JPH0216915B2 - - 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.)
The present invention relates to photoconductive members for electrophotography that are 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, electrophotographic photoconductive members having conventional photoconductive layers composed of a-Si have electrical, optical, and photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness; The reality is that there are points that can be further improved in terms of use environment characteristics such as moisture resistance and stability over time, and it is necessary to improve overall characteristics. For example, when applying it to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When photographic photoconductive members are 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 responsiveness gradually decreases, etc. In many cases, this resulted in some inconveniences. 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 amorphous layer and diffusion of impurities from the support into the amorphous layer may pose problems. Therefore, while efforts are being made to improve the properties of the a-Si material itself, when designing photoconductive members for electrophotography,
It is necessary to devise ways to solve all of the problems mentioned above. 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 and applicability as a photoconductive member used in electrophotographic image forming members, a-
Si, especially a silicon atom, is used as a matrix, and a hydrogen atom (H)
or an amorphous material containing at least one of halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "a- Si
(H, Photoconductive materials not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially as photoconductive materials for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics 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 for electrophotography which has excellent photosensitivity characteristics, is extremely resistant to light fatigue, does not cause any deterioration phenomenon 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 for electrophotography which has high photosensitivity in the entire visible light range, has excellent matching with a photoconductor laser, 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 for electrophotography that has 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 for electrophotography having high signal-to-noise ratio characteristics. The photoconductive member for electrophotography of the present invention includes a support for a photoconductive member for electrophotography (hereinafter referred to as a "photoconductive member"), and a photoconductive member having 1 to 1×10 ⁶ atomic particles on the support.
a first layer region having a layer thickness of 30 Å to 50 μ and containing germanium atoms of ppm and at least partially crystallized;
a second layer region having a layer thickness of 30 Å to 50 μ containing an amorphous material containing germanium atoms of 10 ⁶ atomic ppm and an amorphous material containing no germanium atoms containing at least silicon atoms, and having photoconductivity. a third layer region having a layer thickness of 0.5 to 90μ and an amorphous layer having a layer structure provided in order from the support side, and at least the germanium atoms in the second layer region are It is characterized by being contained in a distribution state that is non-uniform in the thickness direction and more distributed toward the support side. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. 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 configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102 on a support 101 for photoconductive member.
The amorphous layer 102 has a free surface 105 on one end surface. From the support 101 side, the amorphous 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),
It has a layer structure in which a third layer region (S) 104 having photoconductivity is laminated in 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. 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 amorphous layer 102). be done. 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), so the affinity between the first layer region (C) and the second layer region (G) As will be described later, the distribution concentration of germanium atoms C at the support side end is excellent.
By making extremely large, when a semiconductor laser or the like is used, light on the long wavelength side that is almost completely absorbed by the third layer region (S) is transferred to the second layer region (G).
can be absorbed virtually completely,
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, and the vertical axis represents the second layer region.
(G) indicates the layer thickness, t _B is the second layer area on the support side (C)
t _T is the position of the end face of the second side opposite to the support side.
The position of the end face of the layer region (G) is shown. That is, the second layer region (G) containing germanium atoms is from the t _B side.
t Layer formation occurs toward _{the T} side. FIG. 2 shows a first typical example of the distribution state 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 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 Figure 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 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, from position _tB to position _t5 , the distribution concentration C of germanium atoms decreases linearly from concentration _C15 to concentration _C16 , and between position _t5 and position _tT , An example is shown in which the concentration C ₁₆ is set to a constant value. In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and gradually decreases from this concentration C ₁₇ until reaching the position t _{6 .} In the vicinity,
It is rapidly decreased 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 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. It is provided in the layer area (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 amorphous layer constituting the photoconductive member in the present invention is preferably placed on the support side. It is desirable to have a localized region (A) in which germanium atoms are contained 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 μ of 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 5μ thick on the second layer region (G) side from the interface position t _S , or, Layer area ( _LT )
Sometimes it is considered a part of. 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 Cmax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more relative to silicon atoms. 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 obtained. That is, in the present invention, the amorphous 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 Cmax of the distribution concentration exists within a layer thickness of 5 μm (a layer region of 5 μm thickness from t _S ) on the ) side. 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 amorphous 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%, optimally 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) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 1× ¹⁰⁶ atomic ppm, more preferably 100 to 1× ¹⁰⁶ atomic ppm, optimally 500 to
It is desirable that the content be 1×10 ⁶ atomic ppm. In the present invention, the content of germanium atoms contained in the second layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~1×10 ⁶ atomic
ppm, more preferably 100 to 8×10 ⁵ atomic
ppm, preferably 500 to 7×10 ⁵ atomic 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 (G) 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, halogen atoms (X) contained as necessary in the first layer region (C), second layer region (G), and third layer region (S) constituting the amorphous layer Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, to form the first layer region (C) composed of μC-Ge (Si, H, X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. It is made by vacuum deposition method and vacuum evaporation method. For example, to form the first layer region (C) composed of μC-Ge (Si, H, X) by the glow discharge method, basically silicon atoms (Si) can be supplied. Can supply raw material gas and germanium atoms (Ge) for Si 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,
A layer consisting of H, X) may be 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. 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, respectively, and the evaporation sources are heated using a resistance heating method or an electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporated material is heated and evaporated by EB method, etc., 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 source gas for Ge supply that can supply Ge, and a source gas for introducing hydrogen atoms (H) and/or a source 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 ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferred in terms of ease of handling 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 suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. 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, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
A first layer region (C) and a second layer region (G) in which gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr _{2 and} GeI 2 are also effective. These can be mentioned as starting materials for the formation. Among these substances, halides containing hydrogen atoms can be used to generate electrical or photovoltaic electricity at the same time that halogen atoms are introduced into the layer during the formation of the first layer region (C) and the second layer region (G). Since hydrogen atoms, which are extremely effective in controlling physical 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 to 30 atomic%, and optimally 0.01 to 40 atomic%.
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 (C), for example, the support temperature or/and the amount of 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 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
0.01~40atomic%, more preferably 0.05~30atomic
%, 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 (I) for forming the second layer region (G) described above is used. From inside,
A case where the second layer region (G) is formed using the starting material [starting material for forming the third layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying Ge; , can be carried out according to similar methods and conditions. 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 a 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 supplying Si, a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure. to generate a glow discharge, and a-Si
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into the deposition chamber for sputtering. In the present invention, hydrogen atoms (H) contained in the third layer region (S) constituting the amorphous 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 conductive properties of the amorphous layer can be appropriately controlled as desired by containing a substance (D) that controls the conductive properties in the amorphous layer. I can do it. Such substance (D) may be contained evenly in the entire layer region of the amorphous layer, or may be contained locally 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 unevenly 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 a substance. 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 conduction characteristics at least in the second layer region (G) constituting the amorphous layer, the content of the substance (D) can be improved. The conductive properties of the layer region [which may be part or all of the second layer region (G)] can be arbitrarily controlled as desired, and such materials 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 controlling conduction properties is as follows:
The conductive properties required for the layer region (PN) or, if the layer region (PN) is provided in direct contact with the support, the relationship with the properties at the contact interface with the support. etc., can be selected as appropriate based on organic relevance. In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material controlling the conduction characteristics is determined. The content is selected appropriately. In the present invention, the content of the substance (D) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1 ×10 ⁴ atomic ppm, optimally 1
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, when the free surface of the amorphous layer is subjected to polar charging treatment, at least second 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 amorphous layer is subjected to polar charging treatment, holes are injected from the support side through at least the second layer region (G) into the third layer region (S). can be effectively 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 preferably 30 atomic ppm or less. In the present invention, the amorphous layer contains a layer region containing a substance controlling conductivity having a conductivity type of one polarity, and a substance controlling 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 . For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the amorphous layer so as to be in direct contact with each other to form a so-called P-n junction. , a depletion layer can be provided. A substance (D) that controls conduction properties, for example, group group atoms or group atoms, is structurally introduced into the layer region constituting the amorphous layer to create a layer region containing the substance (D). PN), during layer formation,
The starting material for introducing the group atom or the starting material for introducing the group atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the amorphous layer. As a starting material for introducing such group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ ,
Boron hydride such as B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ ,
Examples include boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlC ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ ,
InCl ₃ , TlCl ₃ and the like can also be mentioned. As starting materials for the introduction of group atoms, those effectively used in the present invention 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 , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. 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,
On the surface, NiCr, Al, Cr, Mo, Au, Ir,
Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO
(In ₂ O ₃ +SnO ₂ ) etc., conductivity can be imparted, or if it is a synthetic resin film such as polyester film, NiCr,
Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb,
Vacuum deposition of thin films of metals such as Ta, V, Ti, Pt, etc.
Conductivity is imparted to the surface by providing it on the surface by 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 appropriately determined so as to form a desired photoconductive member.
When flexibility is required as a photoconductive member,
It is made as thin as possible within a range that allows it to fully function as a support. 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 a SiF ₄ gas cylinder diluted with He (99.99% purity, below)
Abbreviated as SiF ₄ /He. ) 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 glass 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, SiH ₄ /He gas from the gas cylinder 1102,
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 the base 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 flow controller 110.
7 and 1108, respectively. Subsequently, the outflow valves 1117, 1118 and the auxiliary valve 11
32 gradually opens to supply each gas to the reaction chamber 1101.
to flow into. 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, the same conditions and procedures are followed except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary. , by maintaining a glow discharge for a desired period of time, a third layer region (G) containing substantially no germanium atoms is formed on the second layer region (G).
layer region (S) can be formed. In order to contain a substance that controls conductivity in an arbitrary layer region of each layer region constituting the amorphous layer, a gas such as B ₂ H ₆ or PH ₈ is added to the deposition chamber 1 during layer formation.
It may be added to the gas introduced into 101. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 11, 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 testing device, corona charged at 5.0 KV for 0.3 seconds, and immediately exposed to 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. 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 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. 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 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 image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 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 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image was evaluated using an electrophotographic image forming member prepared under the same conditions as described above, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. 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

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[Table] ◎: Excellent ○: Good

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[Table] ◎: Excellent ○: Good

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are diagrams for explaining the distribution state of germanium atoms in the amorphous layer, respectively. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
FIG. 8 is an explanatory diagram showing the rate of change curve of the gas flow rate ratio in each embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a layer thickness on the support containing 1 to 1×10 ⁶ atomic ppm of germanium atoms and at least partially crystallized.
a first layer region of 30 Å to 50 μ and a layer thickness of 30 Å to 50 μm containing an amorphous material comprising at least silicon atoms and 1 to 1×10 ⁶ atomic ppm germanium atoms;
A second layer region of 50μ and a third layer region of 0.5 to 90μ thick containing an amorphous material containing at least silicon atoms and no germanium atoms and exhibiting photoconductivity are provided in order from the support side. and an amorphous layer having a layer structure such that germanium atoms are contained in at least the second layer region in a distribution state in which germanium atoms are non-uniform in the layer thickness direction and are distributed more toward the support side. A photoconductive member for electrophotography, which is characterized by: 2. The photoconductive member for electrophotography according to claim 1, wherein any of the first layer region, the second layer region, and the third layer region contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 2, wherein any of the first layer region, the second layer region, and the third layer region contains a halogen atom.