40 atomic%. 8. Claim 2, wherein the amount of hydrogen atoms contained in the second layer region is 0.01 to 40 atomic%.
The photoconductive member described in . 9. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the second layer region is 0.01 to 40 atomic%. 10. The photoconductive member according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the second layer region is 0.01 to 40 atomic%. 11. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the third layer region is 1 to 40 atomic %. 12. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the third layer region is 1 to 40 atomic %. 13. The photoconductive member according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the third layer region is 1 to 40 atomic %. 14. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the fourth layer region is 1 to 40 atomic %. 15. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the fourth layer region is 1 to 20 atomic %. 16 Claim 4, wherein the amount of halogen atoms contained in the fourth layer region is 1 to 20 atomic %, and the amount of hydrogen atoms is 19 atomic % or less.
The photoconductive member described in . 17. 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. 18. The photoconductive member according to claim 1, wherein the first layer region has a layer thickness T of 30 Å to 50 μ. 19. The photoconductive member according to claim 1, wherein the second layer region has a layer thickness T _B of 30 Å to 50 μ. 20. The photoconductive member according to claim 1, wherein the third layer region has a layer thickness T of 0.5 to 90μ. 21. The photoconductive member according to claim 1, wherein the sum of layer thicknesses (T _B +T) of the second layer region and the third layer region is 1 to 100 μ. 22 The method according to claim 1 and claim 21, wherein the layer thickness T _B of the second layer region and the layer thickness T of the third layer region satisfy T _B /T≦1. Photoconductive member. 23 The content of the germanium atoms is 1×
12. The photoconductive member according to claim 11, wherein the second layer region has a layer thickness of 10 ⁵ atomic ppm or more and a layer thickness of 30 μm or less. 24. The photoconductive member according to claim 1, wherein the photoreceptive layer contains a substance that controls conductivity. 25. The photoconductive member according to claim 24, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 26. The photoconductive member according to claim 24, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 27 The atom belonging to group of the periodic table is B,
The photoconductive member according to claim 25, which is selected from Ga. 28 The atom belonging to group of the periodic table is P,
27. The photoconductive member according to claim 26, which is selected from As. 29 The substance controlling the conductivity is 0.01 to 5×
Claim 2 containing 10 ⁴ atomic ppm
The photoconductive member according to item 4. 30. The photoconductive member according to claims 3 and 4, wherein the halogen atom is selected from fluorine and chlorine. 31. The photoconductive member according to claim 1, wherein the fourth layer region has a layer thickness of 0.003 to 3μ. 32 The content of the carbon atoms is 1×10 ^-3 ~
90 atomic % of the photoconductive member according to claim 1.