JPH0220982B2 - - 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 an image forming member for electrophotography, application to a photoelectric conversion/reading device is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes afterimages, or when used repeatedly at high speeds, responsiveness gradually decreases. There were many cases where spots appeared. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. 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. , in particular, an amorphous material having a silicon atom as its base material and containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous material. The layer structure of a photoconductive member made of a-Si (hereinafter referred to as "a-Si (H, The photoconductive members designed and manufactured under such specific specifications not only show extremely superior properties in practical use, but also surpass in every respect when compared with conventional photoconductive members. This is based on the discovery that it has extremely excellent properties as a photoconductive member for electrophotography, and that it has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, 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 (hereinafter referred to as "photoconductive member") which is long-lasting, 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 that has high photosensitivity in the entire visible light range, is particularly good in matching with semiconductor lasers, has excellent interference prevention, and has a fast photoresponse. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. The photoconductive member of the present invention includes a support for the photoconductive member, and a layer having a thickness of 30 Å to 50 μ and made of an amorphous material containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm on the support. A layer structure in which a layer region (G) and a layer region (S) with a layer thickness of 0.5 to 90 μ made of an amorphous material containing silicon atoms (not containing germanium atoms) are provided in order from the support side. Layer thickness 1
It consists of a photoreceptive layer that exhibits photoconductivity of ~100μ,
The photoreceptive layer has a layer region (N) containing 0.001 to 50 atomic% of nitrogen atoms, and the distribution concentration line of nitrogen atoms in the layer region (N) in the layer thickness direction is the same as that of the photoreceptor layer. It increases smoothly and continuously in the direction of the upper end surface,
The maximum distribution concentration of nitrogen atoms is 500 atomic ppm
It is characterized by having the above area. The photoconductive member of the present invention designed to have the above-mentioned 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 properties are stable, it is highly sensitive, and it is highly sensitive.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, is excellent in interference prevention, and has a fast optical response. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. 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 a-
A first layer region (G) 103 composed of Ge (Si, H, X) and a second layer region (S) 104 composed of a-Si (H, X) and having photoconductivity. It has a layered structure laminated in sequence. The germanium atoms contained in the first layer region (G) 103 may be contained so as to be uniformly distributed in the first layer region (G) 103, or the germanium atoms may be contained in the first layer region (G) 103 so as to be uniformly distributed, or Although it is contained evenly in the direction, 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 important to ensure that the content is uniform and evenly distributed in order to make the properties uniform in the in-plane direction. is necessary. In particular, it is evenly contained in the layer thickness direction of the light-receiving layer 102 and the support 101
(the side opposite to the side where the photoreceptive layer 10 is provided)
2) toward the support 10 (surface 105 side of
Either make it so that it is more distributed on the 1st side, or
Alternatively, it is contained in the first layer region (G) 103 so as to have the opposite distribution state. In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the first layer region (G) is as described above in the layer thickness direction, and the distribution state of germanium atoms contained in the first layer region (G) is as described above. It is desirable that the distribution be uniform in the in-plane direction parallel to the surface of the . In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (G), and a light-receiving layer is not provided in such a layer structure. By forming such a photoconductive member, it is possible to obtain a photoconductive member that has excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. Further, in one of the preferred embodiments, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously and evenly distributed in the entire layer region, and germanium atoms The distribution concentration C in the layer thickness direction is from the support side to the second layer region (S)
Since a change is given that decreases toward By extremely increasing the distribution concentration C of germanium atoms in the second layer region (S), when a semiconductor laser or the like is used, light on the long wavelength side, which is almost completely absorbed in the second layer region (S), can be absorbed into the second layer region (S). In the first layer region (G), substantially complete absorption can be achieved, and interference due to reflection from the support surface can be prevented. In addition, in the photoconductive member of the present invention, when silicon atoms are contained in the first layer region (G), the first layer region (G) and the second layer region (S)
Since each of the amorphous materials constituting the two has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. 2 to 10 show typical examples in which the distribution state of germanium atoms contained in the first layer region (G) of the photoconductive member in the present invention is non-uniform in the layer thickness direction. It will be done. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G), and t _B represents the first layer region (G) on the support side. t _T indicates the position of the end surface of the first layer region (G) on the side opposite to the support side. That is, in the first layer region (G) containing germanium atoms, layers are formed from the t _B side toward the t _T side. FIG. 2 shows the first distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction.
A typical example is shown. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region (G) containing germanium atoms is formed and the surface of the first layer region (G) contact, t ₁ Up to the position t1, the distribution concentration C of germanium atoms takes a constant value _C1 and is contained in the first layer region (G) in which germanium atoms are formed, and from the position _t1 the concentration _C2 decreases to the interface. It is gradually and continuously decreased until reaching position _tT . Interface position t _T
The distribution concentration C of germanium atoms is C ₃
It is said that In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. 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 is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction, in the present invention, On the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface _tT side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. A case in which it is provided in the layer 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 on the support side as described above, or on the contrary, on the free surface side. On the other hand, it is desirable to have a localized region (A) containing germanium atoms at a relatively high concentration. For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, the localized region ( _A) is
It is desirable that the distance be within 5μ. In the present invention, the localized region (A) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region (A) is a part or all of the layer region (L _T ) is appropriately determined 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 distribution concentration C _nax of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, and more It is desirable that the layer be formed in such a manner that the concentration can be preferably distributed at 5000 atomic ppm or more, most preferably 1×10 ⁴ atomic ppm or more. That is, in the present invention, in the layer region (G) containing germanium atoms, the maximum value C _nax of the distribution concentration exists within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B) . It is preferable that it be formed in a similar manner. In the present invention, the content of germanium atoms contained in the first layer region (G) may be appropriately determined as desired so as to effectively achieve the object of the present invention. preferably 1 to 10×10 ⁵ atomic ppm, more preferably 100 to 9.5×10 ⁵ atomic ppm, optimally
It is desirable that the content be 500 to 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 photoconductive member has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is preferably between 30 Å and 50 μ, more preferably
It is desirable that the thickness be 40 Å to 40 μ, most preferably 50 Å to 30 μ. Further, the layer thickness T of the second layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. The sum (T _B +T) of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) is based on the characteristics required for both layer regions and the overall photoreceptive layer. It is determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the required properties and the properties required. 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 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×
In the case of 10 ⁵ atomic ppm or more, the layer thickness T _B of the first layer region (G) is desirably made quite thin, preferably 30 μ or less, more preferably 30 μ or less.
It is desirable that the thickness be 25μ or less, optimally 20μ or less. In the present invention, specifically, the halogen atoms (X) contained in the first layer region (G) and/or second layer region (S) constituting the photoreceptive layer as necessary include: Examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the photoconductive member of the present invention, the photoreceptive layer contains a , a layer region (N) containing nitrogen atoms is provided. The nitrogen atoms contained in the photoreceptive layer may be evenly contained in the entire layer area of the photoreceptor layer, or
Alternatively, it may be contained and unevenly distributed only in a part of the layer region of the photoreceptive layer. In the present invention, the distribution state of nitrogen atoms in the layer region (N) is such that even if the distribution concentration C(N) is uniform in the in-plane direction parallel to the surface of the support, Similar to the distribution state of germanium atoms explained using FIGS. 2 to 10, the distribution concentration C(N)
is non-uniform in the layer thickness direction. FIGS. 11 to 16 show typical examples of the distribution of nitrogen atoms in the entire photoreceptive layer.
In these figures, the horizontal axis shows the distribution concentration C(N) of nitrogen atoms in the layer thickness direction, the vertical axis shows the layer thickness of the photoreceptive layer exhibiting photoconductivity, and _tB shows the photoreceptor on the support side. t T indicates the position of the end face (lower end face) of the layer, and t _T indicates the position of the end face (upper end face) of the photoreceptive layer on the side opposite to the support side. The photoreceptive layer is formed from the _tB side toward the _tT side. In the example shown in FIG. 11, no nitrogen atoms are contained in _the layer region from position tB to position _t9 , and in the layer region from position _t9 to free surface position _tT of the photoreceptor layer _t9
The distribution concentration C of nitrogen atoms gradually increases from the t side to the _T side.
(N) increases and reaches t _T , and the distribution concentration C(N) of nitrogen atoms reaches the concentration C ₂₁ . In the example shown in Figure 12, from position t _B to the free surface
Nitrogen atoms are contained in the entire layer region of the photoreceptor layer up to t _T , _and the distribution concentration C(N) is zero at t _B , and increases gradually and smoothly and monotonically up to t _T. The concentration reaches _C22 . In the example shown in Fig. 13, the distribution concentration C(N) of nitrogen atoms in the layer region from position _tB to _t10 varies from zero to
The distribution concentration C(N) of nitrogen atoms increases monotonically up to C ₂₃ and is constant at the concentration C ₂₃ in the layer region from position t ₁₀ to t _T . In the example shown in Fig. 14, in the layer region from position t _B to t ₁₁ , the distribution concentration C (N) of nitrogen atoms is
Slowly decreasing from C ₂₄ to C ₂₅ , from position t ₁₁ to t ₁₂
In the layer region up to t, the distribution concentration C(N) is constant at a concentration C ₂₅ , and in the layer region from position t ₁₂ to t _T , the distribution concentration C(N) of nitrogen atoms is continuous from C ₂₅ to C ₂₆ . It has increased. In the example shown in FIG. 15, there are two layer regions (N) containing nitrogen atoms. That is, in the layer region from position _tB to _t13 , the distribution concentration C(N) of nitrogen atoms decreases from _C27 to zero, and in the layer region from position _t13 to _t14 , nitrogen atoms are not included. In the layer region from position _t14 to _tT , the distribution concentration C(N) increases monotonically from zero to _C28 . In the case of the example shown in FIG. 16, in the layer region from position t _B to t ₁₅ , the distribution concentration of nitrogen atoms C(N)
is constant at C ₂₉ , and in the layer region from position t ₁₅ to t _T , it increases gradually and slowly at first, and then increases sharply and reaches C ₃₀ at t _T. In the present invention, when the main purpose of the layer region (N) containing nitrogen atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is In order to prevent charge injection from the free surface of the photoreceptive layer,
When it is provided near the free surface and the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, it is provided so as to occupy the end layer region (E) of the photoreception layer on the side of the support. provided. In the first case above, the content of nitrogen atoms contained in the layer region (N) is relatively low in order to maintain high photosensitivity, and in the second case, the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain high photosensitivity, and in the second case, the charge from the free surface of the photoreceptor layer is In the third case, it is desirable to use a relatively large amount near the surface in order to prevent the injection of particles, and in the third case, to ensure strong adhesion to the support. In addition, for the purpose of achieving the above three at the same time,
Oxygen containing a large number of nitrogen atoms is distributed at a relatively high concentration on the support side and at a relatively low concentration at the center of the photoreceptive layer. The distribution state of atoms is defined as layer region (O)
It should be formed inside. In the present invention, the content of nitrogen atoms contained in the layer region (N) provided in the photoreceptive layer depends on the characteristics required for the layer region (N) itself, or when the layer region (N) is a support. When provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (N), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The nitrogen atom content is appropriately selected with consideration given to the following. The amount of nitrogen atoms contained in the layer region (N) is
It can be determined as desired depending on the characteristics required of the photoconductive member to be formed, but 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 (N) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness of the photoreceptor layer is equal to the layer thickness T _O of the layer region (N). When the proportion of T is sufficiently large, the upper limit of the content of nitrogen atoms in the layer region (N) is
It is desirable that it be sufficiently smaller than the above value. In the case of the present invention, the ratio of the layer thickness T _O of the layer region (N) to the layer thickness T of the photoreceptive layer is two-fifths.
In such a case, the upper limit of the amount of nitrogen atoms contained in the layer region (N) is preferably
It is desirable that the content be 30 atomic % or less, more preferably 20 atomic % or less, and optimally 10 atomic % or less. In the present invention, the layer region (N) containing oxygen atoms constituting the photoreceptive layer is a localized region where nitrogen atoms are contained at a relatively high concentration on the support side and near the free surface, as described above. It is desirable that the photoreceptive layer has the region (B), and in this case, it is possible to further improve the adhesion between the support and the photoreceptive layer and to improve the receptive potential. The localized region (B) is desirably provided within 5 μm from the interface position t _B or free surface t _T , if explained using the symbols shown in FIGS. 11 to 16. In the present invention, the localized region (B) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B or free surface t _T , or may be the layer region (L _T ). Whether the localized region is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. In the localized region (B), the maximum value C _nax of the distribution concentration C (N) of nitrogen atoms is preferably 500 atomic as the distribution state of the nitrogen atoms contained therein in the layer thickness direction.
It is desirable that the layer be formed in such a manner that the distribution can be such that the concentration is at least ppm, preferably at least 800 atomic ppm, most preferably at least 1000 atomic ppm. That is, in the present invention, the layer region (N) containing nitrogen atoms is 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 that the distribution density C(N) be formed such that the maximum value C _nax exists at . In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the first layer region (G) composed of a-Ge (Si, H, X). It is made by a vacuum deposition method. For example, by using the glow discharge method, the first
To form the layer region (G), basically, a raw material gas for Ge supply that can supply germanium atoms (Ge) and, if necessary, a raw material gas for Si supply that can supply silicon atoms (Si). raw material gas, hydrogen atoms (H)
Raw material gas or/and halogen atom (X) for introduction
A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber to cause a glow discharge to occur on the surface of a predetermined support that has been placed at a predetermined position. a-Ge(Si,H,
A layer consisting of X) may be formed. Furthermore, in order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-Ge (Si, H, X) must be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. Good. In addition, when forming by a sputtering method, for example, a target made of Si, or a target made of Si and Ge in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. Using two of the prepared targets or a mixed target of Si and Ge, the source gas for supplying Ge diluted with a diluent gas such as He or Ar can be added as needed. ,
This is accomplished by introducing a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) into a deposition chamber for sputtering as necessary to form a plasma atmosphere of a desired gas. In order to make the distribution of germanium atoms non-uniform, for example, the Ge
The target may be sputtered while controlling the gas flow rate of the raw material gas for supply according to a desired rate of change curve. 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. In the present invention, halogen compounds that can be suitably used include, specifically, halogen gases such as fluorine, chlorine, bromine, and iodine, 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, and SiBr ₄ . . 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, germanium hydride, which is a raw material gas for Ge supply, and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate, and the first A first layer region (G) is deposited on the desired support by introducing a layer region (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. It may be formed. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. a-Ge (Si,
In order to form the first layer region (G) consisting of H, This can be done by heating and evaporating the source using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material into a desired gas plasma atmosphere. At this time, 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 introduce the gas 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 ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCI ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances may also be mentioned as useful starting materials for forming the first layer region (G). I can do it. Halides containing hydrogen atoms in these materials, when forming the first layer region (G), halogen atoms are introduced into the layer and hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time. Because it is done,
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 or SiH ₄ ,
Silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or a germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H _Ten ,
Germanium hydride such as Ge ₅ H ₁₂ , 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 are allowed to coexist in the deposition chamber. This can also be done by causing electrical discharge. In a preferred example of the present invention, the amount of hydrogen atoms (H) or halogen atoms (X) contained in the first layer region (G) constituting the photoreceptive layer to be formed
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 30 atomic%, optimally 0.1 to 25 atomic%
It is preferable to set it as %. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer region (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer region (S) composed of a-Si(H,X), the starting material () for forming the first layer region (G) described above is Form the first layer region (G) using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying Ge from the inside. It can be carried out in the same manner and under the same 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 second layer region (S) composed of a-Si(H,X). It is made by a vacuum deposition method. For example, in order to form the second 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
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by sputtering, 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, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen The sum of the amounts of atoms (H+X) is
Preferably 1 to 40 atomic%, more preferably 5
It is desirable that the content be ~30 atomic%, optimally 5 to 25 atomic%. In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing nitrogen atoms is used as the starting material for forming the layer described above. 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 (N), a starting material for introducing nitrogen atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing nitrogen atoms (N), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen atoms (N) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), nitrogen atoms (N), and hydrogen atoms (H). It can be used in combination with a raw material gas having two constituent atoms. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N). The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming the layer region (N) is one containing N as a constituent atom or containing N and H. Gaseous or gasified atoms such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. Nitrogen compounds such as nitrogen, nitrides and azides can be mentioned. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Mention may be made of halogenated nitrogen compounds. In the present invention, the layer region (N) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (N) include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), trinitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentaoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms ( Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), which have constituent atoms of Si), oxygen atoms (O), and hydrogen atoms (H). Can be done. To form the layer region (N) containing nitrogen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or a Si ₃ N ₄ wafer, or a Si
This can be carried out by targeting a wafer containing a mixture of Si 3 N 4 and Si ₃ N ₄ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, by using Si and Si ₃ N ₄ as separate targets, or by using a mixed target of Si and Si ₃ N ₄ , a dilution gas atmosphere can be created as a sputtering gas. This is accomplished by sputtering in a gas atmosphere containing at least 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 (N) containing nitrogen atoms is provided when forming a photoreceptive layer, the distribution concentration C of nitrogen atoms contained in the layer region (N) is
In the case of glow discharge, in order to form a layer region (N) having a desired depth profile by changing (N) in the layer thickness direction,
This is accomplished by introducing a starting material gas for introducing nitrogen atoms whose distributed concentration C(N) is to be changed into a deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve. Ru. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, for example, a microcomputer or the like may be used to control the flow rate according to a pre-designed change rate curve to obtain a desired content rate curve. When the layer region (N) is formed by sputtering, the distribution concentration of nitrogen atoms in the layer thickness direction C(N)
In order to form a desired depth profile of nitrogen atoms in the layer thickness direction by changing the depth profile in the layer thickness direction, first, as in the case of the glow discharge method, the starting point for introducing nitrogen atoms is This is accomplished by using the substance in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a mixed target of Si and Si ₃ N ₄ is used, the mixing ratio of Si and Si ₃ N ₄ can be changed in advance in the layer thickness direction of the target. will be accomplished. 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 contains a substance that controls conduction properties. By containing (C), the conductive properties of the layer region (G) and/or the layer region (S) can be arbitrarily controlled as desired. In the present invention, the layer region (PN) containing the substance (C) that controls conduction properties may be provided in a part or all of the photoreceptive layer. Alternatively, the layer region (PN) may be provided in a part or all of the layer region (G) or the layer region (S). Examples of the substance (C) that controls conduction characteristics include impurities that are used in the semiconductor field, and in the present invention, for Si or Ge, p
Examples include a p-type impurity that provides type conduction characteristics, and an n-type impurity that provides n-type conduction characteristics. 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 (C) that controls conduction characteristics contained in the photoreceptive layer is determined by the amount of the substance (C) that controls the conduction characteristics required for the photoreception layer, or the substance (C) that is provided in direct contact with the photoreception layer. It can be selected as appropriate based on the organic relationship, such as the characteristics of other layers and supports to be used, and the relationship with the characteristics of the contact interface with the other layers and supports. In addition, when the substance for controlling the conduction properties is contained in the photoreceptive layer locally in a desired layer region of the photoreceptor layer, particularly at the edge of the photoreceptor layer on the side of the support. When it is contained in a sub-layer region (E), it may differ from the characteristics of another layer region provided in direct contact with the layer region (E) or the characteristics at the contact interface with the other layer region. The content of the substance that controls the conduction properties is selected appropriately, taking into consideration the relationship. 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 × 10 ³ atomic ppm. In the present invention, the content of the substance (C) in the layer region (PN) containing the substance (C) that controls conduction characteristics is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more, optimally
In the case of 100 atomic ppm or more, the substance (C)
is preferably contained locally in a part of the layer region of the light-receiving layer, and is particularly preferably contained unevenly in the support-side end layer region (E) of the light-receiving layer. Among the above, for example, by containing the substance (C) that controls the conduction characteristics in the support-side end layer region (E) of the photoreceptive layer in a content that is greater than or equal to the above-mentioned value. When the substance (C) to be contained is the above p-type impurity, it effectively inhibits the movement of electrons injected from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is subjected to polar charging treatment. In addition, when the substance to be included is the above-mentioned n-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it can be prevented from being injected into the photoreceptor layer from the support side. The movement of holes can be effectively prevented. 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 removed layer region (Z) may contain a substance that controls the conduction characteristics of the other polarity, or a substance that controls the conduction characteristics of the same polarity may be added to the end layer region (E). It may be contained in an amount much smaller than the actual amount contained in. In such a case, the content of the substance (C) that controls the conduction characteristics contained in the layer region (Z) depends on the polarity and content of the substance contained in the end layer region (E). It is determined as appropriate depending on the desire, but preferably from 0.001 to
1000atomic ppm, more preferably 0.05~
500atomic ppm, optimally 0.1-200atomic ppm
It is desirable that this is done. In the present invention, when the end layer region (E) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably , preferably 30 atomic ppm or less. 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 region by directly contacting a layer region containing . Blockage, e.g.
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. a substance (C) that controls conduction properties in the photoreceptive layer;
For example, to structurally introduce a group atom or a group atom, a starting material for introducing a group atom or a starting material for introducing a group atom is added in a gaseous state to a second layer in a deposition chamber during layer formation. It may be introduced together with other starting materials for forming the layer region. As a starting material for introducing such a group atom, 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 ₂ , BCl ₂ , BBr ₃ and the like. In addition,
AlCl ₂ , GaCl ₂ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₂ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such _as PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr 5 and DI ₃ . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₂ , 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. Ru. 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 above metal. Conductivity is imparted to the surface. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like.
Although its shape is determined, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is desirable to have an endless belt shape or a cylindrical shape 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 set to 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. 17 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)
Abbreviation for GeH ₄ /He. ) cylinder, 1104 is a NH ₃ 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 1122 of gas cylinders 112 to 1106 are used.
~1126, confirm that leak valve 1135 is closed, and inlet valve 1112~1
116. After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH 4 /He gas from gas cylinder 1103, GeH ₄ /He gas from gas cylinder 1104
NH ₃ gas valves 1122, 1123, 112
4 and outlet pressure gauges 1127, 1128, 1
Adjust the pressure of 129 to 1Kg/cm ² and open the inflow valve 11.
12, 1113, 1114 gradually, and the mass flow controllers 1107, 1108, 1109
Let them flow into each other. Subsequently, the outflow valve 11
17, 1118, 1119, auxiliary valve 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
The outflow valves 1117 and 111 are adjusted so that the ratio between the GeH ₄ /He gas flow rate and the NH ₃ 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 openings of valve 1118 and valve 1120 are gradually changed according to a pre-designed rate of change curve by controlling the flow rates of GeH ₄ /He gas and NH ₃ gas manually or by using an external drive motor or the like. The distribution concentration of germanium atoms and nitrogen atoms contained in the formed layer is controlled. In the manner described above, glow discharge is maintained for a desired period of time to form a first layer region (G) on the substrate 1137 to a desired layer thickness. First layer region (G) to desired layer thickness
At the stage where the outflow valve 1118 is formed, the outflow valve 1118
A substantial amount of germanium atoms is formed on the first layer region (G) by maintaining the glow discharge for the desired time, following similar conditions and procedures, except for completely closing the cell and changing the discharge conditions as necessary. It is possible to form a second layer region (S) that does not contain any of the above. First layer region (G) and second layer region (S)
In order to contain a substance (C) that controls conductivity, for example, B ₂ H ₆ , PH ₃ etc. is added during the formation of the first layer region (G) and the second layer region (S). The gas 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 17-3) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 17 under the conditions shown in Table 1.
(Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 18, and the distribution concentration of nitrogen atoms is shown in FIG. Each sample obtained in this way was placed in a charging exposure experimental device and corona charged at 5.0KV for 0.3 seconds.
A light image was immediately irradiated. The optical image was generated using a tungsten lamp light source, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developer (including toner and carrier) onto 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 instead of a tungsten lamp as the light source, 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 27-3) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 16 under the conditions shown in Table 3.
(Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 18, and the distribution concentration of nitrogen 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. In addition, 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】

【table】

【table】

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: Germanium atom (Ge)-containing layer: approx. 200℃ Germanium atom (Ge)-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 16 are explanatory views for explaining the distribution state of nitrogen atoms in the photoreceptive layer, respectively. FIG. 17 is a schematic explanatory view of the apparatus used in the present invention, and FIG. 19A and 19B are distribution state diagrams showing the content distribution concentration 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 a layer having a thickness of 30 Å to 30 Å and made of an amorphous material containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm on the support.
A layer in which a layer region (G) with a thickness of 50μ and a layer region (S) with a thickness of 0.5 to 90μ composed of an amorphous material containing silicon atoms (not containing germanium atoms) are provided in order from the support side. a photoreceptive layer exhibiting photoconductivity with a layer thickness of 1 to 100μ, the photoreceptor layer having a layer region (N) containing 0.001 to 50 atomic% of nitrogen atoms; ) has a region in which the distribution concentration line of nitrogen atoms in the layer thickness direction increases smoothly and continuously in the direction of the upper end surface of the photoreceptor layer, and the maximum value of the distribution concentration of nitrogen atoms is 500 atomic ppm or more. A photoconductive member for electrophotography, which is characterized by: 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the layer region (G) and the layer region (S) contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claims 1 and 2, wherein at least one of the layer region (G) and the layer region (S) 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.