JPH0145985B2 - - 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.)
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. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and economic stability, and it is necessary to improve the combined 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 is
In order to increase the resolution, the smaller the irradiation spot is, the larger the irradiation spot becomes, which is a big problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive material used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms (Si) and a germanium atom (Ge) as a matrix, especially an amorphous material that uses these atoms as a matrix and contains at least either a hydrogen atom (H) or a halogen atom (); So-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to generically as "a-SiGe (H,
A photoconductive member manufactured by specifying the structure of a photoconductive member having an amorphous layer composed of " It is superior in all respects to conventional photoconductive materials, especially as a photoconductive material for electrophotography, and has an absorption spectrum on the long wavelength side. This is based on the fact that it has been found to have excellent 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 extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance and excellent electrophotographic 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. Still another object of the present invention is to provide a photoconductive member with sufficiently high dark conductivity and sufficient acceptance potential, and to improve productivity by improving adhesion between each layer. . 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 the photoconductive member, a first amorphous layer ( ) made of an amorphous material having silicon atoms as a host from the support side, and silicon atoms and germanium atoms. a second amorphous layer made of an amorphous material having a matrix of , and the distribution concentration of germanium atoms contained in the second amorphous layer () in the layer thickness direction is higher on the upper surface and/or lower surface side of the second amorphous layer (). It is characterized by The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties, and high pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. 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. Furthermore, there is no layer peeling and productivity is improved. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention. A photoconductive member 100 shown in FIG. 1 has a photoreceptive layer 102 having sufficient volume resistance and photoconductivity on a support 101 for the photoconductive member,
The photoreceptive layer 102 has a first amorphous layer ( ) 102 made of a-Si(H,X) and a-SiGe layer thereon.
Second amorphous layer ( ) 103 consisting of (H,X)
has. The germanium atoms contained in the second amorphous layer () are in the second amorphous layer (),
It is contained non-uniformly in the layer thickness direction. Photoconductivity may be imparted to at least one of the first and second amorphous layers, but a layer that can be sufficiently reached by incident light has an absorption spectrum that better matches the wavelength spectrum of incident light. It is necessary to design the layers so that In the photoconductive member of the present invention, at least one of the first amorphous layer () and the second amorphous layer () contains a substance (C) that controls conductivity. The conductivity of the included layers can be controlled as desired. The substance (C) may be contained in the photoreceptive layer or the first and second amorphous layers so as to be uniformly or non-uniformly distributed in the layer thickness direction. Further, in the layer region (PN) in which the substance (C) is continuously contained, the substance (C) may be contained so as to have a uniform distribution or a continuous non-uniform distribution in the layer thickness direction. For example, the layer thickness of the second amorphous layer () is made thicker than the layer thickness of the first amorphous layer (), and the second amorphous layer () is mainly used as a charge generation layer and a charge transport layer. When used in such a way that the substance (C) that controls conductivity is loaded with the function of Also, the substance (C) that controls conductivity is the second
In the amorphous layer (), it is desirable that the distribution state is increased at or near the interface between the first amorphous layer () and the second amorphous layer (). On the other hand, the layer thickness of the first amorphous layer ( ) is made thicker than the layer thickness of the second amorphous layer ( ), and the second amorphous layer ( ) is mainly used as a charge generation layer. crystalline layer ()
When used with a function as a charge transport layer, the substance (C) governing conductivity should be contained in a state where it is more distributed on the support side of the first amorphous layer (2). is desirable. When considering the adhesion between the support and each layer, oxygen atoms are present at or near the interface between the support and the first amorphous layer () or/and between the first amorphous layer (). It is desirable to contain it so that it is largely distributed at or near the interface of the second amorphous layer (). In order to increase the dark conductivity, the first amorphous layer () or/and the second amorphous layer ()
It may be contained in the photoreceptive layer so as to be uniformly distributed in the layer thickness direction, or in the case of preventing charge injection into the photoreceptive layer and increasing the apparent resistance, it may be contained near the free surface of the photoreceptor layer or It may be contained in a large amount at the interface with the support and/or in the vicinity of the interface. Furthermore, in order to simultaneously measure the adhesion and high resistance of each layer,
Oxygen atoms may be contained in a combination of the above two states. As the substance (C) that controls conductivity contained in the layer region (PN), so-called impurities in the semiconductor field can be mentioned, and in the present invention,
(Si or Ge), P gives P-type conduction characteristics
Mention may be made of n-type impurities and n-type impurities that provide n-type conductivity properties. Specifically, P-type impurities include atoms belonging to Group 3 of the periodic table (Group atoms), such as B (boron), Al (aluminum), and Ga.
(gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, a substance (C) that controls conductivity contained in a layer region (PN) containing a substance (C) that controls conductivity provided in the photoreceptive layer
The content of is determined by the conductive properties required for the layer region (PN) or, if the layer region (PN) is provided in direct contact with the support, the properties at the contact interface with the support. It can be selected as appropriate depending on the organic relationship, such as the relationship with Furthermore, the conduction characteristics are controlled by taking into account the characteristics of other layer regions provided in direct contact with the layer region (PN) and the relationship with the characteristics at the contact interface with the other layer regions. The content of the substance is selected appropriately. In the present invention, the content of the substance controlling conduction properties contained in the layer region (PN) is preferably 0.001 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1×10 atomic ppm. ⁴ atomic ppm, optimally 1-5
It is desirable to set it to ×10 ³ atomic ppm. In the present invention, the content of the substance (C) that governs the conduction characteristics in the layer region (PN) containing the substance (C) is preferably set to 30 atomic ppm or more, more preferably 50 atomic ppm or more, to an optimal value. is 100atomic
ppm or more, for example, when the substance (C) to be contained is the above-mentioned P-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the photoreceptor layer from the support side It is possible to effectively block the movement of electrons injected into the photoreceptor layer, and when the substance (C) to be contained is the n-type impurity, the free surface of the photoreceptive layer is charged to be polar. When you receive it,
The movement of holes injected from the support side into the photoreceptive layer can be effectively prevented. In the above case, the layer region (Z) excluding the layer region (PN) has conduction of a polarity different from the polarity of the substance that controls the conduction characteristics contained in the layer region (PN). A substance that controls the properties may be contained, or a substance that controls the conduction properties of the same polarity may be contained in an amount much smaller than the actual amount contained in the layer region (PN). . In such a case, the content of the substance controlling the conduction characteristics contained in the layer region (Z) may be determined as desired depending on the polarity and content of the substance contained in the layer region (PN). Therefore, it should be determined appropriately, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is preferably 30 atomic It is desirable to keep it below ppm. 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. is provided in direct contact with a layer region containing
A so-called depletion layer can also be provided. For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the photoreceptor layer so as to be in direct contact with each other to form a so-called P-n junction. , a depletion layer can be provided. In the 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 an oxygen atom. The oxygen atoms contained in the photoreceptive layer may be uniformly contained in the entire layer area of the photoreceptive layer, or may be contained and unevenly distributed only in some layer areas of the photoreceptive layer. good. In addition, the distribution state of oxygen atoms is such that even if the distribution concentration C(O) is uniform in the layer thickness direction of the photoreceptive layer, the distribution concentration C(O) is non-uniform in the layer thickness direction. Also good. In the present invention, when the main purpose of the layer region (O) containing oxygen atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is The layer is provided so as to occupy the same area, and is intended to strengthen the adhesion between the support and the first amorphous layer () or/and between the first amorphous layer () and the second amorphous layer (). If the main purpose is to
the support side end layer region of the amorphous layer (), or
It is provided so as to occupy a region near the interface between the first and second amorphous layers. In the former case, the content of oxygen atoms contained in the layer region (O) is relatively small in order to maintain high photosensitivity, and in the latter case, to ensure enhanced adhesion between the layers. It is desirable that a relatively large amount be used. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute it at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or In the surface layer region on the free surface side of the photoreceptive layer, a distribution state of oxygen atoms is formed in the layer region (O) so that oxygen atoms are not actively contained. In addition, when the purpose is to effectively prevent charge injection from the support during charging and increase the apparent dark resistance of the photoreceptive layer, the support side of the first amorphous layer () Oxygen atoms are contained in a high concentration in the first amorphous layer ( ) or in the vicinity of the interface between the first amorphous layer ( ) and the second amorphous layer ( ). In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the photoreceptive layer depends on the characteristics required for the layer region (O) itself, or when the layer region (O) is a support. When provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (O), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in the layer region (O) is
It can be determined as desired depending on the characteristics required of the photoconductive member to be formed, but preferably,
0.001~50atomic%, more preferably 0.002~
It is desirable that it be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, specific examples of the halogen atom (X) contained in the light-receiving layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the first amorphous layer (), it is necessary to prepare a layer region (O) containing oxygen atoms during the formation of the first amorphous layer (). The starting material may be used together with the starting material for forming the first amorphous layer (), and may be contained in the formed layer while controlling its amount. When the glow discharge method is used to form the layer region (O), a material for introducing oxygen atoms is added to a starting material selected as desired from among the starting materials for forming the first amorphous layer (). Starting materials are added. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are oxygen atoms (O) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and three atoms of silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used in combination with a raw material gas having constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . To form the first amorphous layer () containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or SiO ₂ wafer, or a mixture of Si and SiO ₂ is used. This can be done by sputtering the contained wafers in various gas atmospheres, using them as targets. For example, if a Si wafer is used as a target, the source gas for introducing oxygen atoms and optionally hydrogen atoms/and halogen atoms is diluted with a diluent gas as necessary, and the material gas is prepared in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing these gases into the Si wafer and forming a gas plasma of these gases. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when a layer region (O) containing oxygen atoms is provided, the distribution concentration C(O) of oxygen atoms contained in the layer region (O) is changed in the layer thickness direction to obtain a desired value. Distribution state in the layer thickness direction (depth
To form a layer region (O) having a
In the case of glow discharge, the starting material gas for introducing oxygen atoms whose distribution concentration C(O) 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 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 any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (O) is formed by the sputtering method, the distribution concentration C of oxygen atoms in the layer thickness direction
In order to change (O) in the layer thickness direction to form a desired distribution state (depth profile) of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, a method for introducing oxygen atoms is required. This is accomplished by using a starting material in a gaseous state and appropriately varying the gas flow rate when introducing the gas into the deposition chamber as desired. Second, if a sputtering target is used, for example, a mixture of Si and SiO ₂ , the mixing ratio of Si and SiO ₂ should be
This is accomplished by changing the layer thickness of the target in advance. In the present invention, the following can be listed as effective starting materials that serve as raw material gases used to form the first amorphous layer (2). First, silicon hydride (silanes) in a gaseous state or capable of being gasified, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., is effectively used as the starting material for supplying Si. It is commonly used, especially in terms of ease of layer creation work and good Si supply efficiency.
Preferred examples include SiH ₄ and Si ₂ H ₆ . By using these starting materials, it is possible to introduce H as well as Si into the first amorphous layer ( ) formed by appropriately selecting the layer forming conditions. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr ₄ and the like can be mentioned as preferred, and furthermore, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be cited as starting materials for supplying Si for forming an effective charge injection prevention layer. Even when these silicon compounds containing halogen atoms (X) are used, X together with Si can be added to the first amorphous layer () formed by appropriately selecting the layer formation conditions as described above. It can be introduced. In addition to the above-mentioned materials, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used in forming the first amorphous layer () in the present invention include, for example, fluorine, Halogen gases of chlorine, bromine, and iodine, BrF, ClF, ClF ₃ , BrF ₅ ,
Examples include interhalogen compounds such as BrF ₃ , IF ₃ , IF ₇ , ICl and IBr, and hydrogen halides such as HF, HCl, HBr and HI. Examples of raw material gases for oxygen introduction include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), and nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ) silicon atom (Si), oxygen atom (O), hydrogen atom (H) For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) can be mentioned. In the layer region constituting the first amorphous layer (),
In order to structurally introduce a substance (C) that controls conduction properties, such as a group atom or a group atom, a starting material for introducing a group atom or a starting material for introducing a group atom is used during layer formation. The substance may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the amorphous layer. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B ₂ H ₆ , B 4 H 10 , B ₄ H ₁₀ ,
Examples include boron hydrides such as B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlCl ₃ , GaCl ₃ , Ga
(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like 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 , _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 present invention, the amount of hydrogen atoms (H) or halogen atoms (X) contained in the first amorphous layer ()
or the sum of the amounts of hydrogen atoms and halogen atoms (H+
X) is preferably 1 to 40 atomic %, more preferably 5 to 30 atomic %. Hydrogen atoms (H) contained in the first amorphous layer ()
Or/and to control the amount of halogen atoms (X), for example, the support temperature or/and hydrogen atoms (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. The layer thickness of the first amorphous layer ( ) of the present invention is determined whether the first amorphous layer ( ) mainly functions as an adhesion layer between the support and the second amorphous layer ( ). It is determined as appropriate depending on whether it functions as an adhesion layer or a charge transport layer.
In the former case, preferably 1000 Å to 50 μm, more preferably 2000 Å to 30 μm, optimally 2000 Å to
It is desirable that the thickness be 10 μm. In the latter case, preferably 1 to 100 μm, more preferably 1 to 80 μm,
The optimum thickness is preferably 2 to 50 μm. In the photoconductive member of the present invention, when the first amorphous layer is sufficiently thin, the second amorphous layer containing germanium atoms has a property that controls the conduction properties. By locally providing a layer region (PN) containing a substance on the first amorphous layer ( ), the movement of charges injected from the support side to the second amorphous layer ( ) can be prevented. can be effectively prevented. In the photoconductive member of the present invention, high photosensitivity and high dark resistance are achieved, as well as improved adhesion between the first amorphous layer () and the second amorphous layer (). For the purpose of achieving this, the second amorphous layer ( ) contains oxygen atoms. The oxygen atoms contained in the second amorphous layer () may be evenly contained in the entire layer region of the second amorphous layer (), or,
Distribution state of germanium atoms contained in the second amorphous layer ( ) of the conductive member in the layer thickness direction even if they are contained in only a part of the layer region of the second amorphous layer ( ) and unevenly distributed. A typical example is shown. In FIGS. 2 to 13, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the second amorphous layer ( ), and t _B shows the distribution concentration C of germanium atoms ( ), the position of the end face of the second amorphous layer () is
t _T is the second amorphous layer on the side opposite to the support side ( )
Indicates the position of the end face. That is, the second amorphous 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 second amorphous layer ( ) in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B where the surface on which the second amorphous layer ( ) containing germanium atoms is formed contacts the surface of the second amorphous layer ( ). Up to the position _t1 , the distribution concentration C of germanium atoms takes a constant value _C1 , and the second amorphous layer () where germanium atoms are formed is formed.
The concentration C2 is higher than the concentration C2 than the position _t1 , and the interface position _tT is higher than the concentration _C2 .
has been gradually and continuously reduced until . At the interface position _tT , the distribution concentration of germanium atoms C
is assumed to be C ₃ . 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 is a constant value C ₉ , and at the position t _T the concentration C ₁₀
be done. Between position _t3 and position _tT , the distribution concentration C
is linearly decreased from position t ₃ to position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. In the example shown in FIG. 11, the germanium concentration C is constant at ₂₂ from position t _B to t ₉ , and from position t ₉ to position t _B
The germanium concentration has been up to _C23 . In the example shown in FIG. 12, the germanium concentration is substantially zero at position t _B and increases to C ₂₃ at position t _T as shown. In Figure 13, the germanium concentration at position t _B is substantially zero, and the concentration from position t _B to position t ₁₀ is
The germanium concentration increases until C ₂₄ as shown in the figure, and remains constant at C ₂₄ from position t ₁₀ to position t _T. Above, the germanium concentration shown in Figures 2 to 13 is the distribution where the germanium concentration is high near the first amorphous layer ( ) side in Figures 2 to 10, and the distribution in which the germanium concentration is high near the first amorphous layer ( ) side in Figures 2 to 10, and 2 amorphous layer ()
The germanium concentration distribution may be combined with a distribution in which the germanium concentration is high near the free surface of the . As described above with reference to FIGS. 2 to 13, some typical examples of the distribution state of germanium atoms contained in the second amorphous layer ( ) in the layer thickness direction, in the present invention, , on the first amorphous layer () side and on the free surface side of the second amorphous layer (), there are parts with a high distribution concentration C of germanium atoms, and the second amorphous layer () has a high distribution concentration C. In the center,
The distribution concentration C has a portion that is considerably lower than the free surface side of the first amorphous layer () and the second amorphous layer (). It is provided in the quality layer (). The second amorphous layer ( ) constituting the amorphous layer constituting the photoconductive member in the present invention is preferably on the first amorphous layer ( ) side and/or on the second amorphous layer ( ) side as described above. It is desirable to have a localized region (A) containing germanium atoms at a relatively high concentration on the free surface side of the amorphous layer (2). In the present invention, the localized region (A) can be explained using the symbols shown in FIGS. 2 to 13 at the interface position t _B
Alternatively, it is preferable that it be provided within 5μ from _tT . 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 t _T , or may be the entire layer region (L _T ) of the layer region (L _T ). Sometimes it is considered a part. Whether the localized region (A) is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more relative to silicon atoms. ppm or more, optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be obtained. That is, in the present invention, the amorphous layer containing germanium atoms has a layer thickness within 5 μm from the free surface of the first amorphous layer () or the second amorphous layer (). It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists in a layer region with a thickness of 5 μm from _tB . In the present invention, the content of germanium atoms contained in the second amorphous layer (2) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~9.5×
¹⁰⁵ atomic ppm, more preferably 100-8×
10 ⁵ atomic ppm, optimally 500-7×
It is preferable to set it at 10 ⁵ atomic ppm. In the present invention, the content of germanium atoms contained in the second amorphous layer (2) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1~9.5×
¹⁰⁵ atomic ppm, more preferably 100-8.0×
10 ⁵ atomic ppm, optimally 500-7×
It is preferable to set it at 10 ⁵ atomic ppm. In the present invention, specific examples of the halogen atom (X) contained in the second amorphous layer (X) as required include fluorine, chlorine, bromine, and iodine, particularly fluorine. , chlorine can be mentioned as suitable. In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the second amorphous layer ( ) composed of a-SiGe (H,X). It is made by vacuum deposition method. For example, to form the second amorphous layer () made of a-SiGe (H, Raw material gas for supply, raw material gas for Ge supply that can supply germanium atoms (Ge), and raw material gas for introducing hydrogen atoms (H) and/or raw material gas for introducing halogen atoms (X) as necessary. is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a-SiGe (H , X) may be formed. In addition, when forming by sputtering method, for example, 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, or
For supplying Ge diluted with a diluent gas such as He or Ar as necessary, using two targets consisting of this target and Ge, or using a mixed target of Si and Ge. If necessary, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into the deposition chamber for sputtering to form a desired gas plasma atmosphere and target the target. Just spat it out. 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 resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and 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. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. An amorphous layer made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing the second amorphous 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, and raw material gas for supplying Ge is mixed. Germanium hydride and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form a second amorphous layer ().
The second amorphous layer () can be formed by introducing these gases into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. In order to more easily control the ratio of introduction of hydrogen, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , etc. are also effective starting materials for forming the second amorphous layer (). I can list many. Halides containing hydrogen atoms in these substances are hydrogen atoms that are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the second amorphous layer. Since halogen is also introduced, it is used as a suitable raw material for halogen introduction in the present invention. In order to structurally introduce hydrogen atoms into the second amorphous layer (2), in addition to the above, H ₂ or SiH ₄ ,
Silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ，
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc. and silicon or silicon compound for supplying Si coexist in the deposition chamber and discharge is performed. This can also be done by causing . In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second amorphous layer () of the photoconductive member to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. Hydrogen atoms contained in the second amorphous layer ()
In order to control the amount of (H) or/and halogen atom (X), for example, the support temperature or/and hydrogen atom (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge power, etc. may be controlled. In the layer region constituting the second amorphous layer (),
To structurally introduce a substance that controls conduction properties, such as a group atom or a group atom, a starting material for introducing a group atom or a starting material for introducing a group atom is used in a gaseous manner during layer formation. It may be introduced into the deposition chamber together with other starting materials for forming the second amorphous layer. The layer thickness of the second amorphous layer (2) in the photoconductive member of the present invention is such that when the second amorphous layer (2) is mainly used as a photocarrier generation layer, It is determined as appropriate considering the absorption coefficient of the second amorphous layer () with respect to the light source, preferably 1000 Å to 50 μm, more preferably 1000 Å to
The thickness is desirably 30 μm, most preferably 1000 Å to 20 μm. In addition, when the second amorphous layer (2) is mainly used as a layer for generating and transporting photocarriers, the thickness of the second amorphous layer may be determined as desired so that photocarriers are efficiently generated and transported, preferably 1 to 100 μm. , more preferably 1 to 80 μm, most preferably 2 to 50 μm. In the present invention, the layer thickness of the layer region containing a substance that controls conductive properties and provided unevenly on the support side is the thickness of the layer region and the amorphous layer formed on the layer region. The lower limit is preferably 30 Å or more, more preferably 40 Å or more, and optimally 50 Å. The above is desirable. Further, when the content of the substance controlling the conduction properties contained in the layer region is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region is preferably 10 μ or less, more preferably 8μ or less, optimally
It is desirable that the thickness be 5μ or less. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the second amorphous layer (), it is necessary to prepare a layer region (O) containing oxygen atoms during the formation of the second amorphous layer (). The starting material may be used together with the above-mentioned starting material for forming the second amorphous layer (), and the amount thereof may be controlled and contained in the layer to be formed. When a glow discharge method is used to form the layer region (O), oxygen atoms are introduced into a material selected from among the starting materials for forming the second amorphous layer (O) as desired. The starting materials for are added.
As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are oxygen atoms (O) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used in combination with a raw material gas having two constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . To form the first amorphous layer () containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer,
Alternatively, sputtering may be carried out by targeting a wafer containing a mixture of Si and SiO ₂ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a sputtering deposition chamber, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when a layer region (O) containing oxygen atoms is provided when forming the second amorphous layer (), the distribution of oxygen atoms contained in the layer region (O) In order to form a layer region (O) having a desired depth profile in the layer thickness direction by changing the concentration C(O) in the layer thickness direction, in the case of glow discharge, the distribution concentration C( O) while changing the gas flow rate of the starting material for introducing oxygen atoms to be changed as appropriate according to the desired rate of change curve,
This is done by introducing it into the deposition chamber. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (O) is formed by a sputtering method, the distribution concentration of oxygen atoms in the layer thickness direction C(O)
In order to change the depth profile of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, the starting point for introducing oxygen atoms is This is accomplished by using the substance in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be done by changing the mixing ratio of Si and SiO ₂ in advance in the layer thickness direction of the target. 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, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a member for 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 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 preferably 10μ.
This is considered to be the above. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 20 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (99.99% purity, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 diluted with He
B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /He) cylinder, 1106 is NO gas (purity 99.999
%) It is a cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming the first amorphous layer () on the cylindrical substrate 1137, SiH ₄ /He gas is supplied from the gas cylinder 1102, NO gas is supplied from the gas cylinder 1106, and B ₂ H ₆ is supplied from the gas cylinder 1105. /He gas valves 1122, 1126,
Open outlet pressure gauges 1127 and 1125 respectively.
Adjust the pressure of 131, 1130 to 1 Kg/cm ² , gradually open the inflow valves 1112, 1116, 1115, and connect the mass flow controllers 1107, 111.
1 and 1110, respectively. Subsequently, the outflow valves 1117, 1121, 1120 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the outflow valves 1117 and 1 are adjusted so that the ratio of SiH ₄ /He gas flow rate, NO gas flow rate, and B ₂ H ₆ /He gas flow rate becomes a desired value
121, 1120, and reaction chamber 1101.
Vacuum gauge 1136 so that the pressure inside reaches the desired value.
Adjust the opening of the main valve 1134 while checking the reading. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power supply 1140
is set to a desired power to generate glow discharge in the reaction chamber 1101 to form a first amorphous layer ( ) on the substrate 1137 . Next, to give an example of forming the second amorphous layer () on the first amorphous layer (), SiH ₄ /He gas is supplied from the gas cylinder 1102,
GeH ₄ /He gas from 103, gas cylinder 1106
From NO gas, from gas cylinder 1105 B ₂ H ₆ /
He gas valves 1122, 1123, 1126,
Open outlet pressure gauges 1127 and 1125 respectively.
Adjust the pressure of 128, 1131, 1130 to 1Kg/cm ² , and inflow valves 1112, 1113, 111.
6 and 1115 are gradually opened to allow the flow into the mass flow controllers 1107, 1108, 1111, and 1110, respectively. Subsequently, the outflow valve 111
7, 1118, 1121, 1120, gradually open the auxiliary valve 1132 to supply each gas to the reaction chamber 11.
01. At this time, SiH ₄ /He gas flow rate, GeH ₄ /He gas flow rate, NO gas flow rate and B ₂ H ₆ /He
Adjust the outflow valves 1117, 1118, 1121, 1120 so that the ratio with the gas flow rate becomes the desired value, and while watching the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 becomes the desired value. Adjust the opening of main valve 1134. Then, the temperature of the base 1137 is raised to 50°C by the heating heater 1138.
After confirming that the temperature is set in the range of ~400°C, the power source 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101 to form the second amorphous layer (). Form. 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. Each sample obtained in this way was placed in a charging exposure experimental device and subjected to corona discharge for 0.3 seconds at 5.0KV.
A light image was immediately irradiated. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. In the above, each sample was used under the same toner image forming conditions as above, except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a tungsten lamp as the light source, and an electrostatic image was formed. When the image quality of the toner-transferred image was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. Example 1 Each sample as an electrophotographic image forming member (Samples 1-1-1 to 1-1-
10-1 to 16-10-6) were created. At this time, the distribution states of boron atoms, oxygen atoms, and germanium atoms contained in the photoreceptive layer of each sample are shown in FIGS. 14A, 14B, and 15, respectively. The distribution state of boron atoms, oxygen atoms, and germanium atoms in each sample is determined by automatically controlling the opening and closing states of the corresponding valves according to a predetermined rate of change curve of the gas flow rate _{. 6} , NO, and _GeF4 by adjusting the gas flow rates. The distribution state of boron atoms and oxygen atoms in each sample is
Shown in the table. In addition, the distribution state of germanium atoms in each sample is shown in Table 3 for one sample No.
Regarding the sample, each sample was prepared in such a manner as to take the six distribution states (501 to 506) shown in FIG. 15 (the number of samples was 960). Example 2 Using the manufacturing apparatus shown in FIG. 20, each sample (Sample 21-1-21-1 to
10-1 to 28-9-6) were created. At this time, the distribution state of boron atoms, oxygen atoms, and germanium atoms contained in the photoreceptive layer of each sample is shown in FIG.
8 and 19, respectively. The distribution state of boron atoms, oxygen atoms, and germanium atoms in each sample is determined by automatically controlling the opening and closing states of the corresponding valves according to a predetermined rate of change curve of the gas flow rate _{. 6} , NO, and _GeF4 by adjusting the gas flow rates. The distribution of boron atoms and oxygen atoms in each sample is shown in Table 4. In addition, the distribution state of germanium atoms in each sample is set to take the six distribution states (601 to 606) shown in Figure 19 for one sample number shown in Table 4. (432 samples total). When the same image evaluation as in Example 1 was applied to each of these samples, high quality images were obtained in all cases, and no deterioration in image quality was observed even after repeated use 100,000 times. I couldn't help it.

【table】

【table】

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic explanatory diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 13 are
14A, 14B, and 17 are explanatory diagrams for explaining the distribution state of germanium atoms, and FIGS. 15 and 17 are distribution diagrams, respectively, showing the distribution state of boron atoms in Examples. Figure 18 is a distribution diagram showing the distribution state of oxygen atoms in Examples, respectively;
FIG. 16 and FIG. 19 are a distribution diagram showing the distribution state of germanium atoms in the example, and a second distribution diagram, respectively.
FIG. 0 is a schematic diagram showing an example of a manufacturing apparatus for manufacturing the photoconductive member of the present invention. 101...Support, 102...Photoreceptive layer, 10
3...first amorphous layer (), 104...second amorphous layer ().

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, a first amorphous layer ( ) made of an amorphous material having silicon atoms as a matrix, and silicon atoms and germanium atoms from the support side. a second amorphous layer made of an amorphous material having a matrix of Further, the distribution concentration of germanium atoms contained in the second amorphous layer () in the layer thickness direction is higher on the upper surface and/or lower surface side of the second amorphous layer (). Features of photoconductive materials. 2. The photoconductive member according to claim 1, wherein at least one of the first amorphous layer () and the second amorphous layer () contains hydrogen atoms. 3. The photoconductive member according to claim 1, wherein at least one of the first amorphous layer () and the second amorphous layer () contains a halogen atom. 4. The light according to claim 1, wherein at least one of the first amorphous layer () and the second amorphous layer () contains hydrogen atoms and halogen atoms. conductive member. 5. The photoconductive member according to claim 1, wherein at least one of the first amorphous layer () and the second amorphous layer () contains a substance that controls conductivity. . 6. The photoconductive member according to claim 5, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 7. The photoconductive member according to claim 5, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 8. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the first amorphous layer is 1 to 40 atomic %. 9. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the first amorphous layer ( ) is 1 to 40 atomic %. 10 The sum of the amounts of hydrogen atoms and halogen atoms contained in the first amorphous layer () is 1 to
4. The photoconductive member according to claim 4, which has a content of 40 atomic %. 11. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the second amorphous layer is 0.01 to 40 atomic%. 12. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the second amorphous layer is 0.01 to 40 atomic%. 13 The sum of the amounts of hydrogen atoms and halogen atoms contained in the second amorphous layer ( ) is from 0.01 to
4. The photoconductive member according to claim 4, which has a content of 40 atomic %. 14 The amount of germanium atoms contained in the second amorphous layer ( ) is 1 to 9.5×10 ⁵ atomic
The photoconductive member according to claim 1, which is ppm. 15 The atom belonging to Group 1 of the periodic table is B,
The photoconductive member according to claim 6, which is selected from Ga. 16 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member according to claim 7, which is selected from As. 17 The substance controlling the conductivity is 0.001 to 5×
Claim 5 containing 10 ⁴ atomic ppm
The photoconductive member described in . 18 The substance that controls the conductivity is 30 atomic
The photoconductive member according to claim 17, which contains ppm or more. 19 The content of oxygen atoms is 0.001 to 50 atomic
% of the photoconductive member according to claim 1. 20. The photoconductive member according to claims 3 and 4, wherein the halogen atom is selected from fluorine and chlorine.