JPH0225169B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. In some cases, solid-state imaging devices are required to have characteristics such as being harmless 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. The application as an image forming member for photography and the application to a photoelectric conversion/reading device are described in German Published Publication No. 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of environmental characteristics and furthermore, stability over time, and it is necessary to improve the 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. Furthermore, when commonly used halogen lamps and fluorescent lamps are used as light sources, there remains room for improvement in that long wavelength light cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms for control purposes, or other atoms for the purpose of improving other properties, but how these constituent atoms are contained is determined. Problems may therefore 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 and applicability as a photoconductive member used in electrophotographic image forming members, we found that silicon atoms are used as a matrix and hydrogen atoms (H ) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as ``a'' generically. -Si (H, The material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. that you are
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 for electrophotography that has a long lifespan, does not cause any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member for electrophotography that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to 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 for electrophotography having high properties. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member for electrophotography, which has sufficient performance and excellent electrophotographic properties 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,
An object of the present invention is to provide a photoconductive member for electrophotography that has high signal-to-noise ratio characteristics and good electrical contact with a support. The photoconductive member for electrophotography of the present invention (hereinafter simply referred to as "photoconductive member") includes a support for the photoconductive member, and is disposed on the ^support ,
A layer thickness of 30 Å to 50 μ made of an amorphous material containing ppm of germanium atoms continuously and uniformly in the layer thickness direction.
A first layer region and a second layer region having a layer thickness of 0.5 to 90μ and made of an amorphous material containing silicon atoms (but not containing germanium atoms) are provided in order from the support side. It consists of a photoreceptive layer exhibiting photoconductivity with a layer thickness of 1 to 100μ, the first layer region contains a substance controlling conductivity of 0.01 to 5×10 ⁴ atomic ppm, and the photoreceptor layer has 0.0001～
50 atomic % of nitrogen atoms are uniform in the layer thickness direction or there is a portion where the maximum concentration of nitrogen atoms is higher than 500 atomic ppm on the support side, and the interface side of the second layer region is compared to the support side. It is characterized by a considerably low content. The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. 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 diagram schematically showing the layer structure 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 includes germanium atoms, silicon atoms, hydrogen atoms, and halogen atoms (X) as necessary from the support 101 side.
The first layer region (G) 103 is composed of an amorphous material (hereinafter abbreviated as "a-Ge (Si, H, X)") containing at least one of
It has a layer structure in which a second layer region (S) 104 composed of X) and having photoconductivity are laminated in order. The germanium atoms contained in the first layer region (G) 103 are continuous and uniform in the layer thickness direction of the first layer region (G) 103 and in the in-plane direction parallel to the surface of the support 101. It is contained in the first layer region (G) 103 in a distributed state. In the photoconductive member 100 of the present invention, at least the first layer region (G) 103 contains a substance (C) that controls conduction characteristics, and the first layer region (G) 103 has a desired amount of The conduction properties are given. In the present invention, the first layer region (G) 103
The substance (C) that controls the conduction properties contained in
It may be uniformly contained in the entire layer region of the first layer region (G) 103, and the first layer region (G) 1
It may be contained so as to be unevenly distributed in some layer regions of 03. Substance (C) that controls conduction properties in the present invention
When the substance (C) is contained in the first layer region (G) so as to be unevenly distributed in a part of the layer region (G), the layer region (PN) in which the substance (C) is contained
is preferably provided as an end layer region of the first layer region (G). In particular, when the layer region (PN) is provided as the end layer region on the support side of the first layer region (G), the substance (C) contained in the layer region (PN) By appropriately selecting the type and content thereof as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the photoreceptive layer. In the photoconductive member of the present invention, the substance (C) capable of controlling conduction properties is added to the first layer region (G) constituting a part of the photoreceptive layer as described above. It is contained evenly throughout the layer region (G) or unevenly distributed in the layer thickness direction,
Furthermore, a second layer provided on the first layer region (G)
The substance (C) may also be contained in the layer region (S). When the substance (C) is contained in the second layer region (S), the type, amount and content of the substance (C) contained in the first layer region (G) are determined. Depending on the method, the type and amount of the substance (C) to be contained in the second layer region (S), and the manner in which it is contained are appropriately determined. In the present invention, when the substance (C) is contained in the second layer region (S), preferably the substance (C) is contained in the layer region including at least the contact interface with the first layer region (G). It is desirable to include a substance. In the present invention, the substance (C) may be uniformly contained in the entire layer region of the second layer region (S), or may be uniformly contained in a part of the layer region. is also good. When both the first layer region (G) and the second layer region (S) contain a substance (C) that controls conduction characteristics, the substance (C) in the first layer region (G) It is desirable that the layer region containing the substance (C) and the layer region containing the substance (C) in the second layer region (S) be in contact with each other. Further, the substance (C) contained in the first layer region (G) and the second layer region (S) is contained in the first layer region (G) and the second layer region (S). They may be of the same type or different types, and their content may be the same or different in each layer region. However, in the present invention, if the substance (C) contained in each layer region is the same in both, it is necessary to increase the content in the first layer region (G) sufficiently. Alternatively, it is preferable that substances (C) of different types with different electrical properties are contained in each desired layer region. In the present invention, by containing the substance (C) that controls the conduction characteristics at least in the first layer region (G) constituting the photoreceptive layer, the layer containing the substance (C) can be improved. Region [first layer region (G)
It is possible to arbitrarily control the conduction characteristics of the layer (either part or all of the layer region) as desired, but such materials include the so-called
Examples of impurities used in the semiconductor field include p-type impurities that impart p-type conductivity to a-SiGe (H, Examples include n-type impurities that provide n-type conduction characteristics. Specifically, p
Type impurities include atoms belonging to the group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc. It is suitably used for
B, Ga. As the n-type impurity, atoms belonging to the group of the periodic table (group atoms), such as P
(phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and particularly preferably used are P,
It is As. In the present invention, the content in the layer region (PN) in which the substance controlling conduction properties is contained depends on the conduction properties required for the layer region (PN) or the content that the layer region (PN) supports. When it is provided in direct contact with the body, 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, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material controlling the conduction characteristics is determined. The content is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to It is desirable that the content be 1×10 ⁴ atomic ppm, most preferably 1 to 5×10 ³ atomic ppm. In the present invention, the content of the substance (C) that controls conduction characteristics in the layer region (PN) containing the substance (C) is preferably 30 atomic ppm.
As described above, by setting the amount to be more preferably 50 atomic ppm or more, optimally 100 atomic ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, the free surface of the photoreceptive layer is polarized. It is possible to effectively prevent the injection of electrons from the support side into the photoreceptive layer when subjected to treatment, and when the substance to be contained is the n-type impurity,
When the free surface of the photoreceptive layer is polarized, injection of holes from the support side into the photoreceptor layer can be effectively prevented. In the above case, as mentioned above, in the layer region (Z) excluding the layer region (PN),
The layer region (PN) may contain a substance (C) that controls conduction characteristics with a conduction type polarity different from the conduction type polarity of the substance (C) that controls conduction characteristics contained in the layer region (PN), or The substance (C) that controls conductivity and has the same conductivity type may be contained in an amount much smaller than the actual amount contained in the layer region (PN). In such a case, the content of the substance controlling the conduction characteristics contained in the layer region (Z) may be determined as desired depending on the polarity and content of the substance contained in the layer region (PN). Therefore, it should be determined appropriately, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting the layer region containing the material. That is, 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, 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 the photoconductive member, a photoconductive member can be obtained which has excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths including the visible light region. In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, so that the distribution state of germanium atoms in the first layer region (G) and the second layer region is different. When a semiconductor laser etc. with excellent affinity with the region (S) is used, the second
The first layer region (G) can substantially completely absorb light on the longer wavelength side, which is almost completely absorbed in the layer region (S), and eliminates interference due to reflection from the support surface. It can be prevented. Further, in the photoconductive member of the present invention, when silicon atoms are contained in the first layer region (G), the first layer region (G) and the second layer region (S)
Since each of the light-receiving materials constituting the two has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. In the present invention, the content of germanium atoms contained in the first layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~10×
10 ⁵ atomic ppm, more preferably 100×9.5×
10 ⁵ atomic ppm, optimally 500-8×
It is preferable to set it at 10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region (G) and the second layer region (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the photoconductive member has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is preferably 30 Å to 50 μ, more preferably 40 Å to 40 μ, and optimally 50 Å to 30 μ. Further, the layer thickness T of the second layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. The sum of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) (T _B +T) is based on the characteristics required for both layer regions and the overall photoreceptive layer. It is determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the properties and the required properties. 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
It is desirable that appropriate numerical values be selected for each of them so as to satisfy the relationship T _B /T≦1. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (G) is 1×
In the case of 10 ⁵ atomic ppm or more, it is desirable that the layer thickness T _B of the first layer region (G) be as thin as possible, preferably 30μ or less, more preferably
It is desirable that the thickness be 25μ or less, optimally 20μ or less. In the photoconductive member of the present invention, the photoreceptive layer contains a , contains an oxygen atom. 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 and unevenly distributed only in some layer areas of the photoreceptive layer. good. In addition, the distribution state of nitrogen atoms is the distribution concentration C(N)
may be uniform or non-uniform in the thickness direction of the photoreceptive layer. 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 When the main purpose is to strengthen the adhesion between the support and the light-receiving layer, the light-receiving layer is provided so as to occupy the support-side end layer region of the light-receiving layer. In the former case, the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. It is desirable that the amount be relatively large in order to achieve this goal. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute it at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or In the surface layer region on the free surface side of the photoreceptive layer, a nitrogen atom distribution state may be formed in the layer region (N) such that nitrogen atoms are not actively contained. 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 the content 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 T of the photoreceptor layer is equal to the layer thickness To of the layer area (N). If the proportion of nitrogen atoms in the layer region (N) 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, if the ratio of the layer thickness To of the layer region (N) to the layer thickness T of the photoreceptive layer is 2/5 or more, The upper limit of the amount of nitrogen atoms is preferably:
It is desirable that the content be 30 atomic % or less, more preferably 20 atomic % or less, and optimally 10 atomic % or less. 2 to 10 show typical examples of the distribution state of nitrogen atoms contained in the layer region (N) of the photoconductive member in the present invention in the layer thickness direction. 2 to 10, the horizontal axis shows the distribution concentration C of nitrogen atoms, the vertical axis shows the layer thickness of the layer region (N), and t _B is the position of the end surface of the layer region (N) on the support side. , t _T indicates the position of the end surface of the layer region (N) on the side opposite to the support side. That is, the layer region (N) containing nitrogen atoms is formed as a layer from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of nitrogen atoms contained in the layer region (N) in the layer thickness direction. In the example shown in FIG. 2, from the interface position tB where the surface of the support where the layer region (N) containing nitrogen atoms is formed and the surface of the layer region (N) contact, to _the position _t1 . is contained in the layer region (N) where nitrogen atoms are formed, with the distribution concentration C of nitrogen atoms taking a constant value C ₁ , and gradually increases from the concentration C ₂ to the interface position t _T from the position t ₁ . has been continuously decreased. At the interface position _tT , the distribution concentration of nitrogen atoms C
is assumed to be C ₃ . In the example shown in FIG. 3, the distribution concentration C of the contained nitrogen atoms gradually and continuously decreases from the concentration _C4 from the position _tB to the position _tT , and at the position _tT the concentration _C5 decreases. The distribution state is formed as follows. In the case of Fig. 4, the distribution concentration C of nitrogen atoms is constant at the concentration C ₆ from position t _B to position t ₂ , and gradually and continuously decreases between position t ₂ and position t _T. At the position _tT , the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of nitrogen atoms is gradually decreased continuously from the concentration C ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. There is. In the example shown in FIG. 6, the nitrogen atom distribution concentration C is constant at a concentration _C9 between the position _tB and the position _t3 , and the concentration _C10 at the position _tT .
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 nitrogen atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, from position _tB to position _t5 , the distribution concentration C of nitrogen atoms is lower than the concentration _C15 .
An example is shown in which the concentration C ₁₆ is linearly decreased to C 16 and the concentration C ₁₆ is kept at a constant value between the position t ₅ and the position t _T. In the example shown in FIG. 10, the distribution concentration C of nitrogen atoms is a concentration C ₁₇ at position t _B , and at first it gradually decreases from this concentration C ₁₇ until reaching position t ₆ , and then at t ₆ it decreases slowly. 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, the concentration decreases very slowly and reaches 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 nitrogen atoms contained in the layer region (N) in the layer thickness direction, in the present invention, on the support side , the layer region (N) has a portion where the distribution concentration C of nitrogen atoms is high, and the distribution state of nitrogen atoms has a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. It is set in. In the present invention, the layer region (N) containing nitrogen atoms constituting the photoreceptive layer is the localized region (B) containing nitrogen atoms at a relatively high concentration on the support side as described above. It is desirable that the support be provided as having the following properties, and in this case, the adhesion between the support and the light-receiving layer can be further improved. The above localized region (B) can be explained using the symbols shown in FIGS. 2 to 10, by 5μ from the interface position _tB .
It is desirable that it be established within 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 may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. In the localized region (B), the maximum value Cmax of the distribution concentration of nitrogen atoms is preferably 500 atomic ppm or more as the distribution state of the nitrogen atoms contained therein in the layer thickness direction,
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 achieved. That is, in the present invention, the layer region (N) containing nitrogen atoms has the maximum distribution concentration within 5μ in layer thickness from the support side (layer region of 5μ layer from t _B ).
It is desirable that the structure be formed so that Cmax exists. In the present invention, specific examples of the halogen atom (X) contained in the light-receiving layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as. In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the first layer region (G) composed of a-Ge (Si, H, X). It is made by a vacuum deposition method. For example, by using the glow discharge method, the first
In order to form the layer region (G), for example, a Ge supply source gas that can supply germanium atoms (Ge), and a Si supply source gas that can supply silicon atoms (Si) as necessary. A raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. A layer made of a-Ge (Si, H, In addition, when forming by a sputtering method, for example, a target made of Si, or a target made of Si and Ge in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. Using two of the prepared targets or a mixed target of Si and Ge, the raw material gas for supplying Ge diluted with diluting gas such as He or Ar as necessary,
If necessary, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and the raw material gas for supplying Ge while controlling the gas flow rate according to the desired rate of change curve.
All you have to do is sputter the target mentioned above. 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. The first layer region (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically:
For example, silicon halide, which is a raw material gas for supplying Si, germanium hydride, which is a raw material gas for Ge supply, and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate, and the first A first layer region (G) is deposited on the desired support by introducing a layer region (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. It may be formed. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. 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 ,
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 useful 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. Since it will be introduced,
In the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H ₂ or SiH ₄ ,
Silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ，
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc. and silicon or silicon compound for supplying Si coexist in the deposition chamber and discharge is performed. This can also be done by causing In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the first layer region (G) of the photoconductive member to be formed The sum (H+X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the support, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of the starting material used, introduced into the deposition system, the discharge power, etc. In the present invention, in order to form the second layer region (S) composed of a-Si(H,X), the starting material () for forming the first layer region (G) described above is Form the first layer region (G) using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying Ge from the inside. It can be carried out in the same manner and under the same conditions as in the case of 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 glow discharge is generated in the a-
A layer made of Si(H,X) may be formed. 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. A layer containing the substance (C) by structurally introducing a substance (C) that controls conduction properties, for example, group group atoms or group atoms into the layer region (PN) constituting the photoreceptive layer. To form the region (PN), during layer formation, a starting material for introducing group atoms or a starting material for introducing group atoms is added in a gaseous state to a deposition chamber for forming a photoreceptive layer. It may be introduced together with the starting material. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , 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 may 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 ₅ , SbCl ₃ ,
SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. 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), an atomic 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. These can also be mixed and used in a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N). The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming the layer region (N) is one containing N as a constituent atom or containing N and H. Atoms such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. in gaseous or gaseous form 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 contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (N) include oxygen (O ₂ ), ozone (O ₃ ), carbon 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 a layer region (N) containing nitrogen atoms by sputtering, a single crystal or polycrystalline Si wafer or a Si ₃ N ₄ wafer or a Si and
This can be carried out by sputtering a wafer containing a mixture of Si ₃ N ₄ 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 the deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve. . For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by some 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 have to be linear, and a desired content rate curve can also be obtained by controlling the flow rate according to a pre-designed rate-of-change curve using, for example, a microcomputer. 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, if a mixed target of Si and Si ₃ N ₄ is used as a sputtering target, the mixing ratio of Si and Si ₃ N ₄ should be adjusted in the direction of the layer thickness of the target. This is done by changing it in advance. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (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 %. 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, or 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, No, 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 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. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is B ₂ H ₆ gas diluted with He (99.99% purity, hereinafter referred to as B ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is NH ₃ gas (purity 99.999%) cylinder, 1106 is 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
B ₂ H ₆ /He gas, NH ₃ gas from gas cylinder 1105, open valves 1122 to 1125, adjust the pressure of outlet pressure gauges 1127 to 1130 to 1 Kg/cm ² , and gradually open inflow valves 1112 to 1115. , into the mass flow controllers 1107 to 1110, respectively. Subsequently, the outflow valve 111
7 to 1120, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valves 1117 to 112 are adjusted so that the ratio of the SiH ₄ /He gas flow rate, GeH ₄ /He gas flow rate, B ₂ H ₆ /He gas flow rate, and NH ₃ gas flow rate becomes a desired value.
0, 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 heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101 as desired. By maintaining a glow discharge for a time, a layer region (B, N) containing boron atoms (B) and nitrogen atoms (N) in a desired layer thickness and composed of a-SiGe (H, X) is formed on the base 1137. ) is formed. At the stage when the layer regions (B, N) are formed to a desired layer thickness, the outflow valves 1118, 1119, 11
20 on the layer regions (B, N) by maintaining the glow discharge for the desired time according to the same conditions and procedures, except for completely closing each of the layers 20 and changing the discharge conditions as necessary. A layer region (S) composed of a-Si (H, is terminated. When forming the above-mentioned photoreceptive layer, after a desired period of time has elapsed after the start of the layer formation, the layer is transferred to the deposition chamber.
By stopping the inflow of B ₂ H ₆ /He gas or NH ₃ gas, the layer region containing boron atoms (B)
The thickness of each layer of the layer region (N) containing nitrogen atoms can be arbitrarily controlled. Also, according to a desired rate of change curve, the deposition chamber 110
By controlling the gas flow rate of NH ₃ gas to the layer region (N), the distribution state of nitrogen atoms contained in the layer region (N) can be formed as desired. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0kV corona charging,
Clear, high-density images with excellent image clarity and good gradation reproducibility were obtained. Example 2 Using the manufacturing apparatus shown in FIG. 11, layers were formed in the same manner as in Example 1 except that the conditions shown in Table 2 were used to obtain an electrophotographic image forming member. With respect to the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, except that the charging polarity and the charging polarity of the developer were reversed. Clear image quality was obtained. Example 3 Layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 3 were changed using the manufacturing apparatus shown in FIG. 11 to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 In Example 1, GeH ₄ /He gas and SiH ₄ /
Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of He gas. Created. Using the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 4 were obtained. Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained. Example 6 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Tables 6 to 8 to produce each electrophotographic image forming member (sample No. 601, 602, 603) were obtained. Each of the image forming members thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately exposed to a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 2 lux sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on each imaging member surface by cascading a chargeable developer (including toner and carrier) over each imaging member surface. When the toner images on each image forming member were transferred onto transfer paper using 5.0 kV corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 7 Using the manufacturing apparatus shown in FIG. 11, layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Tables 9 and 10 were used to form electrophotographic image forming members ( Sample Nos. 701 and 702) were obtained. For each of the imaging members thus obtained,
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 8 Using the manufacturing apparatus shown in FIG. 11, layers were formed in the same manner as in Example 1 except that the conditions shown in Tables 11 to 15 were used to form each electrophotographic image forming member (sample). No. 801 to 805) were obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 9 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image of an electrophotographic image forming member prepared under the same conditions as described above was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

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[Table] ◎: Excellent ○: Good

[Table] ◎: Excellent ○: Good △: Adequate for practical use

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of nitrogen atoms in the layer region (N), respectively. FIG. 11 is a schematic explanatory diagram of the apparatus used to produce the photoconductive member of the present invention in Examples. 100...Photoconductive member, 101...Support, 1
02...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography ^; A first layer region with a layer thickness of 30 Å to 50 μ made of a crystalline material and a layer thickness of 0.5 to 50 μ made of an amorphous material containing silicon atoms (but not containing germanium atoms).
A second layer region with a thickness of 90μ and a photoreceptive layer exhibiting photoconductivity with a layer thickness of 1 to 100μ are provided in order from the support side, and the first layer region has a layer thickness of 0.01μ.
~5×10 ⁴ atomic ppm of a substance controlling conductivity is contained in the photoreceptive layer, and the photoreceptive layer contains a substance that controls conductivity of 0.0001 to 50 atomic ppm.
% of nitrogen atoms is uniform in the layer thickness direction or has a portion where the maximum concentration of nitrogen atoms is higher than 500 atomic ppm on the support side, and on the interface side of the second layer region compared to the support side. A photoconductive member for electrophotography, characterized in that the content is considerably reduced. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein at least one of the first layer region and the second layer region contains a halogen atom. 4. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 5. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table.