JPH0217022B2 - - 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,
High signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, fast photoresponsiveness, and desired dark resistance placement. 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 photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which require a combined improvement in characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during the period of use, and this kind of When a photoconductive 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, responsiveness gradually decreases, among other disadvantages. There were many cases where problems occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when 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 amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes 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. 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 extensive research and study on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we have discovered that Si is an amorphous material whose matrix is silicon atoms. , especially a silicon atom as a host, a hydrogen atom H or a halogen atom X
An amorphous material containing at least one of the following, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "a-Si (H, ”]
A photoconductive member designed and produced by specifying the layer structure of the photoconductive member, which has a photoreceptive layer that exhibits photoconductivity, as described below, has extremely excellent properties in practical use. In addition to the fact that it is superior in all respects to conventional photoconductive materials, it has particularly excellent properties as a photoconductive material for electrophotography, and on the long wavelength side. This is based on the discovery that it has excellent absorption spectrum characteristics. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member for electrophotography that has a long lifespan, 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 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 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 "photoconductive member"), and germanium atoms and, if necessary, silicon atoms on the support. It is composed of an amorphous material containing 1 to 10 ×
A layer region G containing 10 ⁵ atomic ppm of germanium atoms and having a layer thickness of 30 Å to 50 μm, and a layer region S comprising an amorphous material containing silicon atoms (but not containing germanium atoms) and having a layer thickness of 0.5 to 90 μm. It consists of a photoreceptive layer having a layer thickness of 1 to 100 μm and exhibiting photoconductivity, which is provided in order from the support side, and the photoreceptor layer has a layer thickness of 0.001 to 100 μm with respect to the sum of silicon atoms, germanium atoms, and oxygen atoms. It has 50 atomic% oxygen atoms, and its distribution concentration in the layer thickness direction is C1 and C1, respectively.
The first layer region 1, the third layer region 3, and the second layer region 2, which are C3 and C2, are formed from the support in this order, and the C1, C3, and C2 are C3>C.
1, C3>C2, and either C1 or C2 is not 0. 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 the photoconductive member of the present invention. The photoconductive member 100 shown in FIG.
The photoreceptive layer 102 has a free surface 105 on one end surface. The light-receiving layer 102 is made of an amorphous material (hereinafter a-Ge (Si, H, ”)
The first layer region G103 composed of a-Si(H,
X) and has a layer structure in which a second layer region S104 having photoconductivity is laminated in order. The germanium atoms contained in the first layer region G103 may be contained so as to be uniformly distributed throughout the first layer region G103, or may be contained evenly in the layer thickness direction. However, the distribution concentration may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly contained in order to make the properties uniform in the in-plane direction. is also necessary. In particular, it is contained evenly in the layer thickness direction of the layer region G, and on the side opposite to the side where the support 101 is provided (the surface 105 of the light-receiving layer 102).
It is contained in the first layer region G103 so that it is distributed in a larger amount on the support body 101 side, or vice versa. In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the first layer region G is as described above in the layer thickness direction, and the germanium atoms are distributed in the plane parallel to the surface of the support. It is desirable to have a uniform distribution in the inward direction. In the present invention, germanium atoms are not contained in the second layer region S provided on the first layer region G, and it is difficult to form a photoreceptive layer in such a layer structure. Therefore, it is possible to obtain a photoconductive member that has excellent photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition, the distribution state of germanium atoms in the first layer region G is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the second layer region. When a change that decreases toward S is given, the affinity between the first layer region G and the second layer region S is excellent, and as will be described later, the support side end By making the distribution concentration C of germanium atoms extremely large, when a semiconductor laser or the like is used, light on the long wavelength side that is almost completely absorbed by the second layer region S can be absorbed into the first layer. In region G, it is possible to substantially completely absorb the light and prevent interference due to reflection from the support surface. In addition, when silicon atoms are contained in the first layer region G, which is one of the preferred embodiments of the photoconductive member of the present invention, the first layer region G and the second layer region S Each of the amorphous materials that make up has a common constituent element, silicon atoms, so
Chemical stability is sufficiently ensured at the laminated interface. 2 to 10 show the distribution state of germanium atoms in the layer thickness direction contained in the first layer region G of the photoconductive member when germanium atoms are contained in a non-uniformly distributed manner. A typical example is shown. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region G, and t _B represents the first layer region G on the support side.
The position of the end face of t _T is the first position opposite to the support side.
The position of the end face of the layer region G is shown. That is, the first 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 first layer region G in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region G containing germanium atoms is formed and the surface of the first layer region G are in contact with each other,
Up to the position t ₁ , the distribution concentration C of germanium atoms
is contained in the first layer region G where germanium atoms are formed while taking a constant value of C ₁ , and the position t ₁
The concentration is gradually and continuously decreased from C ₂ to the interface position t _T . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of 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. 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, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position t ₇ , the concentration decreases rapidly at first, and then slowly decreases to C ₁₉ at position t ₇ , and between position t ₇ and t ₈ , is gradually reduced very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region G in the layer thickness direction, in the present invention, In the first layer, the distribution state of germanium atoms has a portion where the distribution concentration C of germanium atoms is high, and a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. The case where it is provided in region G is cited as one of the preferred examples. The first layer region G constituting the photoreceptive layer constituting the photoconductive member in the present invention is preferably a localized region containing germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have A. For example, localized region A can be explained using the symbols shown in FIGS. 2 to 10 by 5μ from interface position _tB .
It is desirable that it be installed within the same range. The above localized region A may be the entire layer region L _T up to 5μ thick from the interface position t _B , or may be the layer region
Sometimes it is considered part of L _T. Whether the localized area A is a part or all of the layer area L _T is determined as appropriate depending on the characteristics required of the photoreceptive 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 value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms,
Preferably 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 layer region G containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (a layer region with a thickness of 5μ from t _B ). In the present invention, the content of germanium atoms contained in the first layer region G is appropriately determined as desired so as to effectively achieve the object of the present invention, but , preferably 1 to 10×10 ⁵ atomic ppm, more preferably 100 to 9.5×10 ⁵ atomic ppm, optimally 500 to
It is desirable that the amount is 8×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region G and the second layer region S is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the desired properties are fully imparted to the member. In the present invention, the layer thickness T _B of the first 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. In addition, the layer thickness T of the second layer region S is usually
0.5-90μ, preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. The sum of the layer thickness T _B of the first layer region G and the layer thickness T of the second layer region S (T _B +T) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the two. In the photoconductive member of the present invention, the above (T _B )
The numerical range of is preferably 1 to 100μ, more preferably 1 to 80μ, and optimally 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
When satisfying the relationship T _B /T≦1, it is desirable to select appropriate numerical values for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9.
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region G is 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the first 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 amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the second layer region S constituting the photoreceptive layer to be formed is preferably 1 to
It is desirable that the content be 40 atomic %, more preferably 5 to 30 atomic %, most preferably 5 to 25 atomic %. In the present invention, specific examples of the halogen atoms X contained in the first layer region G and/or second layer region S constituting the light-receiving layer as necessary include fluorine, chlorine, and bromine. , iodine, and fluorine and chlorine are particularly preferred. In the photoconductive member of the present invention, the photoreceptive layer contains a , a layer region O containing oxygen atoms is provided. The oxygen atoms contained in the photoreceptive layer may be contained evenly in the entire layer area of the photoreceptive layer, or may be contained only in some layer areas of the photoreceptive layer so that they are ubiquitous. Also good. In the present invention, the distribution state of oxygen atoms is nonuniform in the layer thickness direction in the entire photoreceptive layer, as described above, but in the first, second, and third layer regions. Uniform in the layer thickness direction. Figures 11 to 20
The figure shows a typical example of the distribution of oxygen atoms in the entire photoreceptive layer. In each of these figures,
The horizontal axis shows the distribution concentration C and O of oxygen atoms, and the vertical axis shows the layer thickness of the photoreceptive layer. T _B shown on the vertical axis indicates the position of the end surface of the photoreceptive layer on the support side, and t _T indicates the position of the end surface of the photoreceptive layer on the side opposite to the support. That is, the photoreceptive layer is formed from the t _B side toward the t _T side. In the example shown in FIG. 11, from position t _B to position t ₉
From position t ₉ to position t ₁₁ , the distribution concentration C and O of oxygen atoms are assumed to be concentration C ₂₂ , and from position t ₁₁ to position t _T , the concentration is C ₂₁ . C ₂₁ . In the example shown in FIG. 12, the distribution concentrations C and O of oxygen atoms are increased in steps from position t _B to position t ₁₂ to concentration C ₂₃ and from position t ₁₂ to position t ₁₃ to concentration C ₂₄ , From position _t13 to position _tT , the concentration is decreased to _C25 . In the example of FIG. 13, the distribution concentration of oxygen atoms C, O
is the concentration C ₂₆ from position t _B to position t ₁₄ , and the position
From _t14 to position _t15 , the concentration increases stepwise to _C27 , and from position _t15 to position _tT , the concentration is _C28 , which is lower than the initial concentration _C26 . In the example shown in FIG. 14, the distribution concentrations C and O are _C29 from position _tB to position _t10 , decrease to _C30 from position _t16 to position _t17 , and from position _t17 to position Up to t ₁₈ , the concentration C is increased stepwise to ₃₁ , and the position
From t ₁₈ to position t _B , the concentration is reduced to C ₃₀ . In the example shown in FIG. 15, a layer region with high oxygen atom distribution concentrations C and O is provided on the support side of the photoreceptive layer. Such a distribution concentration C of oxygen atoms,
By using O, it is possible to effectively prevent charge injection from the support side when subjected to charging treatment, and at the same time, it is possible to strengthen the adhesion between the support and the photoreceptive layer. Furthermore, by containing oxygen atoms at a lower concentration in the layer region between t ₂₀ and t _T , the dark resistance is further improved without reducing the photosensitivity. In the examples shown in FIGS. 16 to 20, a layer region containing no oxygen atoms is provided in the photoreceptive layer on the support side of the photoreceptor layer or on the opposite side from the support. In the present invention, when the main purpose is to improve photosensitivity and dark resistance, the oxygen atom-containing layer region O provided in the photoreceptive layer occupies the entire layer area of the photoreceptive layer. In order to prevent charge injection from the free surface of the photoreceptive layer, it is provided near the free surface and its main purpose is to strengthen the adhesion between the support and the photoreceptive layer. In this case, it is provided so as to occupy the end layer region of the light-receiving layer on the side of the support. In the first case mentioned above, the content of oxygen atoms contained in the layer region O is relatively low in order to maintain high photosensitivity, and in the second case to prevent charge injection from the free surface of the photoreceptor layer. relatively more to prevent,
In the third case, it is desirable to use a relatively large amount in order to ensure enhanced adhesion to the support. In addition, for the purpose of achieving the above three at the same time,
It is distributed at a relatively high concentration on the support side, at a relatively low concentration at the center of the photoreceptive layer, and in the surface layer region on the free surface side of the photoreceptor layer, a layer with a large number of oxygen atoms is distributed. What is necessary is to form a distribution state of oxygen atoms in the layer region O. In order to prevent charge injection from the free surface, a layer region with a high distribution concentration C and O of oxygen atoms is formed on the free surface side. However, if a layer region with a high distribution concentration C,O comes into contact with the atmosphere, it may adsorb moisture in the air and cause image blurring in the case of electrophotography. Low is desirable. In the present invention, the content of oxygen atoms contained in the layer region O provided in the light-receiving layer depends on the characteristics required of the layer region O itself or when the layer region O is in direct contact with the support. When provided, it can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region O, the characteristics of the other layer region and the relationship with the characteristics at the contact interface with the other layer region are also considered. and the content of oxygen atoms is appropriately selected. The amount of oxygen atoms contained in the layer region O is determined as desired depending on the characteristics required of the photoconductive member to be formed, but the amount of oxygen atoms contained in the layer region O is determined as desired depending on the characteristics required of the photoconductive member to be formed. "T
(SiGeO)) is preferably 0.001
~50atomic%, more preferably 0.002~
It is desirable that it be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region O occupies the entire area of the photoreceptive layer, or even if it does not occupy the entire area of the photoreceptor layer, the ratio of the layer thickness T _O of the layer area O to the layer thickness T of the photoreceptive layer is sufficiently large, it is desirable that the upper limit of the content of oxygen atoms contained in the layer region (O) is sufficiently smaller than the above value. In the case of the present invention, if the ratio of the layer thickness T _O of the layer region O to the layer thickness T of the photoreceptive layer is two-fifths or more, The upper limit of the amount of oxygen atoms is preferably:
30 atomic% or less, more preferably 20 atomic%
Hereinafter, the optimum value is preferably 10 atomic% or less. In the present invention, the layer region O containing oxygen atoms constituting the photoreceptive layer is the localized region B containing oxygen atoms at a relatively high concentration on the support side and near the free surface, as described above. In this case, it is possible to further improve the adhesion between the support and the photoreceptive layer and to improve the reception potential. The localized region B, described using the symbols shown in FIGS. 11 to 20, is preferably provided within 5 μm from the interface position t _B or free surface t _T. In the present invention, the localized region B is the entire layer region L T up to 5μ thick from the interface position t _B or free surface _{t T}
In some cases, it may be considered as a part of the layer region L _T . Whether the localized region B is a part or all of the layer region L _T is appropriately determined depending on the characteristics required of the light-receiving layer to be formed. The localized region B has a distribution concentration C of oxygen atoms as the distribution state of the oxygen atoms contained therein in the layer thickness direction.
It is desirable that the layers be formed so that a distribution state can be obtained in which the maximum value Cmax of O is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more. That is, in the present invention, the layer region O containing oxygen atoms has a distribution concentration C, O within 5 μm in layer thickness from the support side or free surface (layer region 5 μ thick from t _B or t _T ). It is desirable to form it so that a maximum value Cmax exists. In the present invention, the first layer region G composed of a-Ge (Si, H, It is done by a deposition method. For example, to form the layer region G by the glow discharge method, basically a raw material gas for supplying Si that can supply silicon atoms Si and a raw material gas for supplying Ge that can supply germanium atoms Ge are used. , if necessary, a raw material gas for supplying Si that can supply silicon atoms, a raw material gas for introducing hydrogen atoms H, and/or a raw material gas for introducing halogen atoms X into a deposition chamber whose interior can be reduced in pressure. A glow discharge is generated in the deposition chamber by introducing the gas at a desired pressure, thereby forming a layer made of a-Ge (Si, H, Just do it. Furthermore, in order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-Ge (Si, H, X) is formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. That's fine. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into 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 G made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region G containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which is a raw material gas for supplying Si, and
Introducing germanium hydride, which serves as a raw material gas for supplying Ge, and gases such as Ar, H ₂ , He, etc. into a deposition chamber forming a first layer region G at a predetermined mixing ratio and gas flow rate; The first layer region G can be formed on a desired support by generating a glow discharge and forming a plasma atmosphere of these gases, but it is possible to control the introduction ratio of hydrogen atoms. In order to make the process even easier, hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases as desired to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. The first layer made of a-SiGe (H,
To form the layer region G, for example, in the case of the sputtering method, two targets, one made of Si and one made of Ge, or two targets made of Si and Ge are used, and these are placed in 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 respectively housed in a deposition boat as evaporation sources, and these evaporation sources are used in a resistance heating method, Alternatively, it can be carried out by heating and evaporating by electron beam method (EB method) or the like and passing the flying evaporated material through a desired gas plasma atmosphere. In addition, when sputtering a target composed of Si, Ge
The layer region G can also be formed by introducing a raw material gas for supply. In order to make the distribution of germanium atoms non-uniform, for example, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge in accordance with a desired rate of change curve. 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 ,
Gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for forming the first layer region G. In the case of halides containing hydrogen atoms in these substances, when forming the first layer region G, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region G, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Generating a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. But it can be done. In a preferred example of the present invention, the amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X ) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. To control the amount of hydrogen atoms H and/or halogen atoms X contained in the first layer region G, for example, the support temperature or/and the amount of hydrogen atoms H or halogen atoms The amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer region S composed of a-Si (H,
The first layer is formed using starting materials [starting materials for forming the second layer region S] from among the starting materials for forming the layer region G excluding the starting material that becomes the raw material gas for supplying Ge. This can be carried out using the same method and conditions as when forming region G. That is, in the present invention, in order to form the second layer region S composed of a-Si (H, It is done by a deposition method. For example, in order to form the second layer region S composed of a-Si (H, Together with the raw material gas, if necessary, a raw material gas for introducing hydrogen atoms H and/or halogen atoms A layer made of a-Si(H,X) may be formed on the surface of a predetermined support placed at a predetermined position. In addition, when forming by a sputtering method, for example, 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, hydrogen atoms H or / and a gas for introducing halogen atoms X may be introduced into the deposition chamber for sputtering. In the present invention, in order to provide the layer region O containing oxygen atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing oxygen atoms is used as the starting material for forming the photoreceptive layer. It may be used in conjunction with the above, and the amount thereof may be controlled and contained in the formed layer. When a glow discharge method is used to form the layer region O, a starting material for introducing oxygen atoms is added to one selected as desired from among the starting materials for forming the amorphous layer described above. . As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas whose constituent atoms are silicon atoms Si, and a raw material gas whose constituent atoms are oxygen atoms O,
Hydrogen atom H or halogen atom X as necessary
or a raw material gas containing silicon atoms (Si) and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) at a desired mixing ratio. , also in a desired mixing ratio, or silicon atoms, Si
A raw material gas consisting of constituent atoms, silicon atoms Si,
A raw material gas having three constituent atoms, oxygen atom O and hydrogen atom H, can be mixed and used. Alternatively, a raw material gas containing silicon atoms Si and hydrogen atoms H as constituent atoms may be mixed with a raw material gas containing oxygen atoms O as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H Examples include lower siloxanes such as ₃ SiOSiH ₂ OSiH ₃ ). To form the layer region O containing oxygen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or _SiO2 wafer or Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and/or
The raw material gas for introducing the halogen atoms is diluted with a diluting gas as necessary, and introduced into a sputtering deposition chamber to form a gas plasma of these gases to sputter the Si wafer. Good. Alternatively, by using a target other than Si and SiO ₂ or a single target with a mixture of Si and SiO ₂ , the sputtering can be carried out in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms H and/or halogen atoms X as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when a layer region O containing oxygen atoms is provided when forming a photoreceptive layer, the distribution concentration C, O of oxygen atoms contained in the layer region O is changed stepwise in the layer thickness direction. In order to form a layer region O having a desired distribution state (depth profile) in the layer thickness direction, in the case of a glow discharge, the distribution concentration C, O for introducing oxygen atoms should be changed. This is accomplished by introducing a starting material gas into the deposition chamber, with the gas flow rate appropriately varied according to the desired rate of change line. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be appropriately changed by any commonly used method such as manually or by using an externally driven motor. At this time, instead of changing the flow rate manually, it is also possible to control the flow rate according to a pre-designed rate of change line using, for example, a microcomputer to obtain a desired content distribution concentration line. When forming the layer region O by the sputtering method, the desired distribution state (depth profile) of oxygen atoms in the layer thickness direction is obtained by changing the distribution concentration C, O of oxygen atoms in the layer thickness direction. To form,
First, as in the case of the glow discharge method, the starting material for introducing oxygen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is changed as desired. done by. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be done by changing the mixing ratio of Si and SiO ₂ in advance in the layer thickness direction of the target. In the photoconductive member of the present invention, the first layer region G containing germanium atoms and/or the second layer region S not containing germanium atoms include:
By containing the substance C that controls the conduction characteristics, the conduction characteristics of each layer region can be arbitrarily controlled as desired. That is, by providing a layer region PN containing a substance C that controls conduction characteristics in the photoreceptive layer, the conduction characteristics of the layer region PN can be controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, P-type impurities that impart P-type conductivity to Si or Ge, and N-type impurities that impart N-type conductivity to Si or Ge. Examples of n-type impurities that give 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 of the substance that controls the conductive properties contained in the layer region PN is determined by the conductive properties required for the layer region PN or other substances provided in direct contact with the layer region PN. It can be selected as appropriate based on the organic relationship, such as the characteristics of the layer region and the relationship with the characteristics at the contact interface with other layer regions. Furthermore, when the substance C that controls the conduction properties is incorporated locally in a desired layer region of the photoreceptive layer, particularly at the edge of the photoreceptor layer on the side of the support. When it is contained in the substratum region E,
The properties of other layer regions provided in direct contact with the layer region E and the relationship with the properties at the contact interface with the other layer regions are also taken into consideration, and the content of a substance that controls conduction characteristics is determined. The amount is selected accordingly. In the present invention, the content of the substance C 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 to 5×
It is desirable to set it to 10 ³ atomic ppm. In the present invention, the content of the substance C that controls the conduction characteristics in the layer region PN containing the substance C is preferably 30 atomic ppm or more, more preferably
50atomic ppm or more, optimally 100atomic ppm
In the above case, it is preferable that the substance C is locally contained in a part of the layer region of the photoreceptive layer, and it is particularly preferable that the layer region PN is unevenly distributed at the end of the photoreceptor layer on the side of the support. . In the present invention, the layer region PN can be provided in part or all of the layer region G or layer region S constituting the light-receiving layer. Further, the layer region PN may be provided in a part or all of the layer region O, or may be provided so as to include the layer region O as a part thereof. By containing the substance C that controls the conduction characteristics in the support-side end layer region E of the photoreceptive layer so that the content exceeds the above-mentioned value, for example, the substance C to be contained can be the same as the P In the case of type impurities,
When the free surface of the photoreceptive layer is subjected to polar charging treatment, the movement of electrons injected from the support side into the photoreceptor layer can be effectively prevented, and the substance to be contained can be In the case of type impurities, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to effectively prevent the movement of holes injected from the support side into the photoreceptor layer. In this way, when the end layer region E contains a substance that controls conductivity of one polarity, the remaining layer region of the photoreceptive layer, that is, the end layer region E
The layer region Z excluding the portion may contain a substance that controls the conduction characteristics of the other polarity, or the end layer region E may contain a substance that controls the conduction characteristics of the same polarity. It may be contained in an amount much smaller than the actual 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 end layer region E. Although it is determined as appropriate, it is preferably 0.001 to 1000 atomic ppm, more preferably 0.05 to 500 atomic ppm, and optimally 0.1 to 500 atomic ppm.
It is desirable to set it to 200 atomic ppm. In the present invention, when the end layer region E and the layer region Z contain the same type of substance that controls conductivity, the content in the layer region Z is preferably 30 atomic ppm or less. is desirable. In addition to the above-mentioned cases, in the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having one polarity, and a substance controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact layer region by providing it in direct contact with 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 photoreceptive 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. In order to structurally introduce substances that control the conduction properties into the photoreceptive layer, such as group atoms or group atoms, starting materials for introducing group atoms or starting materials for introducing group atoms may be used during layer formation. The substance can be introduced in gaseous form into the deposition chamber together with other starting materials for forming the second layer region. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. As starting materials for introducing such group atom, specifically, for introducing boron atom,
B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ ,
Examples include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition,
AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for 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, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 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. 21 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 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 NO gas (purity 99.99%) cylinder, 1105 is a He gas (purity 99.999%) cylinder, and 1106 is a H ₂ 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.
After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, the main valve 1134 is first opened 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 when forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, NO from gas cylinder 1104
Open the gas valves 1122, 1123, 1124 and check the outlet pressure gauges 1127, 1128, 1129.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 1112,
1113 and 1114 are gradually opened to allow the flow into mass flow controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valve 111
7, 1118, 1119, the auxiliary valves 1132 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
Outflow valves 1117 and 111 are installed so that the ratio of GeH ₄ /He gas flow rate to NO gas flow rate becomes a desired value.
8 and 1119, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the flow rates of GeH ₄ /He gas and NO gas are changed manually or by using an external drive motor or the like to appropriately change the openings of valves 1118 and 1120 according to a pre-designed change rate line. The distribution concentration of germanium atoms and oxygen atoms contained in the layer is controlled. In the manner described above, the glow discharge is maintained for a desired period of time to form the first layer region G on the substrate 1137 to a desired layer thickness. At the stage where the first layer region G has been formed to the desired layer thickness, the desired layer is formed under the same conditions and procedures except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary. By maintaining the glow discharge for a time, the second layer region G is substantially free of germanium atoms.
layer region S can be formed. In order to contain a substance that controls conductivity in the first layer region G and the second layer region S, for example, when forming the first layer region G and the second layer region S,
Gases such as B ₂ H ₆ and PH ₃ may be added to the gas introduced into the deposition chamber 1101. 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 Samples (sample Nos. 11-1 to 17-6) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 21 under the conditions shown in Table 1.
(Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 22, and the distribution concentration of oxygen atoms is shown in FIG. Each sample thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 kV for 0.3 seconds.
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,
All samples had excellent resolution, and clear, high-density images with good gradation reproducibility were obtained. In the above, the toner image forming conditions were the same as above, except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp, and an electrostatic image was formed. When the image quality of the toner-transferred images was evaluated, all samples had excellent resolution, and clear, high-quality images with good gradation reproducibility were obtained. Example 2 Samples (sample Nos. 21-1 to 27-6) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 21 under the conditions shown in Table 3.
(Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 22, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples. Example 3 Samples (sample Nos. 31-1 to 37-6) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 21 under the conditions shown in Table 5.
(Table 6). The concentration distribution of germanium atoms in each sample is shown in FIG. 22, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples. Example 4 Samples (sample Nos. 41-1 to 47-6) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 21 under the conditions shown in Table 7.
(Table 8). The concentration distribution of germanium atoms in each sample is shown in FIG. 22, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples.

【table】

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[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: germanium atom Ge-containing layer
...About 200℃ Germanium atom Ge-free layer
…Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of germanium atoms in the photoreceptive layer, respectively. 11 to 20 are explanatory views for explaining the distribution state of oxygen atoms in the photoreceptive layer, respectively. FIG. 21 is a schematic explanatory view of the apparatus used in the present invention, and FIG. 23 are distribution state diagrams showing the content distribution state of each atom in the embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and an amorphous material containing germanium atoms and optionally silicon atoms on the support; On the other hand, it is composed of a layer region G containing 1 to 10×10 ⁵ atomic ppm of germanium atoms and having a layer thickness of 30 Å to 50 μ and an amorphous material containing silicon atoms (but not containing germanium atoms) and having a layer thickness of 0.5 to 90 μ. The layer region S is composed of a photoreceptive layer having a layer thickness of 1 to 100 μm and exhibiting photoconductivity, which is provided in order from the support side, and the photoreceptor layer is composed of silicon atoms, germanium atoms, and oxygen atoms. 0.001 to sum
A first layer region 1, a third layer region 3, and a second layer region 2 containing 50 atomic% oxygen atoms and having distribution concentrations in the layer thickness direction of C1, C3, and C2, respectively.
A photoconductive member for electrophotography, characterized in that C1, C3, and C2 satisfy C3>C1, C3>C2, and one of C1 and C2 is not 0. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the layer region S and the layer region G contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 2, wherein at least one of the layer region S and the layer region G contains a halogen atom. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the layer region G is non-uniform. 5. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the layer region G is uniform. 6. The photoconductive member for electrophotography according to claim 1, wherein the photoreceptive layer contains a substance that controls conductivity. 7. The photoconductive member for electrophotography according to claim 6, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table. 8. The photoconductive member for electrophotography according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table.