JPH0220984B2 - - 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 spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which require a combined improvement in characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes afterimages, or when used repeatedly at high speeds, the response gradually decreases. There were many cases where spots appeared. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members for electrophotography. The present invention has been made in view of the above points, and includes a
-As a result of comprehensive research and study on Si from the viewpoint of its applicability and responsiveness as a photoconductive member used in electrophotographic image forming members, we have discovered that Si is an amorphous material whose matrix is silicon atoms. , in particular, an amorphous material having a silicon atom as a matrix and containing at least either a hydrogen atom H or a halogen atom X, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as ``a-Si(H,X)'' is used as a generic notation for these materials. The photoconductive materials designed and manufactured under this technology not only exhibit extremely superior properties in practical use, but also surpass in all respects compared to conventional photoconductive materials, especially for electrophotography. This is based on the discovery that it has extremely excellent properties as a photoconductive member, and that it has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member for electrophotography (hereinafter referred to as "photoconductive member") which is long-lasting, does not cause any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponsiveness. Another object of the present invention is to provide charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient properties. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member having high signal-to-noise ratio characteristics. The photoconductive member of the present invention includes a support for a photoconductive member for electrophotography, and an amorphous material containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm based on the sum of silicon atoms on the support. Layer thickness 30Å made up of material
A first layer region G with a thickness of ~50μ and a second layer region S 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. The layer thickness of the layer structure is 1~
A first layer exhibiting photoconductivity of 100μ and a second layer with a layer thickness of 0.003 to 30μ composed of an amorphous material containing silicon atoms and 1×10 ^-3 to 90 atomic % carbon atoms. The first layer contains 0.001 to 50 atomic % of oxygen atoms based on the sum of silicon atoms, germanium atoms, and oxygen atoms, has a smooth concentration distribution, and has a photoreceptive layer that supports the layer. Within a layer thickness of 5μ from the body side or the interface side with the second layer
It is characterized by a maximum concentration distribution of 500 atomic ppm or more. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it is highly sensitive.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast optical response. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. A photoconductive member 100 shown in FIG. 1 includes a first layer 10 on a support 101 for photoconductive member.
2 and a second layer 103, the photoreceptive layer has a free surface 106 on one end face. The first layer 102 is a-
First layer region G1 composed of Ge (Si, H, X)
04 and a-Si(H,X) and a second layer region S105 having photoconductivity are laminated in this order. The germanium atoms contained in the first layer region G104 may be uniformly distributed in the first layer region G104, or may be uniformly contained in the layer thickness direction. However, the distribution concentration may be non-uniform. However, in any case, the content is uniformly distributed in the in-plane direction parallel to the surface of the support, but from the point of view of making the properties uniform in the in-plane direction. is also necessary. Especially,
It is uniformly contained in the layer thickness direction of the first layer 102 and is on the side opposite to the side where the support 101 is provided (the free surface 106 side of the photoreceptive layer).
It is contained in the first layer region G104 so that it is distributed in a larger amount on the support body 101 side, or in the opposite distribution state. In the photoconductive member of the present invention, as described above, the germanium atoms contained in the first layer region G have the distribution state as described above in the layer thickness direction, and the surface of the support It is desirable to have a uniform distribution state in the in-plane direction parallel to . In the present invention, germanium atoms are not contained in the second layer region S provided on the first layer region G, and the first layer cannot be formed in such a layer structure. Accordingly, it is possible to obtain a photoconductive member that has excellent photosensitivity to light having wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths, including the visible light region. Further, in one of the preferred embodiments, the distribution state of the germanium atoms in the first layer region G is such that the germanium atoms are continuously and evenly distributed in the entire layer region, and the germanium atoms are distributed uniformly in the entire layer region. Since the distribution concentration C in the thickness direction is given a change that decreases from the support side toward the second layer region S, the affinity between the first layer region G and the second layer region S is In addition, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support, when a semiconductor laser or the like is used,
Light on the longer wavelength side, which is almost completely absorbed in the second layer region S, can be substantially completely absorbed in the first layer region G, preventing interference due to reflection from the support surface. You can. FIGS. 2 to 10 show typical examples in which the distribution state of germanium contained in the first layer region G of the photoconductive member of the present invention in the layer thickness direction is non-uniform. 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 C ₂ to the interface position t _T . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. 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
It is said to be C ₁₀ . Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of _C11 from position _tB to position _t4 , and
From t ₄ to position t _T , the distribution state is such that the concentration decreases linearly from C ₁₂ to C ₁₃ . 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
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 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 positions t ₆ and ₇ , the concentration decreases rapidly at first, then gradually decreases to a concentration C ₁₉ at position t ₇ , and between positions t ₇ and t ₈ , is gradually reduced 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. The case where it is provided in region G is cited as one of the preferred examples. The first layer region G constituting the first layer constituting the photoconductive member in the present invention is preferably on the support side as described above, or on the contrary, on the free surface side of the photoreceptive layer. It is desirable to have a localized region A in which germanium atoms are contained at a relatively high concentration. For example, localized region A can be explained using the symbols shown in FIGS. 2 to 10 by 5μ from interface position _tB .
It is desirable that it be installed within the same range. 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 area A is a part or all of the layer area L _T is determined as appropriate depending on the characteristics required of the first layer to be formed. The localized region A has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms,
More preferably 5000 atomic ppm or more, optimally 1
It is desirable to form a layer in such a way that a distribution state of 10 ⁴ atomic ppm or more can be obtained. That is, in the present invention, the layer region G containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (a layer region with a thickness of 5μ from t _B ). In the present invention, the content of germanium atoms contained in the first layer region G is appropriately determined as desired so as to effectively achieve the object of the present invention, but , preferably 1 to 10×10 ⁵ atomic ppm, preferably
100-9.5× ¹⁰⁵ atomic ppm, optimally 500-8×
It is desirable to set it to 10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region G and the second layer region S is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the desired properties are fully imparted to the member. In the present invention, the layer thickness t _B of the first layer region G is
Preferably 30 Å to 50 μ, more preferably 40 Å to
It is desirable that the thickness be 40μ, optimally 40Å to 30μ. Further, the layer thickness T of the second layer region S is preferably
0.5-90μ, more preferably 1-80μ, optimally 2
It is desirable that the thickness be ~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 characteristics required for the entire first 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 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 as follows:
When satisfying the relationship T _B /T≦1, it is desirable to select appropriate numerical values for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region G is 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the first layer region G
It is desirable that the thickness be quite thin, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less. In the present invention, the halogen atoms X contained in the first layer region G and the second layer region S constituting the first layer are specifically fluorine, chlorine, bromine, Examples include iodine, and particularly preferred are fluorine and chlorine. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the photoreceptive layer, A layer region O containing oxygen atoms is provided. The oxygen atoms contained in the first layer may be uniformly contained in the entire layer region of the first layer, or may be contained uniformly in only a part of the layer region of the first layer. It may be allowed to exist. In the present invention, the distribution state of oxygen atoms in the layer region O is such that even if the distribution concentration CO is uniform in the in-plane direction parallel to the surface of the support, it is uneven in the layer thickness direction. Uniform. In the example shown in FIG. 11, from position t _B to position t ₉
The distribution concentration of oxygen atoms in the layer region up to CO
In the layer region from position t ₉ to position ₁₀ , the concentration of oxygen atoms increases sharply from _{t 9 to} t ₁₀ , and at t ₁₀ , the distribution concentration of oxygen atoms reaches the peak value C ₂₂ . position t ₁₀
In the layer region from t to position _t11 , the distribution concentration CO of oxygen atoms decreases to a concentration _C21 at position _tT . In the example shown in FIG. 12, from position t _B to position t ₁₂
The distribution concentration of oxygen atoms in the layer region up to CO is the concentration
C ₂₃ , and in the layer region from position t ₁₂ to t ₁₃ , t ₁₂
The distribution concentration of oxygen atoms, CO, increases rapidly until t ₁₃ , and at position t ₁₃ , the distribution concentration of oxygen atoms takes a peak value C ₂₄ , and in the layer region from position t ₁₃ to position t _T , the distribution concentration of oxygen atoms, CO, decreases to almost zero. Decrease. In the example shown in FIG. 13, from position t _B to position t ₁₄
In the layer region up to, the distribution concentration CO of oxygen atoms gradually increases from C ₂₅ to C ₂₆ , and the distribution concentration CO of oxygen atoms reaches a peak value C ₂₆ at position t ₁₄ . In the layer region from position t ₁₄ to position t _T , the distribution concentration of oxygen atoms is
CO decreases rapidly to a concentration C ₂₅ at position t _T. In the example shown in FIG. 14, the distribution concentration CO of oxygen atoms is a concentration C ₂₇ at the position t _B , and the distribution concentration CO decreases until the position t ₁₅ , and becomes the concentration C ₂₈ at t ₁₅ . position t ₁₅
In the layer region from to position t ₁₆ , the distribution concentration CO of oxygen atoms is constant at the concentration C ₂₈ . In the layer region from position t ₁₆ to position t ₁₇ , the distribution concentration CO of oxygen atoms increases, and the distribution concentration CO at position t ₁₇ reaches its peak value.
Take C ₂₉ . In the layer region from position _t17 to position _tT , the distribution concentration CO of oxygen atoms decreases to a concentration _C28 at position _tT . In the present invention, when the main purpose of the layer region O provided in the first layer containing oxygen atoms is to improve photosensitivity and dark resistance, the entire layer region of the first layer is In order to prevent charge injection from the free surface of the photoreceptive layer,
When it is provided near the free surface side and the main purpose is to strengthen the adhesion between the support and the light-receiving layer, it should be provided so as to occupy the end layer area E of the first layer on the support side. provided. In the first case mentioned above, the content of oxygen atoms contained in the layer region O is made relatively low in order to maintain high photosensitivity, and in the second case the content of oxygen atoms contained in the layer region O is made relatively low in order to maintain high photosensitivity, and in the second case to prevent the injection of charges from the free surface of the photoreceptor layer. In the third case, it is desirable to use a relatively large amount in order to reliably strengthen the adhesion to the support. In addition, for the purpose of achieving the above three at the same time,
distributed at a relatively high concentration on the support side and distributed at a relatively low concentration at the center of the first layer,
In the interface layer region on the free surface side of the first layer, a distribution state of oxygen atoms such that the number of oxygen atoms is increased can be formed in the layer region O. In the present invention, the content of oxygen atoms contained in the layer region O provided in the first layer is as follows:
In terms of organic relationships, such as the characteristics required for itself, or, if the layer region O is provided in direct contact with the support, the relationship with the characteristics at the contact interface with the support. , can be selected as appropriate. 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 preferably 0.001.
~50atomic%, more preferably 0.002~
It is desirable that it be 40 atomic %, optimally 0.003 to 30 atomic %. In the present invention, whether or not the layer region O occupies the entire area of the first layer, the layer thickness T of the first layer is equal to the layer thickness T ₀ of the layer region O. When the proportion of oxygen atoms in the layer region O 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, if the ratio of the layer thickness T ₀ of the layer region O to the layer thickness T of the first layer is two-fifths or more, the content in the layer region O is The upper limit of the amount of oxygen atoms is preferably:
30atomic% or less, more preferably 20atomic%
Hereinafter, the optimum value is preferably 10 atomic% or less. In the present invention, the layer region O containing oxygen atoms constituting the first layer is a region O containing oxygen atoms at a relatively high concentration on the support side and near the free surface, as described above. It is desirable that the support be provided as having a contact area B, and in this case, it is possible to further improve the adhesion between the support and the first layer and to improve the acceptance potential. The localized region B can be explained using the symbols shown in FIGS. 11 to 14 at the interface position t _B or t _T
It is desirable that the distance be within 5μ. 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 t _T , or may be a part of the layer region L _T. In some cases. 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 first layer to be formed. Localized region B has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of oxygen atoms is preferably 500 atomic ppm or more,
More preferably 800 atomic ppm or more, optimally
It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be obtained. That is, in the present invention, the layer region O containing oxygen atoms has a distribution concentration within 5 μm in layer thickness from the interface on the support side or free surface side (layer region 5 μ thick from t _B or t _T ). It is desirable to form it so that a maximum value Cmax exists. In the present invention, the first layer region G composed of a-Ge (Si, H, It is done by a deposition method. For example, in order to form the first layer region G composed of a-Ge (Si, H, A raw material gas for supplying Si that can supply silicon atoms Si as needed, a raw material gas for introducing hydrogen atoms H, and/or a raw material gas for introducing halogen atoms X into a deposition chamber whose interior can be reduced in pressure. A glow discharge is generated in the deposition chamber by introducing the gas at a desired pressure state, and a.
A layer consisting of -Ge (Si, H, X) may be formed. In addition, in order to contain germanium atoms in a non-uniform distribution state, the distribution concentration of germanium atoms is controlled according to the desired rate of change curve, and a-Ge (Si,
A layer consisting of H, X) may be formed. In addition, when forming by sputtering method, for example, Ar,
Using a target made of Si, or two targets made of Si and Ge in an atmosphere of an inert gas such as He or a mixed gas based on these gases, or using Si and a target made of Ge. If desired, use a mixed target of Ge.
A raw material gas for supplying Ge diluted with a diluent gas such as He or Ar, and a gas for introducing hydrogen atoms H or/and halogen atoms X as necessary, are introduced into the deposition chamber for sputtering to obtain the desired gas. This is achieved by creating a plasma atmosphere of In order to make the distribution of germanium atoms non-uniform, for example, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially in terms of ease of handling during layer creation work and good Si supply efficiency. Preferred examples include SiH ₄ and Si ₂ H ₆ . Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer region G made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When forming 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 measurement 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. a-SiGe by ion plating method
In order to form the first layer region G consisting of (H, This can be done by heating and evaporating the material using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material through a desired gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br ₂ ,
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 with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
This can also be done by causing a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. . In a preferred example of the present invention, the amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of hydrogen atoms and halogen atoms (H+X) contained in the first layer region G constituting the first layer to be formed 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 %. To control the amount of hydrogen atoms H 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 system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer region S composed of a-Si (H,
The first layer is formed using starting materials [starting materials for forming the second layer region S] from among the starting materials for forming the layer region G excluding the starting material that becomes the raw material gas for supplying Ge. This can be carried out using the same method and conditions as when 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, Together with the raw material gas, if necessary, a raw material gas for introducing hydrogen atoms H and/or halogen atoms A layer made of a-Si(H,X) may be formed on the surface of a predetermined support placed at a predetermined position. 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 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 preferably 1 to
40 atomic %, more preferably 5-30 atomic %,
The optimum range is preferably 5 to 25 atomic %. In the present invention, in order to provide the layer region O containing oxygen atoms in the first layer, the starting material for introducing oxygen atoms is added to the above-mentioned first layer forming layer when forming the first layer. It may be used together with the starting material to control its amount in the formed layer. When a 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 first 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 containing silicon atoms as constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms as constituent atoms and oxygen atoms O and hydrogen atoms H
A raw material gas having constituent atoms is mixed at a desired mixing ratio, or a raw material gas having silicon atoms Si and three of silicon atoms Si, oxygen atoms O, and hydrogen atoms H are mixed. It can be used in combination with a raw material gas having constituent atoms. Alternatively, a raw material gas containing silicon atoms Si and hydrogen atoms H as constituent atoms may be mixed with a raw material gas containing oxygen atoms O as constituent atoms. Specifically, for example, oxygen O ₂ , ozone O ₃ , nitrogen monoxide NO, nitrogen dioxide NO ₂ , nitrogen monooxide
N ₂ O, nitrogen sesquioxide N ₂ O ₃ , nitrogen tetroxide N ₂ O ₄ ,
The constituent atoms are nitrogen pentoxide N ₂ O ₅ , nitrogen trioxide NO ₃ , silicon atom Si, oxygen atom O, and hydrogen atom H. Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). To form the layer region O containing oxygen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or _SiO2 wafer or Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a sputtering deposition chamber, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms H and/or halogen atoms X as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example mentioned above is
It can also be used as an effective gas in sputtering. In the present invention, when forming a layer region O containing oxygen atoms when forming the first layer, the distribution concentration C 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 depth profile in the layer thickness direction, in the case of glow discharge, the starting material gas for introducing oxygen atoms whose distribution concentration CO should be changed is
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 line. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, for example, a microcomputer or the like may be used to control the flow rate according to a pre-designed change rate curve to obtain a desired content rate curve. When the layer region O is formed by the sputtering method, the distribution concentration CO of oxygen atoms in the layer thickness direction is changed in the layer thickness direction to form a desired distribution state (depth profile) of oxygen atoms in the layer thickness direction. First, as in the case of the glow discharge method, the 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. It is achieved by changing. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be done by changing the mixing ratio of Si and SiO ₂ in advance in the layer thickness direction of the target. In the photoconductive member of the present invention, the first layer region G containing germanium atoms and/or the second layer region S not containing germanium atoms contains a substance C that controls conduction properties. Thereby, the conduction characteristics of the layer region G and/or the layer region can be controlled as desired. In the present invention, a substance C that controls conduction properties is used.
The layer region PN containing may be provided in a part or the entire layer region of the first layer. Or layer area PN
may be provided in a part or all of the layer region G or layer region S. Examples of the substance C that controls conduction characteristics include so-called impurities in the semiconductor field.
In the present invention, a P-type impurity that imparts P-type conductivity to SiGe and an n-type impurity that imparts N-type conductivity can be used. Specifically, P-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance C that controls the conductive properties contained in the first layer is determined by the conductive properties required for the first layer or the substance C that is provided in direct contact with the first layer. The layer can be appropriately selected depending on the organic relationship, such as the characteristics of the other layer or support, and the relationship with the characteristics of the contact interface with the other layer or support. In addition, when the substance controlling the conduction properties is contained in the first layer locally in a desired layer region of the first layer, it is particularly preferable to When it is contained in the support side end layer region E, the relationship with the characteristics of other layer regions provided in direct contact with the layer region E and the characteristics at the contact interface with the other layer regions. The content of the substance that controls the conduction characteristics is appropriately selected with consideration given to the following. In the present invention, the content of the substance C that controls conduction properties contained in the layer region PN is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably
0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5×
It is desirable to set it to 10 ³ atomic ppm. In the present invention, the content of the substance C controlling the conduction characteristics in the layer region PN containing the substance C is preferably 30 atomic ppm or more, more preferably
50atomic ppm or more, optimally 100atomic ppm
In the above case, it is desirable that the substance C be locally contained in a part of the layer region of the first layer,
In particular, it is desirable to contain it unevenly in the support side end layer region E of the first layer I. Among the above, the support side end layer region E of the first layer
For example, when the substance C to be contained is the above-mentioned P-type impurity, by including the substance C that controls the conduction characteristics in a content exceeding the above-mentioned value, the photoreceptor layer can be improved. It is possible to effectively prevent the movement of electrons injected from the support side into the photoreceptive layer when the free surface is subjected to polar charging treatment, and when the substance to be contained is the above n-type impurity. When the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to effectively prevent the movement of holes injected from the support side into the photoreceptor layer. In this way, when the end layer region E contains a substance that controls conduction characteristics of one polarity, the remaining layer region of the first layer, that is, the portion excluding the end layer region E The layer region Z may contain a substance that controls the conduction characteristics of the other polarity, or the substance that controls the conduction characteristics of the same polarity may be contained in a smaller amount than the actual amount contained in the end layer region E. It may also be contained in a much smaller amount. In such a case, the content of the substance C that controls the conduction properties contained in the layer region Z is as follows:
Although it is appropriately determined as desired depending on the polarity and content of the substance contained in the end layer region E, it is preferably 0.001 to 1000 atomic ppm or more, more preferably 0.05 to 500 atomic ppm or more. The optimum content is preferably 0.1 to 200 atomic ppm. In the present invention, when the end layer region E and the layer region Z contain a substance that controls the same kind of conductivity, the content in the layer region Z is preferably 30 atomic ppm or less. desirable. In addition to the above-mentioned case, the present invention includes a layer region containing a substance that controls conductivity having one polarity in the first layer, and a layer region that controls conductivity having the other polarity. It is also possible to provide a layer region containing a substance in direct contact and to provide a so-called depletion layer in this contact region. For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the first layer so as to be in direct contact with each other to form a so-called P-n junction. Thus, a depletion layer can be provided. In order to structurally introduce a substance C for controlling conduction properties into the first layer, such as a group atom or a group atom, a starting material for introducing a group atom or a group atom for introducing a group atom is added during layer formation. The starting materials may 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 introducing such a group atom, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing such a group atom, for introducing a boron atom,
B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₃ ,
Examples include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition,
AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, effective starting materials for introducing a group atom 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 , and _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. In the photoconductive member 100 shown in FIG. 1, a second layer 10 is formed on a first layer 102.
3 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. The second layer in the present invention consists of silicon atoms, Si
and carbon atom C, and hydrogen atom H or / as necessary
and an amorphous material containing a halogen atom X (hereinafter referred to as
"a-(Si _x C _1-x ) _y (H, X) _1-y " However, 0<x, y
<1)). The second layer composed of a-(Si _x C _{1-x ) y} (H, This is accomplished by law, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having a photoconductive material, and it is easy to introduce carbon atoms and silicon atoms together with silicon atoms into the second layer to be manufactured. A discharge method or a sputtering method is preferably employed. Furthermore, in the present invention, the second layer may be formed by using both the glow discharge method and the sputtering method within the same apparatus system. To form the second layer by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y ( _H , The mixture is mixed at a fixed mixing ratio and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into plasma gas by generating a glow discharge, and the gas is already deposited on the support. a-
(Si _x C _1-x ) _y (H, X) _1-y may be deposited. In the present invention, a-(SixC _1-x ) _y (H,X) _1-y
The raw material gas for formation is a gaseous substance whose constituent atom is at least one of silicon atom Si, carbon atom C, hydrogen atom H, and halogen atom X, or a gasified substance that can be gasified. Most can be used. When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as required. According to or/and a source gas containing X as a constituent atom are mixed at a desired mixing ratio, or a source gas containing Si as a constituent atom and a source gas containing Si,
A raw material gas containing three constituent atoms of C and H, or
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. Raw material gases serving as constituent atoms may be mixed and used. In the present invention, suitable halogen atoms X contained in the second layer include F, Cl, Br,
I, particularly F and Cl are preferred. In the present invention, raw material gases that can be effectively used to form the second layer include gaseous materials or substances that can be easily gasified at normal temperature and normal pressure. In the present invention, gases such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ containing Si and H as constituent atoms are effectively used as the raw material gas for forming the second layer. Silicon hydride gas such as silanes, saturated hydrocarbons containing C and H as constituent atoms, e.g. saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, ethylene hydrocarbons having 2 to 3 carbon atoms, Examples include acetylene hydrocarbons, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₅ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylenic hydrocarbons include: Acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogens include fluorine,
Halogen gases such as chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , ClF ₅ ,
BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHB ₃ ,
Examples of silicon hydride include silanes such as SiH ₄ , Si ₂ H ₈ and Si ₄ H ₁₀ . In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
_CH2F2 , _CH3F , _CH3Cl , _CH3Br , _{CH3I ,}
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ and SF ₅ , Si(CH ₃ ) ₄ ,
Alkyl silicides such as Si(C ₂ H ₅ ) ₄ and SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These second layer-forming substances are used in such a way that the second layer to be formed contains silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio. It is selected and used as desired when forming the second layer. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiH ₂ Cl ₃ can contain halogen atoms. _{A- ( Si x _} C _1-x ) _y (Cl+
H) A second layer consisting of _1-y can be formed. To form the second layer by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are necessary. Depending on the situation, sputtering may be performed in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing C and H or/and The Si wafer may be sputtered by forming a gas plasma of the above gas. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as necessary by using Si and C as separate targets or by using a mixed target of Si and C. This is done by sputtering inside.
As the material gas for introducing C, H, and X, the material for forming the second layer shown in the glow discharge example described above can also be used as an effective material in the sputtering method. In the present invention, the diluent gas used when forming the second layer by the glow discharge method or sputtering method is a so-called rare gas, such as He,
Preferable examples include Ne, Ar, and the like. The second layer in the present invention is carefully formed to provide the desired properties. In other words, substances containing Si, C, and optionally H or/and In the present invention, a that exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive.
-(Si _x C _{1-x ) y} (H, For example, to provide the second layer with the main purpose of improving electrical voltage resistance, a-(Si _x C _1-x ) _y (H,
X) _1-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use. In addition, if a second layer is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the degree of electrical insulation described above will be relaxed to some extent, and the material will have a certain degree of sensitivity to the irradiated light. As an amorphous material, a-(Si _x C _1-x ) _y (H, X) _1-y
is created. a-(Si _x C _1-x ) _y (H, X) ₁ on the surface of the first layer
When forming the _second layer consisting of
a-(Si _x C _1-x ) _y (H,
X) It is desirable that the temperature of the support during layer formation be strictly controlled so that _1-y can be formed as desired. In the present invention, the formation of the second layer is carried out by appropriately selecting the optimum range in accordance with the method of forming the second layer in order to effectively achieve the desired purpose. ~400℃, more preferably 50~
The temperature is desirably 350°C, most preferably 100-300°C. Glow discharge method and sputtering method are used to form the second layer, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. Adoption of the ring method is advantageous, but when forming the second layer by these layer forming methods, the discharge power during layer formation is set at a-( Si _x C _1-x ) _y
(H, X) This is one of the important factors that influences the properties of _1-y . The discharge power condition for effectively producing a-(Si _x C _1-x ) _y (X) _1-y with good productivity, which has the characteristics to achieve the purpose of the present invention, is preferably 10 to 10. 300W, more preferably 20-250W, optimally
It is desirable that the power be 50 to 200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr. In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and discharge power for creating the second layer, but these layer creation factors can be determined independently and separately. Instead, the desired characteristic a-(Si _x C _1-x ) _y (H,X) ₁
Preferably, the optimum value of each layer formation factor is determined based on mutual organic relationships such that a second layer consisting of _-y is formed. The amount of carbon atoms contained in the second layer in the photoconductive member of the present invention is the same as the conditions for forming the second layer, so that the second layer can be formed to obtain the desired characteristics to achieve the object of the present invention. This is an important factor.
The amount of carbon atoms contained in the second layer in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer. That is, the general formula a-(Si _x C _1-x ) _y (H, X) _1-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ". However, 0<a<1 ),
Amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C _1-b ) _c H _1-c ". However, 0<b, c<1) , an amorphous material (hereinafter referred to as "a-(Si _d
C _1-d ) _e (H,X) _1-e ”. However, 0<d, e
<1). In the present invention, when the second layer is composed of a-Si _a C _1-a , the amount of carbon atoms contained in the second layer is preferably 1×10 ⁻³ to 90 atomic%,
More preferably 1-80 atomic%, optimally 10-80 atomic%
A desirable value is 75 atomic%.
That is, if we use the representation of a in the previous a-Si _a C _1-a , a
is preferably 0.1 to 0.99999, more preferably 0.2 to
0.99, optimally 0.25-0.9. In the present invention, the second layer is a-(Si _b C _1-b ) _c
When composed of H _1-c , the amount of carbon atoms contained in the second layer is preferably 1 × 10 ^-3 ~
90 atomic%, more preferably 1~
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%.
It is desirable that the hydrogen content be within these ranges, and photoconductive members formed with hydrogen contents within these ranges can be sufficiently applied as excellent materials in practical applications. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is preferably 0.1 to 0.99999, more preferably 0.1 to
0.99, optimally 0.15~0.9, c preferably 0.6~
0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. When the second layer is composed of a-(Si _d C _1-d ) _e (H,X) _1-e , the content of carbon atoms contained in the second layer is as follows: Preferably 1×10 ^-3
~90 atomic%, more preferably 1-90 atomic%,
The optimum value is 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 20 atomic%.
The halogen atom content is preferably 18 atomic %, most preferably 2 to 15 atomic %, and photoconductive members prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably
It is desirable that it be 19 atomic % or less, more preferably 13 atomic % or less. That is, d of the previous a-(Si _d C _1-d ) _e (H, X) _1-e ,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8-0.99, more preferably
It is desirable that it be between 0.82 and 0.99, most preferably between 0.85 and 0.98. The number range of the layer thickness of the second layer in the present invention is:
This is one of the important factors for effectively achieving the purpose of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. In addition, the thickness of the second layer is determined based on the characteristics required for each layer region, including the amount of carbon atoms contained in the layer and the thickness of the first layer. It is necessary to decide as appropriate based on the desired relationship. In addition, it is desirable to consider the economical aspects including productivity and mass production. The thickness of the second layer in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 20μ,
The optimum value is 0.005 to 10μ. 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 Pb, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If 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 a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to
It is considered to be 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 15 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 NO gas (purity 99.99%) cylinder, 1105 is He 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, the valves of the gas cylinders 1102 to 1106 are connected to
22 to 1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112
~1116, confirming that the outflow valves 1117~1121 and auxiliary valves 1132, 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.
Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, NO from gas cylinder 1104
Open the gas valves 1122, 1123, 1124 and check the outlet pressure gauges 1127, 1128, 1129.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 1112,
1113 and 1114 are gradually opened to allow the flow into mass flow controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valve 111
7, 1118, 1119, the auxiliary valves 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
Outflow valves 1117 and 111 are installed so that the ratio of GeH ₄ /He gas flow rate to NO gas flow rate becomes a desired value.
8 and 1119, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the openings of the valves 1118 and 1120 are gradually changed according to a pre-designed rate of change curve by controlling the flow rates of GeH ₄ /He gas and NO gas manually or using an externally driven motor. The distribution concentration of germanium atoms and oxygen atoms contained in the formed layer is controlled. In the manner described above, the glow discharge is maintained for a desired period of time to form the first layer region G on the substrate 1137 to a desired layer thickness. 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 the substance C that controls conductivity in the first layer region G and the second layer region S, for example, B ₂ Gases such as H ₆ and PH ₃ may be added to the gas introduced into the deposition chamber 1101. To form the second layer on the first layer formed to the desired thickness as described above, for example, by operating the same valve as when forming the first layer.
This is accomplished by diluting each of SiH ₄ gas and C ₂ H ₄ gas with a diluent gas such as He as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the second layer, for example, SiF ₄ gas and C ₂ H ₄ gas, or
This is done by adding Si ₈₂ gas and forming a second layer in the same manner as above. It goes without saying that all outflow valves other than those for the gases necessary to form each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow out of the reaction chamber 1101. Valve 1
In order to avoid gas remaining in the gas piping leading from 117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, and the auxiliary valve 11
32, 1133 and fully open the main valve 1134 to temporarily evacuate the system to high vacuum, as necessary. The amount of carbon atoms contained in the second layer is, for example, SiH ₄ gas when using the glow discharge method;
The flow rate ratio of the C ₂ H ₄ gas introduced into the reaction chamber 1101 can be changed as desired, or if the layer is formed by sputtering, sputtering of the silicon wafer and graphite wafer can be used to form the target. It can be controlled as desired by changing the area ratio or by changing the mixing ratio of silicon powder and graphite powder and molding the target. The amount of halogen atoms X contained in the second layer is determined by the amount of raw material gas for introducing halogen atoms,
For example, this can be done by adjusting the flow rate when SiF ₄ gas is introduced into the reaction chamber 1101. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Samples (sample Nos. 11-1 to 17-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 15 under the conditions shown in Table 1.
(Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen atoms in each sample is shown in FIG. Each sample thus obtained was placed in a charging exposure experimental device and corona charged at 5.0KV for 0.3 seconds.
A light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 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 chargeable developer (including toner and carrier) over the imaging member surface. When the toner image on the image forming member was transferred onto transfer paper using 5.0 KV corona charging, all samples had excellent resolution and clear, high-density images with good gradation reproducibility were obtained. In the above, the toner image forming conditions were the same as above, except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp, and an electrostatic image was formed. When the image quality of the toner-transferred images was evaluated, all samples had excellent resolution, and clear, high-quality images with good gradation reproducibility were obtained. Example 2 Samples (sample Nos. 21-1 to 27-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 15 under the conditions shown in Table 3.
(Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When these samples were subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was repeatedly tested 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples. Example 3 Sample No. 11-1, 12-1, 13-1 of Example 1 except that the layer creation conditions were as shown in Table 5.
Each of the electrophotographic image forming members (Samples No. 11-1-1 to 11-1
-8, 12-1-1 to 12-1-8, 13-1-1 to 13
-1-8) were created. Each of the electrophotographic image forming members thus obtained was individually installed in a copying machine, and the electrophotographic image forming members corresponding to each example were prepared under the same conditions as described in each example. For each, the overall image quality of the transferred image was evaluated and the durability was evaluated through repeated and continuous use. Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability after repeated and continuous use. Example 4 Exactly the same as No. 11-1 of Example 1 except that during layer formation, the target area ratio of the silicon wafer and graphite was changed and the content ratio of silicon atoms and carbon atoms in the layer was changed. Each of the imaging members was made by the method. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated 50,000 times, and then image evaluation was performed, and the results shown in Table 7 were obtained. Example 5 Sample No. 5 is the same as Example 1 except that when forming the layer, the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the layer.
Each of the image-forming members was produced by the same method as in Example 12-1. For each of the image forming members thus obtained, the steps up to transfer were repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 8 were obtained. Example 6 Sample No. of Example 1 was used, except that during layer formation, the flow rate ratio of SiH ₄ gas, SiF ₄ gas, and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the layer. Each of the imaging members was made in exactly the same manner as in .13-1. The image forming member thus obtained was subjected to image formation, development, and development as described in Example 1.
After repeating the cleaning process about 50,000 times, image evaluation was performed, and the results shown in Table 9 were obtained. Example 7 Sample No. 1 of Example 1 except for changing the layer thickness.
Each of the image-forming members was produced by the same method as in Example 14-1. Imaging as described in Example 1;
The development and cleaning steps were repeated to obtain the results shown in Table 10.

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[Table] ◎: Very good ○: Good △: Sufficient for practical use ×: Image defects occur

[Table] ◎: Very good ○: Good △: Sufficient for practical use ×: Image defects occur

[Table] ◎: Very good ○: Good △: Adequate for practical use ×: Image defects occur

[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 configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 each illustrate the distribution state of germanium atoms in the first layer region G. Explanatory diagrams for the purpose, Figures 11 to 14
Each figure is an explanatory diagram for explaining the distribution state of oxygen atoms in the first layer, FIG. 15 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
Each figure is a distribution state diagram showing the content distribution state of each atom in each example of the present invention. 100...Photoconductive member, 101...Support, 10
2...first layer, 103...second layer.

Claims (1)

[Claims] 1. 1 to 10× with respect to the sum of the support for a photoconductive member for electrophotography and the silicon atoms on the support.
A first layer region G with a thickness of 30 Å to 50 μ made of an amorphous material containing 10 ⁵ atomic ppm of germanium atoms, and a layer made of an amorphous material containing silicon atoms (but not germanium atoms). Thickness 0.5~90μ
a first layer exhibiting photoconductivity with a layer thickness of 1 to 100 μm, and a second layer region S of 1×10 −3 to 1×10 ^{−3 μm} thick with silicon atoms;
and a second layer with a layer thickness of 0.003 to 30 μ made of an amorphous material containing 90 atomic % of carbon atoms, and the first layer is made of silicon atoms, germanium atoms, and oxygen atoms. for the sum of atoms
Contains 0.001 to 50 atomic % of oxygen atoms, has a smooth concentration distribution, and has a concentration of 500 atomic ppm within a layer thickness of 5 μ from the support side of the layer or the interface side with the second layer.
A photoconductive member for electrophotography, characterized by having the maximum concentration distribution as described above. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region G and the second layer region S contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claims 1 and 2, wherein at least one of the first layer region G and the second layer region S contains a halogen atom. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region G is non-uniform. 5. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region G is uniform. 6. The photoconductive member for electrophotography according to claim 1, wherein the first layer contains a substance that controls conductivity. 7. The photoconductive member for electrophotography according to claim 6, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table. 8. The photoconductive member for electrophotography according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table.