JPH0220103B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which require a combined improvement in characteristics. For example, when applied to electrophotographic image forming members, when trying to achieve high light sensitivity 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 photoconductive When a component is used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases. There were many cases where this occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when using a commonly used halogen lamp or fluorescent lamp as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when forming a photoconductive layer with an a-Si material, 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 and applicability as a photoconductive member used in electrophotographic image forming members, we found that silicon atoms are used as a matrix, hydrogen atoms H or Amorphous materials containing at least one of the halogen atoms , It not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material 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 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,
Another 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 electrophotographic photoconductive member of the present invention is composed of a support for the electrophotographic photoconductive member and an amorphous material containing silicon atoms and 1 to 9.5×10 ⁵ atomic ppm germanium atoms on the support. Layer thickness: 30Å~
A layer structure in which a first layer region with a thickness of 50μ and a second layer region with a layer thickness of 0.5 to 90μ made of an amorphous material containing silicon atoms (not containing germanium atoms) are provided in order from the support side. A photoconductive member for electrophotography (hereinafter referred to as "photoconductive member") comprising: a photoconductive layer having a layer thickness of 1 to 100 μm and exhibiting photoconductivity; The distribution state of germanium atoms in the layer region is non-uniform in the layer thickness direction, with a high part of 1000 atomic ppm or more on the support side and a considerably lower part on the interface side compared to the support side. The photoreceptive layer contains 0.001~
It is characterized by containing 50 atomic% of oxygen atoms. 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. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. 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. A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102 on a support 101 for photoconductive member.
The amorphous layer 102 has a free surface 105 on one end surface. The amorphous layer 102 is made of a-Si containing germanium atoms from the support 101 side.
(H,X) (hereinafter abbreviated as "a-SiGe(H,X)") and a-SiGe
(H, The germanium atoms contained in the first layer region G103 are continuous in the layer thickness direction of the first layer region G103 and on the side opposite to the side where the support body 101 is provided ( It is contained in the first layer region G103 so that it is more distributed on the support 101 side than on the surface 105 side of the amorphous layer 102. In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the first layer region G is as described above in the layer thickness direction, and the germanium atoms are distributed in the plane parallel to the surface of the support. It is desirable to have a uniform distribution in the inward direction. In the present invention, germanium atoms are not contained in the second layer region S provided on the first layer region G, and an amorphous layer is formed in such a layer structure. Therefore, the photoconductive member can be made to have excellent photosensitivity to light in the entire range of 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, and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the second layer. Since the change decreases toward the region S, the affinity between the first layer region G and the second layer region S is excellent, and as will be described later, there is a change in the affinity between the first layer region G and the second layer region S. By making the distribution concentration C of germanium atoms extremely large, when a semiconductor laser or the like is used, light on the long wavelength side, which is hardly absorbed by the second layer region S, can be transferred to the first layer region G. It is possible to substantially completely absorb the light, and interference due to reflection from the support surface can be prevented. Furthermore, in the photoconductive member of the present invention, since each of the amorphous materials forming the first layer region G and the second layer region S has a common constituent element, silicon atoms. , chemical stability is sufficiently ensured at the laminated interface. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the first layer region G of the photoconductive member of the present invention in the layer thickness direction. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region G, and t _B represents the first layer region G on the support side.
The position of the end face of t _T is the first position opposite to the support side.
The position of the end face of the layer region G is shown. That is, the first layer region G containing germanium atoms is from the t _B side.
t Layer formation occurs toward _{the T} side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer region G in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region G containing germanium atoms is formed and the surface of the first layer region G are in contact with each other,
Up to the position t ₁ , the distribution concentration C of germanium atoms
is contained in the first layer region G where germanium atoms are formed while taking a constant value of C ₁ , and the position t ₁
The concentration is gradually and continuously decreased from _C2 to the interface position _tT . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₃ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. reduced, and at position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased 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
C ₁₀ will be done. Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region G in the layer thickness direction, in the present invention, In the first layer, the distribution state of germanium atoms has a portion where the distribution concentration C of germanium atoms is high, and a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. It is provided in area G. The first layer region G constituting the amorphous layer constituting the photoconductive member in the present invention is preferably a localized region containing germanium atoms at a relatively high concentration toward the support side, as described above. It is desirable to have region A. In the present invention, the localized region A is defined as the interface position by using the symbols shown in FIGS. 2 to 10.
It is desirable that it be provided within 5μ from _tB . In the present invention, the localized region A may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or 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 determined as appropriate depending on the characteristics required of the amorphous layer to be formed. Localized region A has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of germanium atoms is usually 1000 atomic ppm or more, preferably 1000 atomic ppm or more relative to silicon atoms.
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the amorphous 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 first layer region is appropriately determined as desired so as to effectively achieve the object of the present invention, but is usually 1 to 9.5× 10 ⁵ atomic ppm,
Preferably 100-8.0× ¹⁰⁵ atomic ppm, optimally
It is desirable that the content be 500 to 7×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region G and the second layer region S is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the desired properties are fully imparted to the member. In the present invention, the layer thickness T _B of the first layer region G is
Usually 30Å~50μ, preferably 40Å~40μ,
The optimum thickness is preferably 50 Å to 30 μ. In addition, the layer thickness T of the second layer region S is usually
0.5-90μ, preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. The sum of the layer thickness T _B of the first layer region G and the layer thickness T of the second layer region S (T _B +T) is based on the characteristics required for both layer regions and the characteristics required for the entire amorphous layer. It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the properties. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is usually 1 to 100μ,
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are usually T _B /
When satisfying the relationship T≦1, it is desirable that appropriate numerical values be selected for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region G is 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the first layer region G
It is desirable that the thickness be as thin as possible, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less. In the photoconductive member of the present invention, 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 of the layer region G. Since the distribution concentration C in the thickness direction is given a change that decreases from the support side toward the free surface side of the amorphous layer, the rate of change curve of the distribution concentration C can be arbitrarily designed as desired. Therefore, an amorphous layer having the required properties can be realized as desired. For example, the distribution concentration C of germanium in the first layer region G is set to be sufficiently high on the support side and as low as possible on the free surface side of the amorphous layer. By imparting a change to the distribution concentration curve of germanium atoms, it is possible to increase the photosensitivity to light having wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer region G on the side of the support, when a semiconductor laser is used, Light on the long wavelength side that cannot be absorbed sufficiently in the second layer region S can be substantially completely absorbed in the layer region G, effectively preventing interference due to reflection from the support surface. I can do it. In the photoconductive member of the present invention, in order to achieve high photosensitivity and high dark resistance, as well as to improve the adhesion between the support and the amorphous layer, contains an oxygen atom. The oxygen atoms contained in the amorphous layer may be uniformly contained in the entire layer region of the amorphous layer, or may be contained in only some layer regions of the amorphous layer so that they are unevenly distributed. You can let me. In addition, even if the distribution state of oxygen atoms is uniform in the distribution concentration of C and O in the thickness direction of the amorphous layer,
Similar to the distribution state of germanium atoms explained using FIGS. 2 to 10, the distribution concentrations C and O may be non-uniform in the layer thickness direction. When the distribution concentration C and O of oxygen atoms are non-uniform in the layer thickness direction, the distribution state of oxygen atoms is as follows:
This can be explained in the same way as the case of germanium atoms using FIGS. 10 to 10. In the present invention, when the main purpose of the layer region O provided in the amorphous layer containing oxygen atoms is to improve photosensitivity and dark resistance, the entire layer region of the amorphous layer is If the main purpose is to strengthen the adhesion between the support and the amorphous layer, it is provided so as to occupy the end layer area of the amorphous layer on the side of the support. . In the former 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 latter case, the content of oxygen atoms contained in the layer region O is set to be relatively low in order to maintain high photosensitivity, and in the latter case, the content of oxygen atoms contained in the layer region O is set to be relatively low to ensure that the adhesion with the support is strengthened. Therefore, it is desirable to have a relatively large amount. In addition, in order to achieve both the former and the latter simultaneously, 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 amorphous layer. Alternatively, in the surface layer region on the free surface side of the amorphous layer, a distribution state of oxygen atoms may be formed in the layer region O such that oxygen atoms are not actively contained. In the present invention, the content of oxygen atoms contained in the layer region O provided in the amorphous layer depends on the characteristics required of the layer region O itself or when the layer region O is in direct contact with the support. In the case where the support is provided, 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 characteristics of the other layer region and the relationship with the characteristics at the contact interface with the other layer region are also considered. and the content of oxygen atoms is appropriately selected. The amount of oxygen atoms contained in the layer region O is determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001.
~50atomic%, preferably 0.002~40atomic
%, preferably 0.003 to 30 atomic%. In the present invention, whether the layer region O occupies the entire area of the amorphous layer or even if it does not occupy the entire area of the amorphous layer, the layer thickness To of the layer region O is equal to the layer thickness T of the amorphous layer. When the proportion is sufficiently large, it is desirable that the upper limit of the content of oxygen atoms contained in the layer region O is sufficiently smaller than the above value. In the case of the present invention, when the ratio of the layer thickness To of the layer region O to the layer thickness T of the amorphous layer is two-fifths or more, the oxygen contained in the layer region O is The upper limit of the amount of atoms is usually 30 atomic%
below, preferably below 20 atomic%, optimally
It is desirable that the content be 10 atomic% or less. In the present invention, the layer region O containing oxygen atoms constituting the amorphous layer has a localized region B containing oxygen atoms at a relatively high concentration on the support side as described above. It is preferable that the amorphous layer is provided as a layer, and in this case, the adhesion between the support and the amorphous layer can be further improved. The localized region B is desirably provided within 5μ from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region B may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. Localized region B has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of oxygen atoms is usually 500 atomic ppm or more, preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more.
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the layer region O containing oxygen atoms has a layer thickness of 5 μm or less from the support side (t _B
It is desirable that the maximum value Cmax of the distribution concentration exists in a layer region with a thickness of 5μ to 5μ. In the present invention, specific examples of the halogen atoms X contained in the first layer region G and second layer region S constituting the amorphous layer as necessary include fluorine, chlorine, bromine, Examples include iodine, and particularly preferred are fluorine and chlorine. In the present invention, in order to form the first layer region G composed of a-SiGe (H, done by. For example, by glow discharge method, a-SiGe
To form the first layer region G composed of (H,X), basically silicon atoms Si can be supplied.
The raw material gas for Si supply, the raw material gas for Ge supply that can supply germanium atoms Ge, and the raw material gas for introducing hydrogen atoms H or/and the raw material gas for introducing halogen atoms X as necessary are kept under reduced pressure inside. The gas is introduced into the deposition chamber under a desired pressure state to generate a glow discharge in the deposition chamber, and the distribution concentration of germanium atoms contained on the surface of a predetermined support, which has been placed at a predetermined position, is adjusted to the desired concentration. It is sufficient to form a layer made of a-SiGe (H,X) while controlling it according to a rate of change curve. 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 the Ge supply diluted with a diluent gas such as He or Ar as necessary. In accordance with this, a gas for introducing hydrogen atoms H or/and halogen atoms X is introduced into a deposition chamber for sputtering,
While forming a plasma atmosphere of the desired gas,
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 matter is heated and evaporated by a method such as the like, 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 ,
Germanium hydride in a gaseous state or capable of being gasified, such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., can be cited as one 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 and good Ge supply efficiency. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, Preferred examples include halogen compounds that can be gasified. Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer region G made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region G containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which is a raw material gas for supplying Si, and
Introducing germanium hydride, which serves as a raw material gas for supplying Ge, and gases such as Ar, H ₂ , He, etc. into a deposition chamber forming a first layer region G at a predetermined mixing ratio and gas flow rate; The first layer region G can be formed on a desired support by generating a glow discharge and forming a plasma atmosphere of these gases, but it is possible to control the introduction ratio of hydrogen atoms. In order to make the process even easier, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for forming the first layer region G. In the case of halides containing hydrogen atoms in these substances, when forming the first layer region G, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region G, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ and germanium or germanium compound for supplying Ge, or GeH ₄ , Se ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ，
Generating a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. But it can be done. In a preferred example of the present invention, the amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of the amounts of hydrogen atoms and halogen atoms ( H+X) is usually 0.01 to 40 atomic%, preferably 0.05 to 30 atomic%
The optimum range is preferably 0.1 to 25 atomic%. To control the amount of hydrogen atoms H and/or halogen atoms X contained in the first layer region G, for example, the support temperature or/and the amount of hydrogen atoms H or halogen atoms The amount of starting material introduced into the deposition apparatus, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer region S composed of a-Si (H,
The first layer is formed using starting materials [starting materials for forming the second layer region S] from among the starting materials I for forming the layer region G excluding the starting material that becomes the raw material gas for G supply. This can be performed according to the same method and conditions as in the case of forming region G. That is, in the present invention, in order to form the second layer region S composed of a-Si (H, It is done by a deposition method. For example, in order to form the second layer region S composed of a-Si (H, Introducing a raw material gas for introducing hydrogen atoms H and/or for introducing halogen atoms X as necessary into a deposition chamber whose interior can be reduced in pressure together with the raw material gas to cause a glow discharge method in the deposition chamber, A layer made of a-Si (H, In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms H or / and a gas for introducing halogen atoms X may be introduced into the deposition chamber for sputtering. In the photoconductive member of the present invention, the second layer region S, which is provided on the first layer region G containing germanium atoms and does not contain germanium atoms, is provided with a substance that controls conduction properties. By containing it, the conductive properties of the layer region S can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-
P gives P-type conduction characteristics to Si(H,X)
type impurities, and n-type impurities that provide n-type conductivity properties. Specifically, P-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance that controls conduction characteristics contained in the second layer region S is
organic relationships, such as the conduction characteristics required for the layer region S, the characteristics of other layer regions provided in direct contact with the layer region S, and the relationship with the characteristics at the contact interface with the other layer regions; You can select as appropriate. In the present invention, the content of the substance controlling conduction properties contained in the second layer region S is usually 0.001 to 1000 atomic ppm, preferably 0.001 to 1000 atomic ppm.
0.05-500atomic ppm, optimally 0.1-200atomic
It is preferable to set it in ppm. In order to structurally introduce a substance controlling the conductivity properties into the second layer region S, such as a group atom or a group atom, a starting material for introducing a group atom or a group atom is added during layer formation. The starting materials for introduction can be introduced in gaseous form into the deposition chamber together with other starting materials for forming the second layer region. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing silicon atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Silicon hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include silicon halides such as _BBr3 . Other examples include AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ and TlCl ₃ . 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 , A: Br 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, in order to provide the layer region O containing oxygen atoms in the amorphous layer, the starting material for introducing oxygen atoms is added to the above-mentioned amorphous layer forming material during the formation of the amorphous layer. It may be used together with the starting materials and contained in the layer to be formed while controlling its amount. When the glow discharge method is used to form the layer region O, a starting material for introducing oxygen atoms is added to one selected as desired from among the starting materials for forming the amorphous layer described above. . As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas whose constituent atoms are silicon atoms Si, and a raw material gas whose constituent atoms are oxygen atoms O,
Hydrogen atom H or halogen atom X as necessary
A raw material gas having constituent atoms is mixed at a desired mixing ratio, or a raw material gas having silicon atoms Si and a raw material gas having oxygen atoms O and hydrogen atoms H are used. , also in a desired mixing ratio, or silicon atoms, Si
A raw material gas with constituent atoms, silicon atoms Si,
A raw material gas having three constituent atoms, oxygen atom O and hydrogen atom H, can be mixed and used. Alternatively, a raw material gas containing silicon atoms Si and hydrogen atoms H as constituent atoms may be mixed with a raw material gas containing oxygen atoms O as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H), such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H Examples include lower siloxanes such as ₃ SiOSiH ₂ OSiH ₃ ). In order to form the first amorphous layer I containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer, or a mixture of Si and SiO ₂ is used. This can be carried out by sputtering the wafers in various gas atmospheres, using them as targets. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
Then, the raw material gas for introducing halogen atoms is diluted with a diluent 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 an amorphous layer, the distribution concentration C, O of oxygen atoms contained in the layer region O is changed in the layer thickness direction. In order to form a layer region O having a desired distribution state (depth profile) in the layer thickness direction, in the case of glow discharge, a starting material gas for introducing oxygen atoms whose distribution concentration C, O should be changed is used. ,
This is accomplished by introducing the gas 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 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 forming the layer region O by the sputtering method, the distribution concentration C, O of oxygen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth) of oxygen atoms in the layer thickness direction.
Firstly, as in the case of the glow discharge method, a starting material for introducing oxygen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is adjusted as desired. Therefore, it can be achieved by changing it appropriately. Second, if a target for sputtering is used, for example, a mixture of Si and SiO ₂ , the mixing ratio of Si and SiO ₂ should be varied in advance in the direction of the layer thickness of the target. It is accomplished by In the present invention, the amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X ) is usually 1~
Desirably, the content is 40 atomic %, preferably 5 to 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, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of such an electrically insulating support is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 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 SiF ₄ gas diluted with He (purity 99.99%, 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 an amorphous 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
The outflow valves 1117 and 111 are adjusted so that the ratio between the GeH ₄ /He gas flow rate and the No gas flow rate becomes the 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 GeH ₄ /He gas is controlled manually or by an externally driven motor or the like at the valve 11 according to a pre-designed rate of change curve.
The distribution concentration of germanium atoms contained in the formed layer is controlled by gradually changing the openings of 18. In the manner described above, the first layer region G is formed on the base 1137 to a desired layer thickness by maintaining the glow discharge for a desired time. At the stage where the first layer region G has been formed to the desired layer thickness, the discharge valve 1118 is completely closed, and the discharge conditions are changed as necessary for the desired period of time according to the same conditions and procedures. By maintaining the glow discharge, it is possible to form a second layer region S substantially free of germanium atoms on the first layer region G. In order to contain a substance that controls conductivity in the second layer region S, a gas such as B ₂ H ₆ or PH ₃ is introduced into the deposition chamber 1101 when forming the second layer region S. All you have to do is add it to the gas you introduce. 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. 11, GeH ₄ /He was deposited on a cylindrical Al substrate under the conditions shown in Table 1 and according to the rate of change curve of the gas flow rate ratio shown in FIG.
An image forming member for electrophotography was obtained by forming a layer by changing the gas flow rate ratio of gas and SiH ₄ /He gas with the elapsed time of layer formation. 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 a light image was immediately irradiated using a tungsten lamp light source to transmit a light amount of 2 lux.sec. It was irradiated through a 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 resolution and good gradation reproducibility were obtained. Example 2 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 13 under the conditions shown in Table 2. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 3 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 14 under the conditions shown in Table 3. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH 4 /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 15 under the conditions shown in Table _4. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 5 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 16 under the conditions shown in Table 5. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 6 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 17 under the conditions shown in Table 6. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 7 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 18 under the conditions shown in Table 7. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 8 In Example 1, instead of SiH ₄ /He gas,
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that Si ₂ H ₆ /He gas was used and the conditions shown in Table 8 were used. 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, instead of SiH ₄ /He gas,
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that SiF ₄ /He gas was used and the conditions shown in Table 9 were used. 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 10 In Example 1, instead of SiH ₄ /He gas,
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that (SiH ₄ /He+SiF ₄ /He) gas was used and the conditions shown in Table 10 were used. 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 11 In Examples 1 to 10, the conditions for creating the second layer were
Each of the electrophotographic image forming members was produced under the same conditions as shown in each Example except that the conditions shown in Table 11 were used. 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 11A were obtained. Example 12 In Examples 1 to 10, the conditions for creating the second layer were
Each of the electrophotographic image forming members was produced under the same conditions as shown in each example except that the conditions shown in Table 12 were used. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 12A were obtained. Example 13 Using the manufacturing apparatus shown in FIG. 11, GeH ₄ /He gas and SiH ₄ /He gas were produced under the conditions shown in Table 13 and according to the change rate curve of the gas flow rate ratio shown in FIG. 19.
Layer formation was performed under the same conditions as in Example 1, except that the gas flow rate ratio of NO gas and SiH ₄ /He gas was changed as well as the elapsed time for layer formation, and an electrophotographic image forming member was obtained. Ta. 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 14 Using the manufacturing apparatus shown in FIG. 11, GeH ₄ /He gas and SiH ₄ /He gas were produced under the conditions shown in Table 14 and according to the change rate curve of the gas flow rate ratio shown in FIG. 20.
Layer formation was carried out under the same conditions as in Example 1 except that the gas flow rate ratio of NO gas and SiH ₄ /He gas was varied with the elapsed time of layer formation 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 15 In Examples 1 to 10, the same toner as in Example 1 was used except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp to form an electrostatic image. When the image quality of the toner transfer images was evaluated for each of the electrophotographic image forming members prepared under the same image forming conditions as in Examples 1 to 10, it was found that the images had excellent resolution and good gradation reproducibility. Clear, high-quality images were obtained.

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[Table] ◎: Excellent ○: Good

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[Table] ◎: Excellent ○: Good

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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...
Approx. 200℃ Germanium atom (Ge)-free layer...Approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are diagrams for explaining the distribution state of germanium atoms in the amorphous layer, respectively. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
FIG. 0 is an explanatory diagram showing a change rate curve of the gas flow rate ratio in each example of the present invention. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer.

Claims (1)

[Claims] 1. A support for a photoconductive member for electrophotography, and silicon atoms on the support at a concentration of 1 to 9.5×10 ⁵ atomic ppm.
A first layer region with a layer thickness of 30 Å to 50 μ made of an amorphous material containing germanium atoms, and a 0.5 to 90 μ thick layer made of an amorphous material containing silicon atoms (but not germanium atoms). The layer thickness 1 of the layer structure in which the second layer region is provided in order from the support side
A photoconductive member for electrophotography, comprising a photoreceptive layer having a photoconductivity of ~100μ, wherein the distribution state of germanium atoms in the first layer region is as described above. On the support side
The light-receiving layer has a high content of 1000 atomic ppm or more, and has a considerably lower content on the interface side than on the support side, and is in a non-uniform distribution state in the layer thickness direction. A photoconductive member for electrophotography, characterized in that it contains oxygen atoms. 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 distribution state of germanium atoms in the first layer region is such that more germanium atoms are distributed toward the support side.