JPH0145992B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. In some cases, solid-state imaging devices are required to have characteristics such as being harmless to the human body and being able to easily process afterimages within a predetermined time. In particular, 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 harmlessness 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/reading device 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 in order to improve overall characteristics. For example, when using an image forming member for electrophotography, when attempting to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases, etc. There were many cases where problems 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, there is still room for improvement in that when a commonly used halogen lamp or fluorescent lamp is used as a light source, it is not possible to effectively use light on the longer wavelength side. In addition, if the amount of irradiated light that reaches the support increases without being sufficiently absorbed in the photoconductive layer, the reflectance of the support itself to the light that passes through the photoconductive layer will decrease. When the value 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, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and control of electrical conductivity are added. For this reason, boron atoms, phosphorus atoms, etc., or other atoms for improving properties, are contained in the photoconductive layer as constituent atoms, but the manner in which these constituent atoms are contained depends on the may cause problems in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of the photocarrier generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side in a dark area may not be sufficiently prevented. There are many cases. 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 it is an issue that should be solved in order to improve stability over time. It is. 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 comprehensive research and consideration of Si from the viewpoint of its usability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we have discovered that silicon atoms (Si) and germanium atom (Ge) as a matrix, and a hydrogen atom
(H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter collectively referred to as these] As a notation, “a-SiGe(H,
A photoconductive member having a photoreceptive layer exhibiting photoconductivity consisting of " Not only does it exhibit extremely excellent properties, but it also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography, and it also has outstanding properties on the long wavelength side. This is based on the discovery that it has excellent absorption spectrum characteristics. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is extremely durable, does not exhibit 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 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 layer of laminated layers, and to have a dense and stable structural arrangement;
An object of the present invention is to provide a photoconductive member with high layer quality. Another object of the present invention is to have charge retention ability during charging treatment 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 which has excellent electrophotographic properties with sufficient electrophotographic properties and whose properties hardly deteriorate even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. The photoconductive member of the present invention includes a support for the photoconductive member and a photoreceptive layer showing photoconductivity and made of an amorphous material containing silicon atoms and germanium atoms as a matrix, The receptor layer contains a substance that controls conductivity and carbon atoms, and the distribution concentration of germanium atoms in the photoreceptor layer decreases from the support side to the opposite side from the support side. It is characterized by The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics. In particular, when used as an image forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics 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. In addition, the photoconductive member of the present invention has a strong photoreceptive layer itself formed on the support and excellent adhesion to the support, and can be repeatedly used continuously at high speed for a long time. be able to. 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 for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 is made of a-SiGe (H,
X), contains carbon atoms, and has a photoreceptive layer 102 having photoconductivity. Photoreceptive layer 102
The germanium atoms contained therein are continuous in the layer thickness direction of the photoreceptive layer 102 and on the side opposite to the side where the support 101 is provided (the free surface of the photoreceptor layer 102). It is contained in the photoreceptive layer 102 so that it is more distributed on the support side (the interface side of the photoreceptive layer 102 with the support 101) than on the side). In the photoconductive member of the present invention, the distribution state of germanium atoms contained in the photoreceptive layer is as described above in the layer thickness direction, and in the in-plane direction parallel to the surface of the support. A uniform distribution is desirable. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the photoreceptive layer of the photoconductive member of the present invention in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis represents the content C of germanium atoms, the vertical axis represents the layer thickness of the photoreceptive layer exhibiting photoconductivity, and _tB represents the surface of the photoreceptive layer on the support side. t _T indicates the position on the surface of the photoreceptive layer opposite to the support side. That is, the photoreceptive layer containing germanium atoms is formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the photoreceptive layer in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B where the surface _of the support where the photoreceptive layer containing germanium atoms is formed and the surface of the photoreceptive layer contact, the germanium atoms are Distribution concentration C is C ₁
Germanium atoms are contained in the formed photoreceptive layer while maintaining a constant value, and the distribution concentration C ₂ is gradually and continuously decreased from the position t ₁ 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 is
It is said to be C ₁₀ . Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and from this concentration C ₁₇ it gradually decreases until reaching the position t ₆ , and then at t ₆ . It decreases rapidly near the position, and becomes the concentration _C18 at the 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 reduced very slowly, reaching the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the photoreceptive layer in the layer thickness direction, in the present invention, germanium atoms are The light-receiving layer is provided with a distribution state of germanium atoms having a portion where the distribution concentration C of atoms is high, and a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. There is. The photoreceptive layer constituting the photoconductive member of the present invention preferably has a localized region (A) containing germanium atoms at a relatively high concentration on the support side as described above. desirable. In the present invention, the localized region (A) can be explained using the symbols shown in FIGS. 2 to 10, and can be defined as the interface position.
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 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region (A) is a part or all of the layer region (L _T ) is appropriately determined according to the characteristics required of the photoreceptive layer to be formed. The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value C _nax of the distribution concentration C 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 1×10 ⁴ atomic ppm or more. That is, in the present invention, the photoreceptive layer containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value C _nax of the distribution concentration C exists within 5 μm (a layer region with a thickness of 5 μm from t _B ). In the present invention, the content of germanium atoms contained in the photoreceptive layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but the content of germanium atoms contained in the photoreceptive layer is Preferably 1
~9.5× ¹⁰⁵ atomic ppm, more preferably 100-8
×10 ⁵ atomic ppm, optimally 500 to 7×
10 ⁵ atomic ppm. In the photoconductive member of the present invention, the distribution state of germanium atoms in the photoreceptive layer is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is supported. Since the change decreases from the body side toward the free surface side of the photoreceptive layer, it is possible to obtain the required characteristics by arbitrarily designing the rate of change curve of the distribution concentration C as desired. The photoreceptive layer can be realized as desired. For example, the distribution concentration C of germanium atoms in the photoreceptive layer can be changed so that the distribution concentration C of germanium is sufficiently increased on the support side and as low as possible on the free surface side of the photoreceptor layer. By providing a distribution density curve, photosensitization can be achieved for light of 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 photoreceptive layer on the support side, when a semiconductor laser is used, the laser irradiation side of the photoreceptor layer is Light on the long wavelength side that is not fully absorbed can be substantially completely absorbed in the support side end layer region of the photoreceptive layer, effectively preventing interference due to opposition from the support surface. You can. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the photoreceptive layer, the photoreceptive layer contains Contains carbon atoms. The carbon atoms contained in the photoreceptive layer may be uniformly contained in the entire layer area of the photoreceptive layer, or may be contained in only some layer areas of the photoreceptive layer and unevenly distributed. . Further, the distribution state of carbon atoms may be such that the distribution concentration C (C) is uniform in the layer thickness direction of the photoreceptive layer, or the distribution state of germanium atoms as explained using FIGS. 2 to 10. Similarly, it may be non-uniform in the layer thickness direction. The distribution state of carbon atoms when the distribution concentration C (C) of carbon atoms is non-uniform in the layer thickness direction can be explained in the same way as the case of germanium atoms using FIGS. 2 to 10. In the present invention, when the main purpose of the layer region (C) containing carbon atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is When the main purpose is to strengthen the adhesion between the support and the light-receiving layer, the light-receiving layer is provided so as to occupy the support-side end layer region of the light-receiving layer. In the former case, the content of carbon atoms in the layer region (C) is kept relatively low in order to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. Therefore, it is desirable to have a relatively large amount. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute it at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or In the surface layer region on the free surface side of the light-receiving layer, a distribution state of carbon atoms may be formed in the layer region (C) such that carbon atoms are not actively contained therein. In the present invention, the layer region provided in the photoreceptive layer
The content of carbon atoms contained in (C) depends on the characteristics required for the layer region (C) itself, or when the layer region (C) is provided in direct contact with the support. It can be selected as appropriate based 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 (C), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of carbon atoms contained in the layer region (C) 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~
40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region (C) occupies the entire area of the photoreceptive layer or does not occupy the entire area of the photoreceptor layer, the layer thickness T ₀ of the layer area (C) is equal to the layer thickness T of the photoreceptor layer. When the proportion of carbon atoms in the layer region (C) is sufficiently large, it is desirable that the upper limit of the content of carbon atoms contained in the layer region (C) is sufficiently smaller than the above value. In the case of the present invention, if the layer thickness T ₀ of the layer region (C) accounts for two-fifths or more of the layer thickness T of the photoreceptive layer, The upper limit of the amount of carbon atoms contained in is preferably 30 atomic%
Hereinafter, it is more preferably 20 atomic % or less, optimally 10 atomic % or less. In the present invention, the layer region (C) containing carbon atoms constituting the photoreceptive layer is the localized region (B) containing carbon atoms at a relatively high concentration on the support side as described above. It is desirable that the support be provided as having the following properties, and in this case, the adhesion between the support and the light-receiving layer can be further improved. The localized region (B) is desirably provided within 5 μm 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 5μ thick from the interface position _B , or it may be a part of the layer region (L _T ). In some cases. Whether the localized region (B) is a part or all of the layer region (L _T ) is appropriately determined depending on the characteristics required of the photoreceptive layer to be formed. The localized region (B) has a distribution concentration C of carbon atoms as the distribution state of the carbon atoms contained therein in the layer thickness direction.
(C) The layer is formed so that a distribution state can be obtained in which the maximum value C _nax is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more. That is, in the present invention, the layer region (C) containing carbon atoms has a layer thickness of 5 μm or less from the support side (t _B
The maximum value C _nax of the distribution concentration C (C) in the layer region with a thickness of 5μ from
It is desirable that the structure be formed in such a way that it exists. In the photoconductive member of the present invention, the photoreceptive layer containing germanium atoms contains a substance (C) that controls the conduction characteristics, so that the conduction characteristics of the photoreceptor layer can be controlled as desired. It can be controlled arbitrarily. Such substances (C) include so-called impurities in the semiconductor field, and in the present invention, a-
For SiGe (H, 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 Ge are particularly preferably used. As n-type impurities, atoms belonging to the group of the periodic table (group atoms), such as P (phosphorus), As (arsenic),
Sb (antimony), Bi (bismuth), etc. are used, and P and As are particularly preferably used. In the present invention, the content of the substance (C) that controls the conduction properties contained in the photoreceptive layer is determined based on the conduction properties required for the photoreceptor layer, or the content of the substance (C) that controls the conduction properties contained in the photoreceptor layer. It can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support provided. In addition, when the substance for controlling the conduction properties is contained in the photoreceptive layer locally in a desired layer region of the photoreceptor layer, particularly at the edge of the photoreceptor layer on the side of the support. When containing in the substratum region (E),
The content of the substance that controls the conduction properties is determined by taking into account the characteristics of other layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the other layer regions. Selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the photoreceptive layer is preferably as follows:
0.01~5× ¹⁰⁴ atomic ppm, more preferably 0.5~
1×10 ⁴ atomic ppm, optimally 1-5×
10 ³ atomic ppm. In the present invention, the content of the substance (C) that controls conduction characteristics in the layer region containing the substance is preferably 30 atomic ppm or more, preferably 50 atomic ppm or more.
ppm or more, optimally 100 atomic ppm or more, the substance (C) is preferably contained locally in some layer regions of the photoreceptive layer, especially at the edge of the support side of the photoreceptive layer. It is desirable to have it unevenly distributed in the substratum region (E). Among the above, by containing a substance that controls the conduction characteristics in the support side end layer region (E) of the photoreceptive layer in a content that is equal to or more than the above value, for example, the substance to be contained can be When (C) is the above-mentioned p-type impurity, it effectively prevents injection of electrons from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is subjected to polar charging treatment. and when the substance to be contained is the n-type impurity,
When the free surface of the photoreceptive layer is polarized, injection of holes from the support side into the photoreceptor layer can be effectively prevented. In this way, when the end layer region (E) contains a substance that controls conductivity of one polarity, the remaining layer region of the photoreceptive layer, that is, the end layer region (E)
The layer region (Z) excluding the part may contain a substance that controls the conduction characteristics of the other polarity, or the material that controls the conduction characteristics of the same polarity may be added to the end layer region (Z). ) may be contained in an amount much smaller than the actual amount contained in (). In such a case, the content of the substance controlling the conduction properties contained in the layer region (Z) can be determined as desired depending on the polarity and content of the substance contained in the end layer region (E). Although it is determined appropriately according to the
It is estimated to be 200 atomic ppm. In the present invention, when the end layer region (E) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is as follows:
It is desirable to set it to 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having one polarity, and a substance controlling conductivity having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing . clogging, e.g. in the photoreceptive layer;
A depletion layer can be provided by providing the layer region containing the p-type impurity and the layer region containing the n-type impurity in direct contact to form a so-called pn junction. In the present invention, specific examples of the halogen atom (X) contained in the light-receiving layer as required include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. In the present invention, the photoreceptive layer composed of a-SiGe (H, will be accomplished. For example, by the glow discharge method, a-
To form a photoreceptive layer composed of SiGe (H, Ge) raw material gas for supply,
Raw material gas or / for introducing hydrogen atoms (H) as necessary
and a raw material gas for introducing halogen atoms (X),
The distribution of germanium atoms contained on the surface of a predetermined support that has been placed at a predetermined position in advance by introducing a gas at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. While controlling the concentration according to the desired rate of change curve, a-
A layer made of SiGe(H,X) may be formed.
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 targets, or with Si
Using a Ge mixed target, source gas for Ge supply diluted with diluent gas such as He or Ar as necessary, and hydrogen atoms (H) as necessary.
Or/and a gas for introducing halogen atoms (X),
The target is sputtered while introducing it into a deposition chamber for sputtering and forming a plasma atmosphere of a desired gas, and controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. Good. In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the above method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for supplying Ge 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 ,
Germanium hydride in a gaseous state or that can be gasified, such as Ge ₉ H ₂₀ , can be effectively used. In particular, GeH _{4 , Ge2H6 , Ge3H8}
are listed as preferred. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogen compounds, and gaseous or gasifiable halogens such as silane derivatives substituted with interhalogen compounds. Compounds are mentioned as preferred. Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. A light-receiving layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying Si, germanium hydride is used as a raw material gas for supplying Ge, Ar,
Gases such as H ₂ and He are introduced at a predetermined mixing ratio and gas flow rate into the deposition chamber where the photoreceptive layer is formed, and a glow discharge is generated to form a plasma atmosphere of these gases. In particular, it is possible to form a light-receiving layer on a desired support, but in order to make it easier to control the ratio of hydrogen atoms introduced, hydrogen gas or hydrogen may be added to these gases. A layer may be formed by mixing a desired amount of silicon compound gas containing atoms. 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, such as H ₂ or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a gaseous plasma atmosphere. 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,
Hydrogenated germanium halides such as GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc. Halogen compounds containing hydrogen atoms as one of their constituents GeF ₄ , GeCl ₄ , GeBr ₄ ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as effective starting materials for forming the photoreceptor layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the photoreceptive layer. , is used as a suitable raw material for introducing halogen in the present invention. In order to structurally introduce hydrogen atoms into the photoreceptive layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ and a germanium compound for supplying Ge, or GeH ₄ ,
Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ ,
This can also be done by coexisting germanium hydride such as Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , and silicon or a silicon compound for supplying Si in the deposition chamber to generate a discharge. I can do it. In a preferred example of the present invention, the amount of hydrogen atoms (H) contained in the light receiving layer of the light guide member to be formed,
Or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably
0.01-40atomic%, more preferably 0.05-30atomic%
%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the photoreceptive layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) contained What is necessary is to control the amount of starting material used for this purpose introduced into the deposition system, the discharge power, etc. In the present invention, in order to provide the layer region (C) containing carbon atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing carbon atoms is added to the above-mentioned starting material for forming the photoreceptive layer. It may be used together with the starting material and contained in the formed layer while controlling its amount. When a glow discharge method is used to form the layer region (C), a starting material for introducing carbon atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for introducing carbon atoms, most of the gaseous substances having at least carbon atoms as a constituent atom or the gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (C), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and carbon atoms (C) is used.
and hydrogen atoms (H) as constituent atoms. The raw material gas is also mixed at a desired mixing ratio, or the raw material gas whose constituent atoms are silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) are mixed. It is possible to mix and use a raw material gas having three constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
A raw material gas containing carbon atoms (C) as constituent atoms may be mixed with a raw material gas containing carbon atoms (C) as constituent atoms. Examples of those having C and G as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
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: Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. In addition to these, alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₄ ) ₄ can be cited as raw material gases containing Si, C, and H as constituent atoms. In the present invention, the layer region (C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effects obtained by carbon atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (C) include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), trinitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms The constituent atoms are (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 ). Effective raw material gases for introducing nitrogen atoms (N) used to introduce nitrogen into the layer region (C) include those containing N as a constituent atom or containing N and H as constituent atoms. For example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ )
Nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and azide compounds can be mentioned. In addition to this, in addition to introducing nitrogen atoms (N),
Nitrogen halides such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be used since they can also introduce halogen atoms (X). To form a layer region (C) containing carbon atoms by sputtering, a single crystal or polycrystalline
This can be carried out by sputtering a Si wafer, a C wafer, or a wafer containing a mixture of Si and C in various gas atmospheres. For example, if a Si wafer is used as a target, carbon 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, by using Si and C as separate targets or by using a single mixed target of Si and C, at least hydrogen atoms can be formed in an atmosphere of diluted gas as sputtering gas or at least hydrogen atoms. (H)
Or/and by sputtering in a gas atmosphere containing halogen atoms (X) as constituent atoms. As the raw material gas for carbon atom introduction, the raw material gas for carbon atom introduction 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 (C) containing carbon atoms is provided when forming a photoreceptive layer, the layer region (C)
In order to change the distribution concentration C(C) of carbon atoms contained in (C) in the layer thickness direction and form a layer region color having a desired depth profile in the layer thickness direction, glow discharge is required. In this case, in order to change the distribution concentration C(C), the starting material gas for introducing carbon atoms 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 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 means such as manually or by 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 to a rate-of-change curve designed in advance to obtain a desired content rate curve. When forming the layer region (C) by the sputtering method, the distribution concentration C (C) of carbon atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth) of carbon atoms in the layer thickness direction. First, as in the glow discharge method, the starting material for introducing carbon atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is controlled. This can be done by appropriately changing it as desired. Second, the target for sputtering,
For example, if a target containing a mixture of Si and C is used, this can be done by changing the mixing ratio of Si and C in advance in the direction of the layer thickness of the target. In order to structurally introduce a substance that controls conduction properties, such as a group atom or a group atom, into the photoreceptive layer, a starting material for introducing a group atom or a group atom is introduced during layer formation. The starting materials for forming the photoreceptor layer may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the photoreceptor layer. As a starting material for introducing such 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. As starting materials for introducing such group atom, specifically, for introducing boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as BBr ₃ . 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 , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. The layer thickness of the photoreceptive layer in the photoconductive member of the present invention is appropriately determined as desired so that photocarriers generated in the photoreceptor layer are efficiently transported, and is preferably 1 to 100 μm. More preferably 1~
80μ, optimally 2 to 50μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as 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. It is desirable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the conductive treated surface side. For example, if it is glass, its surface may include NiCr, Al, etc.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd,
Conductivity can be imparted by providing a thin film made of 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, Au,
A thin film of metal such as 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 above metal. conductivity is imparted to the 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 shown in FIG. If used as a member, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that the 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, in manufacturing and handling of the support,
From the viewpoint of mechanical strength, etc., the thickness is preferably 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of an apparatus for manufacturing the photoconductive member of the present invention. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is B ₂ H ₆ gas diluted with He (purity 99.99%, hereinafter referred to as B ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is C ₂ H ₄ gas (purity 99.999%) cylinder, 1106 is H ₂ gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, the main valve 1134 is first opened to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH 4 /He gas from gas cylinder 1103, GeH ₄ /He gas from gas cylinder 1104
B ₂ H ₆ /He gas, C ₂ H ₄ from gas cylinder 1105
Gas is supplied to the mass flow controllers 1107 to 1110 by opening the valves 1122 to 1125 to adjust the pressure of the outlet pressure gauges 1127 to 1130 to 1 Kg/cm ² and gradually opening the inflow valves 1112 to 1115.
Let them flow into each other. Subsequently, the outflow valve 11
17 to 1120, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101.
At _{this time , the} outflow _valves 1117 _~
1120 and 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. Then, the temperature of the base 1137 becomes higher than that of the heating heater 1.
After confirming that the temperature is set in the range of 50 to 400 °C by 138, the power supply 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101, while at the same time generating a pre-designed rate of change curve. Therefore, the GeH ₄ /He gas flow rate is controlled by gradually changing the opening of the valve 1118 manually or by means such as an externally driven motor, so that the germanium atoms contained in the formed layer are controlled. Control distribution concentration. In this way, a-SiGe (H, A layer region (B, C) composed of X) is formed to a desired layer thickness. At the stage when the layer regions (B, C) have been formed to the desired layer thickness, the same conditions are applied except that the outflow valves 1119 and 1120 are completely closed, respectively, and the discharge conditions are changed as necessary. By maintaining the glow discharge for a desired time according to the procedure, the layer regions (B, C) contain neither boron atoms (B) nor carbon atoms (C), but according to the rate of change curve described above. A distribution state of germanium atoms is formed.
An upper layer region composed of a-SiGe (H,X) is formed to complete the formation of the photoreceptive layer. When forming the above-mentioned photoreceptive layer, after a desired period of time has elapsed after the start of the layer formation, the deposition chamber is
By stopping the flow of B ₂ H ₆ /He gas or C ₂ H ₄ gas, the layer thicknesses of the layer region containing boron atoms (B) and the layer region containing carbon atoms (C) can be adjusted as desired. can be controlled. Also, according to a desired rate of change curve, the deposition chamber 110
By controlling the gas flow rate of C ₂ H ₄ gas to the layer region (C), the distribution state of carbon atoms contained in the layer region (C) can be formed as desired. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. 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 immediately irradiated with a light image. A tungsten lamp light source was used to irradiate the optical image, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developer (including toner and carrier) onto the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was 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. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 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. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 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. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 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. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 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 The conditions in Table 1 in Example 1 were changed from Table 8 to
Layer formation was carried out under the same conditions as in Example 1, except that the conditions shown in Table 10 were used to obtain electrophotographic image forming members (Samples Nos. 801 to 803). For each of the image forming members thus obtained,
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 9 Using the production apparatus shown in FIG. 11, GeH ₄ /GeH 4 /
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of He 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 immediately irradiated with a light image. A tungsten lamp light source was used to irradiate the optical image, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developer (including toner and carrier) onto the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 10 Using the manufacturing apparatus shown in FIG. 11, GeH 4 /GeH ₄ /
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of He 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 immediately irradiated with a light image. A tungsten lamp light source was used to irradiate the optical image, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developer (including toner and carrier) onto the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 11 Using the production apparatus shown in FIG. 11, the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas was adjusted according to the rate of change curve of gas flow rate ratio shown in FIG. 13 under the conditions shown in Table 13. An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 10, with the other conditions being the same as in Example 10, while changing the layer formation time. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 12 GeH ₄ /He gas, SiH ₄ /He gas,
The gas flow rate ratio of C ₂ H ₄ gas and SiH ₄ /He gas was changed with the elapsed layer formation time, and other conditions were as in the example.
Layer formation was carried out in the same manner as in 10 to obtain an electrophotographic image forming member. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 13 GeH ₄ /He gas, SiH ₄ /He gas,
The gas flow rate ratio of C ₂ H ₄ gas and SiH ₄ /He gas was changed with the elapsed layer formation time, and other conditions were as in the example.
Layer formation was carried out in the same manner as in 10 to obtain an electrophotographic image forming member. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 14 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. 16 under the conditions shown in Table 16. Layers were formed under the same conditions as in Example 10, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 15 Using the manufacturing apparatus shown in FIG. 11, the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas was adjusted according to the change rate curve of the gas flow rate ratio shown in FIG. 17 under the conditions shown in Table 17. An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 10, with the other conditions being the same as in Example 10, while changing the layer formation time. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 16 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 18. Layers were formed under the same conditions as in Example 10, except that the ratio was changed with the elapsed time of layer formation, to obtain an electrophotographic image forming member. Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 17 The conditions in Table 12 in Example 10 were changed from Table 19 to Table 19.
Layer formation was carried out under the same conditions as in Example 10, except that the conditions shown in Table 21 were used to obtain electrophotographic image forming members (sample Nos. 1901 to 1903). Examples of the image forming member thus obtained
When an image was formed on transfer paper under the same conditions and procedures as in Example 10, an extremely clear image quality was obtained. Example 18 Using the manufacturing apparatus shown in FIG. 11, GeH 4 /GeH ₄ /
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of He 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 immediately irradiated with a light image. A tungsten lamp light source was used to irradiate the optical image, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developer (including toner and carrier) onto the imaging member surface. The toner image on the imaging member
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 19 The same procedure as in Examples 1 and 10 was carried out, except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of the tungsten lamp as the light source to form an electrostatic image. When we evaluated the image quality of toner transfer images on electrophotographic image forming members prepared under the same toner image forming conditions as in Examples 1 and 10, we found that they were clear, with excellent resolution and good gradation reproducibility. High quality images were obtained.

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

[Brief explanation of drawings]

FIG. 1 is a schematic 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 photoreceptive layer, respectively.
FIG. 11 is a schematic explanatory diagram of the apparatus used for manufacturing the photoconductive member of the present invention, and FIGS. 12 to 18 respectively show rate of change curves of the gas flow rate ratio in the embodiments of the present invention. It is an explanatory diagram. 100...Photoconductive member, 101...Support, 1
02...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A photoconductive material comprising a support for a photoconductive member and a photoconductive photoreceptive layer made of an amorphous material containing silicon atoms and germanium atoms, The layer contains a substance that controls conductivity and carbon atoms, and the distribution concentration of germanium atoms in the photoreceptive layer decreases from the support side to the opposite side from the support side. Features of photoconductive materials. 2. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms. 3. The photoconductive member according to claim 1, wherein the photoreceptive layer contains halogen atoms. 4. The photoconductive member according to claim 1, wherein the photoreceptive layer contains hydrogen atoms and halogen atoms. 5. The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table. 6. The photoconductive member according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 7 The amount of hydrogen atoms contained in the photoreceptive layer is
The photoconductive member according to claim 2, wherein the content is 0.01 to 40 atomic%. 8. Claim 3, wherein the amount of halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%.
The photoconductive member described in . 9. The photoconductive member according to claim 3, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the photoreceptive layer is 0.01 to 40 atomic%. 10. The photoconductive member according to claim 1, wherein the amount of germanium atoms contained in the first layer region is 1 to 9.5×10 ⁵ atomic ppm. 11. The photoconductive member according to claim 1, wherein the photoreceptive layer has a layer thickness of 1 to 100 μm. 12 The atom belonging to Group 1 of the periodic table is B,
The photoconductive member according to claim 5, which is selected from Ga. 13 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member according to claim 6, which is selected from As. 14 The substance controlling the conductivity is 0.01 to 5×
Claim 1 containing 10 ⁴ atomic ppm
The photoconductive member described in . 15 The substance that controls the conductivity is 30 atomic
The photoconductive member according to claim 14, which contains ppm or more. 16. The photoconductive member according to claim 1, wherein the distribution concentration of the carbon atoms decreases from the support side toward the opposite side from the support side. 17 The content of carbon atoms is 0.001 to 50 atomic
% of the photoconductive member according to claim 1. 18 The maximum value of the distribution concentration of the carbon atoms is
Claim 2 which is 500 atomic ppm or more
The photoconductive member according to item 8. 19. The photoconductive member according to claims 3 and 4, wherein the halogen atom is selected from fluorine and chlorine.