JPH0145988B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet rays,
The present invention relates to photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, gamma rays, etc. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and economic stability, and it is necessary to improve 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 has often been observed that residual potential remains during use, and this type of When a conductive member is repeatedly used for a long period of time, fatigue due to repeated use accumulates, and a so-called ghost phenomenon occurs in which an afterimage occurs. In addition, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur. 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. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . 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 material used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms (Si) and germanium atom (Ge) as a matrix, and a hydrogen atom
(H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as these generic terms] The notation is “a-SiGe(H,
A photoconductive member designed and produced with the structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity consisting of " Not only does it exhibit extremely excellent properties, but it also surpasses conventional photoconductive members in every respect, and in particular, it has extremely excellent properties as a photoconductive member for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics 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 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 provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. 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 excellent electrophotographic properties with sufficient performance and with almost no deterioration of the properties observed even in a humid atmosphere. 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,
It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. The photoconductive member of the present invention has a support for the photoconductive member, and a photoreceptive layer that exhibits photoconductivity and is made of an amorphous material containing silicon atoms and germanium atoms, and The receiving layer has a layer region (O) containing the oxygen atoms, and the distribution concentration line indicating the distribution concentration of oxygen atoms in the layer region (O) in the layer thickness direction has a smooth changing portion. and the maximum value of the distribution density is located inside near the surface of the photoreceptive layer opposite to the support. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, in the photoconductive member of the present invention, the photoreceptive layer formed on the support is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used. 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. 1 is made of a-SiGe (H,
X), contains oxygen atoms, and has a photoreceptive layer 102 having photoconductivity. The germanium atoms contained in the photoreceptive layer 102 may be contained so as to be evenly distributed in the photoreceptive layer 102, or may be contained evenly in the layer thickness direction. However, the distribution density may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly contained in order to make the properties uniform in the in-plane direction. is also necessary. In particular, it is evenly contained in the layer thickness direction of the light-receiving layer 102, and the side opposite to the side where the support 101 is provided (the surface 104 side of the light-receiving layer 102)
The photoreceptor is distributed more toward the support side (the interface side between the photoreceptor layer 102 and the supporter 101), or vice versa. Contained in layer 102. In the photoconductive member of the present invention, the germanium atoms contained in the photoreceptive layer are distributed in the layer thickness direction as described above, and in parallel to the surface of the support. It is desirable to have a uniform distribution in the in-plane direction. FIGS. 2 to 10 show typical examples in which the distribution state of germanium atoms contained in the photoreceptive layer of the photoconductive member of the present invention in the layer thickness direction is non-uniform. 2 to 10, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the photoreceptive layer showing photoconductivity, and t _B is the position of the surface of the photoreceptive layer on the support side. , t _T indicates the position of the surface of the photoreceptive layer on the side opposite to the support side. That is, the photoreceptive layer containing germanium atoms is formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the photoreceptive layer in the layer thickness direction. In the example shown in FIG. 2, the distribution concentration of germanium atoms is from the interface position t _B to the position t ₁ where the surface where the photoreceptive layer containing germanium atoms is formed and the surface of the photoreceptor layer are in contact. Germanium atoms are contained in the photoreceptive layer formed while C takes a constant value of C ₁ , and the interface position t _T is higher than the position t ₁ .
The distribution concentration is gradually and continuously decreased from _C2 until . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is a constant value of concentration _C5 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 gradually decreases 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 .} 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 photoreceptive layer in the layer thickness direction, in the present invention, germanium atoms are The light-receiving layer is provided with a distribution state of germanium atoms having a portion where the distribution concentration C of atoms is high, and a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. If so, this is one of the preferred examples. The photoreceptive layer constituting the photoconductive member of the present invention preferably contains germanium atoms at a relatively high concentration on the support side as described above, or on the contrary, on the free surface side. It is desirable to have a localized region (A) that is 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. The above localized region (A) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or it may be a part of the layer region (L _T ). . 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,
It is desirable that the layer be formed in such a manner that the concentration can be more preferably 5000 atomic ppm or more, most preferably 1×10 ⁴ atomic ppm or more. That is, in the present invention, the photoreceptive layer 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 (layer region with a thickness of 5μ from t _B ). In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but it is preferably 1 to 9.5×10 ⁵ atomic ppm, more preferably 100 to
8×10 ⁵ atomic ppm, optimally 500 to 7×
It is desirable to set it to 10 ⁵ atomic ppm. The distribution state of germanium atoms in the photoreceptive layer is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction is C.
is from the support side to the free surface side of the photoreceptive layer,
When a decreasing change or the opposite change is given, the required characteristics can be achieved by arbitrarily designing the rate of change curve of the distribution concentration C as desired. A desired photoreceptive layer can be realized. For example, change the distribution concentration C of germanium in the photoreceptive layer so that it is sufficiently increased on the support side and as low as possible on the free surface side of the photoreception layer. By giving the atomic distribution concentration curve, including the visible light region,
It is possible to increase photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively long wavelengths, and it is also possible to effectively prevent interference with coherent light such as laser light. I can do it. Furthermore, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the photoreceptive layer on the side of the support, the laser irradiation surface of the photoreceptor layer is improved when a semiconductor laser is used. It is possible to substantially completely absorb light on the long wavelength side that is not fully absorbed by the support side end layer region of the photoreceptive layer, effectively eliminating interference due to reflection from the support surface. can be prevented. In the photoconductive member of the present invention, in order to increase photosensitivity and dark resistance, and furthermore to prevent charge injection from the free surface of the photoreceptive layer, oxygen is contained in the photoreceptive layer. Contains atoms. The oxygen atoms contained in the photoreceptive layer may be uniformly contained in the entire layer area of the photoreceptive layer, or may be contained only in some layer areas of the photoreceptive layer so that they are distributed ubiquitously. Also good. Even if the distribution concentration C(O) of oxygen atoms in the layer region (O) containing oxygen atoms is uniform on the surface and in-plane direction of the photoreceptive layer support, The layer is non-uniform in the thickness direction. In the present invention, in order to more effectively achieve the object of the present invention, the distribution concentration curve of oxygen atoms in the layer thickness direction in the layer region (O) is smooth in the entire region. Oxygen atoms are contained in the layer region (O) so as to be continuous. Furthermore, by designing the distribution concentration curve so that its maximum distribution concentration Cmax exists inside the photoreceptive layer,
The effects described below are clearly exhibited. In the present invention, the maximum distribution concentration Cmax
is preferably provided near the surface of the photoreceptive layer opposite to the support (the free surface side in FIG. 1). In this case, by appropriately selecting the maximum distribution concentration Cmax, it is possible to effectively prevent charges from being injected from the free surface side of the photoreceptive layer into the inside of the photoreceptive layer when the photoreceptive layer is subjected to charging treatment from the free surface side. I can do it. In addition, near the free surface, the distribution concentration of oxygen atoms increases toward the free surface with the maximum distribution concentration Cmax.
By including oxygen atoms in the photoreceptive layer so that they decrease more steeply, durability in a humid atmosphere can be further improved. In the present invention, the oxygen atom distribution concentration curve has the maximum distribution concentration Cmax inside the photoreceptive layer, but the distribution concentration curve is designed so that the maximum distribution concentration exists toward the support side. By containing oxygen atoms, it is possible to improve the adhesion between the support and the photoreceptive layer and to prevent charge injection. In the present invention, oxygen atoms are desirably contained in the central layer region of the photoreceptive layer in an amount that does not reduce photosensitivity even though it strives to increase dark resistance. In the present invention, the maximum distribution concentration of oxygen atoms
Cmax is the sum of silicon atoms, germanium atoms, and oxygen atoms (hereinafter referred to as "T (SiGeO)")
, preferably 67 atomic% or less, more preferably 50 atomic% or less, optimally 40 atomic%
The following is desirable. FIGS. 11 to 14 show typical examples of the distribution of oxygen atoms in the entire photoreceptive layer.
In the description of these figures, the symbols used without exception have the same meanings as used in FIGS. 2 to 10. In the example shown in FIG. 11, from position t _B to position t ₉
The oxygen atom concentration is assumed to be C ₂₁ from position t ₉ to position
The oxygen atom concentration increases until t ₁₀ , and the oxygen atom concentration reaches its peak value at position t ₁₀ .
C becomes ₂₂ . The oxygen atom concentration decreases from the position t ₁₀ to the position t ₁₁ and reaches the oxygen atom concentration C ₂₁ at the position t _T. In the example shown in FIG. 12, from position t _B to position t ₁₂
From position t ₁₂ to position t ₁₃ , the oxygen atom concentration is C ₂₃ .
At position _t13 , the oxygen atom concentration takes a peak value _C24 , and decreases from position _t13 to position _tT until the oxygen atom concentration becomes almost zero. In the example shown in FIG. 13, from position t _B to position t ₁₄
The oxygen atom concentration increases slowly from _C25 to _C26 until the point _t14 , and the oxygen atom concentration reaches a peak value _C26 . The oxygen atom concentration rapidly decreases from position t ₁₄ to position t _T , and at position t _T the oxygen atom concentration becomes C ₂₅ . In the example shown in FIG. 14, the oxygen atom concentration decreases from position t _B to position t ₁₅ with an oxygen atom concentration C ₂₇ , and from position t ₁₅ to position _{t 16 ,} the oxygen atom concentration decreases to C _28. constant. The oxygen atom concentration increases from position _t16 to position _t17 , and at position _t17 , the oxygen atom concentration reaches a peak value _C29 . The oxygen atom concentration decreases from position _t17 to position _tT , and reaches the oxygen atom concentration _C28 at position _tT . In the present invention, when the main purpose of the layer region (O) containing oxygen 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 the main purpose of providing the film near the free surface is to strengthen the adhesion between the support and the light-receiving layer, it is provided so as to occupy the end layer region of the light-receiving layer on the support side. In the first case, the content of oxygen atoms contained in the layer region (O) is kept relatively low in order to maintain high photosensitivity, and in the second case to prevent charge injection from the free surface of the photoreceptor layer. In the latter case, it is desirable to use a relatively large amount 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. What is necessary is to form a distribution state of oxygen atoms in the layer region (O). In order to prevent charge injection from the free surface, a layer region (O) with a high distribution concentration of oxygen atoms is formed on the free surface side. However, if a layer region with a high distribution concentration of oxygen atoms comes into contact with the atmosphere, it may adsorb moisture in the air and cause image blurring when used for electrophotography. A low concentration is desirable. In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the photoreceptive layer depends on the characteristics required for the layer region (O) itself, or when the layer region (O) 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 (O), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in the layer region (O) is
Although it can be determined as desired depending on the characteristics required of the photoconductive member to be formed, it is preferably 0.001 to 50 atomic%, more preferably 0.002 to 40 atomic%, and most preferably 0.003〜
A desirable value is 30 atomic%. In the present invention, whether the layer region (O) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is equal to the layer thickness To of the layer area (O). If the proportion of oxygen atoms in the layer region (O) is sufficiently large, the upper limit of the content of oxygen atoms in the layer region (O) 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 To of the layer region (O) to the layer thickness T of the photoreceptive layer is two-fifths.
In such cases, the upper limit of the amount of oxygen atoms contained in the layer region (O) is T (SiGeo).
preferably 30 atomic% or less, more preferably 20 atomic% or less, optimally 10 atomic%
% or less. In the present invention, the layer region (O) containing oxygen atoms constituting the photoreceptive layer is a localized region where oxygen 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 area (B) be provided, and in the former case,
It is possible to further improve the adhesion between the support and the photoreceptive layer and to improve the reception potential. The localized region (B) 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 may be 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 value C _nax of the distribution concentration of oxygen atoms is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally
It is desirable to form a layer so that a distribution state of 1000 atomic ppm can be achieved. That is, in the present invention, the layer region (O) containing oxygen 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 preferable that the halogen atom (X) is formed such that the maximum distribution concentration (C _nax ) exists in the photoreceptive layer. In the photoconductive member of the present invention, the photoreceptive layer contains fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. By containing a substance, the conduction characteristics of the photoreceptive layer can be controlled as desired.As such, examples of the substance include so-called impurities in the semiconductor field, and the present invention In this case, a-SiGe constituting the formed photoreceptive layer
For (H, Specifically, the P-type impurities include atoms belonging to Group 3 of the periodic table (Group atoms);
For example, there are B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance that controls the conduction properties contained in the photoreceptive layer depends on the conduction properties required for the photoreception layer or the support provided in direct contact with the photoreception layer. It can be selected as appropriate based on the organic relationship, such as the relationship with the characteristics at the contact interface with the body. 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 sublayer region, the characteristics of other layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the other layer regions are also taken into consideration. The content of the substance controlling the conduction properties is selected appropriately. In the present invention, the content of the substance controlling conduction properties contained in the photoreceptive layer 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 is desirable. In the present invention, the content of the substance controlling conduction characteristics in the layer region containing the substance is preferably 30 atomic ppm or more, more preferably
50atomic ppm or more, optimally 100atomic ppm
In the above case, the substance is desirably contained locally in a part of the layer region of the light-receiving layer, and is particularly preferably unevenly distributed in the end layer region of the light-receiving layer on the side of the support. Among the above, by containing a substance that controls the conduction characteristics in the support side end layer region (E) of the photoreceptive layer in a content that is equal to or more than the above value, for example, the substance to be contained can be In the case of the above-mentioned P-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, injection of electrons from the support side into the photoreceptor layer can be effectively prevented, In addition, when the substance to be contained is the n-type impurity described above, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to effectively prevent holes from being injected from the support side into the photoreceptor layer. can be 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 controlling 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). Although it is determined appropriately according to desire, preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the 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 case, in the present invention, a layer region containing a substance controlling conductivity having one polarity in the photoreceptive layer;
It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance controlling conductivity having the other polarity. For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form a so-called p-n junction. , a depletion layer can be provided. In the present invention, the photoreceptive layer composed of a-SiGe (H, will be accomplished. For example, by the glow discharge method, a
- To form a photoreceptive layer composed of SiGe (H, Raw material gas for supply and, if necessary, raw material gas for hydrogen atom (H) introduction or/
and introducing a raw material gas for introducing halogen atoms (X) into a deposition chamber whose interior can be reduced in pressure at a desired gas pressure to generate a glow discharge within the deposition chamber;
A layer made of a-SiGe (H, In addition, in order to contain germanium atoms in a non-uniform distribution state, the distribution concentration of germanium atoms must be controlled according to a desired rate of change curve.
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
Using a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or using two targets made of this target and Ge, or Si and Ge
Using a mixed target of
This is accomplished by introducing a gas for introducing halogen atoms (X) into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas. In order to make the distribution of germanium atoms non-uniform, 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. In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the above method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. A light-receiving layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically silicon halide, which is a raw material gas for supplying Si, germanium hydride, and Ar, which are raw material gases for supplying Ge, are manufactured using the glow discharge method. ,
Gases such as H ₂ and He are introduced into a deposition chamber where a photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. A light-receiving layer can be formed on a desired support by using these gases, but in order to more easily control the ratio of hydrogen atoms introduced, hydrogen gas or hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of a silicon compound gas containing . Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as effective starting materials for forming the photoreceptor layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the photoreceptive layer. , is used as a suitable raw material for introducing halogen in the present invention. In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Generating a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. But it can be done. In a preferred example of the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the photoreceptive layer of the photoconductive member to be formed is preferably 0.01~
40atomic%, more preferably 0.05-30atomic%,
The optimum range is preferably 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the photoreceptive layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) contained What is necessary is to control the amount of starting material used for this purpose introduced into the deposition system, the discharge force, etc. The layer thickness of the photoreceptive layer in the photoconductive member of the present invention is appropriately determined as desired so that photocarriers generated in the photoreceptor layer are efficiently transported, and is preferably 1 to 100 μm. More preferably 1
It is desirable that the thickness be ~80μ, optimally 2~50μ. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing oxygen atoms is 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 (O), a starting material for introducing oxygen atoms is added to the starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), 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 oxygen atoms (O) 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), oxygen atoms (O), 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 an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H), for example,
Lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃₎ can be mentioned. crystalline or polycrystalline
Si wafer or _SiO2 wafer or Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
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, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when a layer region (O) containing oxygen atoms is provided when forming a photoreceptive layer, the distribution concentration C of oxygen atoms contained in the layer region (O) is
In the case of glow discharge, in order to form a layer region (O) having a desired depth profile by changing (O) in the layer thickness direction,
This is accomplished by introducing a starting material gas for introducing oxygen atoms whose distribution concentration C(O) 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, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (O) is formed by a sputtering method, the distribution concentration of oxygen atoms in the layer thickness direction C(O)
In order to change the depth profile of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, the starting point for introducing oxygen 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 target containing a mixture of Si and SiO ₂ is used, this can be done by changing the mixing ratio of Si and SiO ₂ in advance in the layer thickness direction of the target. In order to structurally introduce a substance that controls conduction properties, such as a group atom or a group atom, into the photoreceptive layer, a starting material for introducing a group atom or a group atom is introduced during layer formation. The starting materials for forming the photoreceptor layer may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the photoreceptive layer. As the starting material for introducing the group atom, it is desirable to use 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 , _DCl5 , _PBr3 , _PBr5 , and _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. In the present invention, the layer thickness of the layer region constituting the light-receiving layer and containing a substance that controls conduction properties and provided unevenly on the support side is defined as the thickness of the layer region formed on the layer region and the layer region formed on the layer region. The lower limit is preferably 30 Å or more, more preferably 40 Å or more, and the optimum It is desirable that the thickness be 50 Å. Further, when the content of the substance that controls conduction properties contained in the layer region is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region is preferably 10 μ or less, more preferably 8 μ. Hereinafter, the optimum value is preferably 5μ or less. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pd,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that the desired photoconductive member is formed, but if the photoconductive member is required to be flexible, the thickness of the support may be determined appropriately so that the photoconductive member cannot fully perform its function as a support. It is made as thin as possible within the range. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to use
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 SiF ₄ gas diluted with He (99.99% purity, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is NO gas (purity
99.999%) cylinder, 1106 is _H2 gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, NO from gas cylinder 1105
Open the gas valves 1122, 1123, 1124 and check the outlet pressure gauges 1127, 1128, 1129.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 1112,
1113 and 1114 are gradually opened to allow the flow into mass flow controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valve 111
7, 1118, 1119, the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
Outflow valves 1117 and 111 are installed so that the ratio of GeH ₄ /He gas flow rate to NO gas flow rate becomes a desired value.
8 and 1119, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the flow rate of NO gas and/or GeH ₄ /He gas is gradually changed by manually or using an externally driven motor or the like to gradually change the opening of the valve 1118 according to a pre-designed rate of change curve. The distribution concentration of germanium atoms contained in the layer is controlled. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 15, samples (sample Nos. 11-1 to 13-1) as electrophotographic image forming members were prepared on a cylindrical Al substrate under the conditions shown in Table 1.
4) were prepared respectively (Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen 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. A light image was generated using a tungsten lamp light source, and a light intensity of 2ux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
All samples had excellent resolution, and clear, high-density images with good gradation reproducibility were obtained. In the above, the toner image forming conditions were the same as above, except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp, and an electrostatic image was formed. When the image quality of the toner-transferred images was evaluated, all samples had excellent resolution, and clear, high-quality images with good gradation reproducibility were obtained. Example 2 Samples as electrophotographic image forming members (Samples No. 21-1 to No. 23-
4) were prepared respectively (Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples.

【table】

【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℃ 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 oxygen 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 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 photoconductive material comprising a support for a photoconductive member and a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, The layer has a layer region (O) containing the oxygen atoms, and the distribution concentration line indicating the distribution concentration of oxygen atoms in the layer region (O) in the layer thickness direction has a smooth changing portion. A photoconductive member characterized in that the maximum value of the distribution density is located inside the photoreceptive layer near a surface opposite to the support. 2. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms. 3. The photoconductive member according to claim 1, wherein the photoreceptive layer contains halogen atoms. 4. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms and halogen atoms. 5. The photoconductive member according to claim 1, wherein the distribution concentration of germanium atoms in the photoreceptive layer decreases from the support side toward the opposite side from the support side. 6. The photoconductive member according to claim 1, wherein the distribution concentration of germanium atoms in the photoreceptive layer is uniform in the layer thickness direction. 7. The photoconductive member according to claim 1, wherein the photoreceptive layer contains a substance that controls conductivity. 8. The photoconductive member according to claim 7, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 9. The photoconductive member according to claim 7, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 10. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%. 11. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%. 12. The photoconductive member according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%. 13. The photoconductive member according to claim 1, wherein the amount of germanium atoms contained in the photoreceptive layer is 1 to 9.5×10 ⁵ atomic ppm. 14 The atom belonging to Group 1 of the periodic table is B,
The photoconductive member according to claim 8, which is selected from Ga. 15 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member according to claim 9, which is selected from As. 16 The substance controlling the conductivity is 0.01 to 5×
Claim 7 containing 10 ⁴ atomic ppm
The photoconductive member described in . 17 The substance that controls the conductivity is 30 atomic
The photoconductive member according to claim 16, which contains ppm or more. 18 The content of oxygen atoms is 0.001 to 50 atomic
% of the photoconductive member according to claim 1. 19 The maximum value of the distribution concentration of oxygen atoms is
Claim 1 which is 500 atomic ppm or more
The photoconductive member described in . 20. The photoconductive member according to claims 3 and 4, wherein the halogen atom is selected from fluorine and chlorine.