JPH0215062B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. Solid-state imaging devices are sometimes 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.
German Publication No. 2,855,718 describes its application as an electrophotographic image forming member, and German Publication No. 2,933,411 describes its application to a photoelectric conversion/reading device. 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 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, the response gradually decreases. There were many cases where spots appeared. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms Amorphous materials based on silicon atoms, especially amorphous materials containing at least either hydrogen atoms (H) or halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon Consisting of silicon or halogen-containing hydrogenated amorphous silicon (hereinafter "a-Si(H,X)" will be used as a generic term for these),
A photoconductive member that is designed and produced with the layer structure of a photoconductive member having a photoreceptive layer that exhibits photoconductivity specified as explained below not only exhibits extremely excellent properties in practical use. , it is superior in all respects to conventional photoconductive materials, has particularly excellent properties as a photoconductive material for electrophotography, and has excellent absorption on the long wavelength side. This is based on the discovery that it has excellent spectral 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 that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. The photoconductive member for electrophotography of the present invention includes a support for the photoconductive member for electrophotography, and a layer having a thickness of 30 mm formed of an amorphous material containing germanium atoms on the support.
A first layer region (H) having a thickness of Å to 50μ and a second layer region (S) having a layer thickness of 0.5 to 90μ and made of an amorphous material containing silicon atoms (but not containing germanium atoms) serve as the support. Layer thickness 1 to 100μ provided sequentially from the body side
A photoconductive member for electrophotography, comprising a photoreceptive layer having a photoconductivity of 0.001.
It is characterized by containing ~50 atomic % of nitrogen atoms, having a smooth concentration distribution, and having a maximum distribution concentration of 500 atomic ppm or more within 5 μm of layer thickness from the support side or free surface side of the layer. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. The photoconductive member for electrophotography of the present invention (hereinafter abbreviated as photoconductive member) has no influence of residual potential on image formation, has stable electrical characteristics, has high sensitivity, and has a high signal-to-noise ratio. It has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. 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-
First layer region (G)1 composed of Ge (Si, H, X)
03 and a-Si(H,X) and a second layer region (S) 104 having photoconductivity are laminated in this order. The germanium atoms contained in the first layer region (G) 103 may be uniformly distributed throughout the first layer region (G) 103, or may be distributed uniformly in the layer thickness direction. Although it is evenly contained, the distribution concentration may be non-uniform. However, in any case, it is evenly distributed in the in-plane direction parallel to the surface of the support, but from the point of view of making the properties uniform in the in-plane direction, is also necessary. Especially,
It is evenly contained in the layer thickness direction of the light-receiving layer 102 and is on the side opposite to the side where the support 101 is provided (the surface 105 side of the light-receiving layer 102).
It is contained in the first layer region (G) 103 so that it is distributed more toward the support 101 side than the other side, or so that it is distributed in the opposite direction. . 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, including the visible light region,
The photoconductive member can be made to have excellent photosensitivity to light having wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths. 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 are Since the distribution concentration C in the layer thickness direction is given a change that decreases from the support side toward the second layer region (S), the first layer region (G) and the second layer region (S) By making the distribution concentration C of germanium atoms extremely large at the edge of the support as described later, the second layer can be used when a semiconductor laser or the like is used. Light on the long wavelength side, which is almost completely absorbed in the region (S), can be virtually completely absorbed in the first layer region (G), preventing interference due to reflection from the support surface. You can. Furthermore, in the photoconductive member of the present invention, each of the amorphous materials constituting the first layer region (G) and the second layer region (S) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. FIGS. 2 to 10 show typical examples in which the distribution state of germanium contained in the first layer region (G) of the photoconductive member in the present invention is uneven in the layer thickness direction. . In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer region.
(G) indicates the layer thickness, and t _B is 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 _tB 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 ₃ at position t _T . In the case of Figure 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. reduced, and at position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased from the concentration C ₃ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
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. One preferable example is the case where it is provided in the layer region (G). 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 back side. 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, it is desirable that the localized region (A) be provided within 5 μm from the interface position t _B. 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 according to 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,
More preferably 5000 atomic ppm or more, optimally 1
It is desirable to form a layer in such a way that a distribution state of 10 ⁴ atomic ppm or more can be obtained. 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) 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, preferably
100-9.5× ¹⁰⁵ atomic ppm, optimally 500-8×
It is desirable to set it to 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 T _B of the first layer region (G) is
Preferably 30 Å to 50 μ, more preferably 40 Å to
It is desirable that the thickness be 40μ, optimally 50Å to 30μ. 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. Layer thickness T _B of the first layer region (G) and second layer region (S)
The sum of the layer thicknesses T (T _B +T) of the layers of the photoconductive member is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired during design. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. In a more preferred embodiment of the present invention, the above layer thickness T _B and layer thickness T are 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 halogen atoms (X) contained in the first layer region (G) and second layer region (S) constituting the light-receiving layer as necessary include fluorine atoms. , chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the photoreceptive layer, the photoreceptive layer contains , 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,
Alternatively, it may be contained only in a part of the layer region of the photoreceptive layer and may be distributed ubiquitously. In the present invention, even if the distribution state of nitrogen atoms in the layer region (N) is uniform in the in-plane direction parallel to the surface of the support, the distribution state of nitrogen atoms in the layer region (N) is uniform. It is non-uniform in the thickness direction. In the example shown in FIG. 11, from position t _B to position t ₉
In the layer region up to, the distribution concentration of nitrogen atoms C
The concentration of (O) is _C21 , and in the layer region from position _t9 to position _t10 , it increases sharply from _t9 to _t10 ,
At t ₁₀ , the distribution concentration of nitrogen atoms reaches a peak value C ₂₂ .
In the layer region from position _t10 to position _t11 , the distribution concentration C(N) of nitrogen atoms decreases, and at position _tT the concentration _C21 decreases.
becomes. In the example shown in FIG. 12, from position t _B to position t ₁₂
In the layer region from t 12 to t 13, the distribution concentration C(N) of nitrogen atoms is taken as the concentration C ₂₃ , and in the layer region from position t ₁₂ to t ₁₃ , it increases rapidly from t ₁₂ to t 13, and at position t ₁₃ , the nitrogen atom distribution concentration C(N) is C ₂₃ . The distribution concentration C(N) of nitrogen atoms takes a peak value _C24 , and decreases until the distribution concentration C(N) of nitrogen atoms becomes almost zero in the layer region from position _t13 to position _tT . In the example shown in FIG. 13, from position t _B to position t ₁₄
In the layer region up to, the distribution concentration C(N) of nitrogen atoms is
The distribution concentration C(N) of nitrogen atoms gradually increases from C ₂₅ to C ₂₆ and reaches a peak value C ₂₆ at position t ₁₄ .
In the layer region from position t ₁₄ to position t _T , the distribution concentration C(N) of nitrogen atoms decreases rapidly, and at position _{t T} the concentration C ₂₅
becomes. In the example shown in FIG. 14, the distribution concentration C(N) of nitrogen atoms at position t _B is concentration C ₂₇ , and the distribution concentration C (N) decreases until position t ₁₅ , and at t ₁₅ , the concentration C (N) becomes C ₂₈ . Become.
In the layer region from position _t15 to position _t16 , the distribution concentration C(N) of nitrogen atoms is constant at a concentration _C28 . position
In the layer region from t ₁₆ to position t ₁₇ , the distribution concentration C(N) of nitrogen atoms increases, and the distribution concentration C at position t ₁₇ increases.
(N) takes the peak value _C29 . In the layer region from position _t17 to position _tT , the distribution concentration of nitrogen atoms C(N)
decreases to a concentration C ₂₈ at position _tT . 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 should be 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 mentioned above, the content of nitrogen atoms contained in the layer region (N) is made 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 a 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 a high photosensitivity; In the third case, it is desirable to use a relatively large amount to prevent injection, 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,
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. The distribution state of nitrogen atoms is defined as the layer region (N).
It should be formed inside. However, in order to prevent charge injection from the free surface, the distribution concentration of nitrogen atoms C(N) on the free surface side is
When a layer region (N) with a high concentration of nitrogen atoms is formed, when the layer region with a high distribution concentration of nitrogen atoms C(N) comes into contact with the atmosphere,
In the case of electrophotography, it is desirable that the distribution concentration C(N) of nitrogen atoms is low in the immediate vicinity of the free surface, since moisture in the air may be adsorbed and cause image blurring. 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 attached to the 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 oxygen atoms contained in the layer region (N) is preferably 30 atomic% or less, more preferably 20 atomic%.
% or less, preferably 10 atomic% or less. In the present invention, the layer region (N) containing nitrogen atoms constituting the photoreceptive layer contains nitrogen atoms at a relatively high concentration on the support side and near the free surface, as described above. It is desirable that the photoreceptive layer is provided with a localized 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 14. 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 the layer region ( L _T )
Sometimes it is considered a part of. 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. The localized region (B) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum distribution concentration C _nax of oxygen atoms is preferably 500 atomic ppm or more,
More preferably 800 atomic ppm or more, optimally
It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be obtained. 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, to form the first layer region (G) composed of a-Ge (Si, H, X) by the glow discharge method, germanium atoms (Ge) can basically be supplied. Raw material gas for Ge supply, raw material gas for Si supply that can supply silicon atoms (Si), raw material gas for introducing hydrogen atoms (H), and/or raw material gas for introducing halogen atoms (X), if necessary. A raw material gas 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, thereby depositing a-Ge on the surface of a predetermined support that has been placed at a predetermined position. A layer consisting of (Si, H, 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 sputtering method, for example, a target composed of Si or a target composed of Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using two targets composed of Ge,
Or using a mixed target of Si and Ge,
If necessary, raw material gas for supplying Ge diluted with diluting gas such as He or Ar, and gas for introducing hydrogen atoms (H) or/and halogen atoms (X) as necessary for sputtering. This is accomplished by introducing the desired gas into a deposition chamber and creating a plasma atmosphere of the desired gas. 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 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. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be 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 the raw material gas for supplying Si, and
Germanium hydride, which is the source gas for supplying Ge, and gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber to form the first layer region (G) at a predetermined mixing ratio and gas flow rate. The first layer region (G) can be formed on the desired support by generating a glow discharge and forming a plasma atmosphere of these gases, but the introduction of hydrogen atoms In order to more easily control the ratio, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases 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. a-SiGe by ion plating method
In order to form the first layer region (G) consisting of (H, This can be done by heating and evaporating the evaporation source using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material through 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 , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances may also be mentioned as effective starting materials for forming the first layer region (G). I can do it. The halides containing hydrogen atoms in these substances introduce halogen atoms into the layer when forming the first layer region (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. 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 amount of hydrogen atoms contained in the first layer region (G) constituting the photoreceptive layer to be formed, The sum of the amounts of halogen atoms (H+X) is preferably 0.01 to 40 atomic%, more preferably 0.05
It is desirable to set it to ~30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the layer region (G) in FIG. The amount of the starting material used to contain the atoms (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 (I) for forming the first layer region (G) described above is used. From inside,
When forming 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; , following similar methods and conditions. That is, in the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the 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. A-Si is deposited on the surface of a predetermined support that has been placed at a predetermined position.
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into the deposition chamber for sputtering. In the present invention, hydrogen atoms (H) contained in the second layer region (S) constituting the photoreceptive layer to be formed
, the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%.
It is desirable that it be 30 atomic %, most preferably 5 to 25 atomic %. In the present invention, 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 added to the above-mentioned starting material for forming the photoreceptive layer. It may be used together with the starting material and contained in the formed layer while controlling its amount. 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. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has a nitrogen atom (N) as a constituent atom with the raw material gas which has a nitrogen atom (N) as a constituent atom. Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) used when forming the layer region (N) include those in which N is a constituent atom or N and H are constituent atoms. Atoms such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), and other gaseous or gasifiable substances. Mention may be made of nitrogen, nitrogen compounds such as nitrides and azides. 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 oxygen 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 pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atom (O), and hydrogen atom (H) as constituent atoms, such as lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). I can do it. 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 sputtering deposition chamber, 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 nitrogen atoms, the raw material gas for introducing nitrogen 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) containing no germanium atoms
The layer region (G) and/or the layer region (S) are contained in the layer region (G) and/or the layer region (S) by containing a substance (C) that controls conduction properties.
The conduction properties of can be arbitrarily controlled as desired. In the present invention, the substance (C) that controls conduction properties
The layer region (PN) containing may be provided in a part or the entire layer region 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 substances (C) that control conduction characteristics include so-called impurities in the semiconductor field.
In the present invention, a p-type impurity that imparts p-type conductivity to Si or Ge, and an n-type impurity that imparts n-type conductivity to Si or Ge can be mentioned. 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 the conduction properties contained in the photoreceptive layer is determined by the content of the substance (C) that controls the conduction properties required for the photoreception layer, or is provided in direct contact with the photoreception layer. Relationships with the characteristics of other layers and supports, and the characteristics at the contact interface with other layers and supports, etc.
Depending on the organic relationship, it can be selected as appropriate. 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 containing in the substratum region (E),
The properties of the 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 considered, and the material controlling the conduction properties is determined. The content is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is as follows:
Preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5
It is desirable to set it to ×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 100atomic
ppm or more, the substance (C) is preferably contained locally in some layer regions of the photoreceptive layer, and is particularly unevenly distributed in the layer region (E) at the end of the photoreceptive layer on the side of the support. It is desirable to contain it so as to Among the above, 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,
For example, when the substance (C) to be contained is the p-type impurity described above, 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 is inhibited. can be effectively prevented,
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, the movement of holes injected from the support side into the photoreceptor layer is inhibited. 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 layer region (Z) excluding the part may contain a substance that controls the conduction characteristics of the other polarity, or the material that controls the conduction characteristics of the same polarity may be added to the end layer region (Z). ) 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 desired depending on the situation, but preferably 0.001 to 1000 atomic ppm,
More preferably 0.05-500 atomic ppm, optimally
It is desirable to set it to 0.1-200 atomic ppm. 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 It is desirable to set it to 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 . 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 pn junction. A depletion layer can be provided. In order to structurally introduce a substance (C) that controls conduction properties into the photoreceptive layer, such as a group atom or a group atom, a starting material for introducing a group atom or a group atom is introduced during layer formation. The starting materials for forming the second layer region can be introduced in gaseous form into the deposition chamber together with the other starting materials for forming the second 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 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. 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 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 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 the desired photoconductive member is formed, but when 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 a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to
It is considered to be 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 15 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is a 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 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming 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 the valves 1118 and 1120 are gradually changed by controlling the flow rates of GeH ₄ /He gas and NH ₃ gas manually or by using an external drive motor, etc., according to a pre-designed rate of change curve. The distribution concentration of germanium atoms and nitrogen atoms contained in the layer formed by this method is controlled. In the manner described above, the glow discharge is maintained for a desired time to form a first layer region on the substrate 1137 to a desired layer thickness.
Form (G). At the stage where the first layer region (G) has been formed to the desired layer thickness, the same conditions and procedures are followed except for completely closing the outflow valve 1116 and changing the discharge conditions as necessary. By maintaining the glow discharge for a desired period of time, a second layer region (S) substantially free of germanium atoms can be formed on the first layer region (G). In order to contain a substance (C) that controls conductivity in the first layer region (G) and the second layer region (S),
When forming the first layer region (G) and the second layer region (S), a gas such as B ₂ H ₆ or PH ₃ is supplied to the deposition chamber 11.
It may be added to the gas introduced into 01. 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 17-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate under the conditions shown in Table 1 using the manufacturing apparatus shown in FIG. 15.
(Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of nitrogen atoms in each sample 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 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 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 27-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 15 under the conditions shown in Table 3.
(Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, 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. 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】

【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
...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 14 are explanatory views for explaining the distribution state of nitrogen atoms in the photoreceptive layer, respectively. FIG. 15 is a schematic explanatory view of the apparatus used in the present invention, and FIG. 17 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 a first layer region (G) with a layer thickness of 30 Å to 50 μ made of an amorphous material containing germanium atoms on the support. and a second layer region (S) with a layer thickness of 0.5 to 90 μ made of an amorphous material containing silicon atoms (but not containing germanium atoms) are provided in order from the support side. A photoconductive member for electrophotography comprising a photoreceptive layer exhibiting photoconductivity, the photoreceptor layer containing nitrogen atoms in a content of 0.001 to 50 atomic%,
The concentration distribution is smooth and 500 atoms within 5μ in layer thickness from the support side or free surface side of the layer.
A photoconductive member for electrophotography, characterized by having a maximum distribution concentration of ppm or more. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. 3. The electrophotographic light according to Claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. conductive member. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (S) is non-uniform. 5 Claim 1 in which the germanium atoms are uniformly distributed in the first layer region (S)
A photoconductive member for electrophotography as described in 1. 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 that controls 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.