JPH0220098B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, chemical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as use environment characteristics. Although individual improvements have been made in terms of stability, stability over time, and durability, the reality is that there is still room for further improvement in terms of improving overall properties. It is. For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use. When used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon in which an afterimage occurs. In addition, 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 some cases, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. That is, for example, the lifetime of the photocarrier generated in the formed photoconductive layer by light irradiation is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area. There were cases where this occurred. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members for electrophotography. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we found that silicon atoms are used as a matrix, hydrogen atoms H or Amorphous material containing at least one of halogen atoms X, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon Use “X)”]
A photoconductive member designed and produced in such a way that the layer structure of the photoconductive member having a photoconductive layer composed of the following is specified not only shows extremely excellent properties in practical use, but also This is based on the discovery that it is superior in all respects to conventional photoconductive members, and has particularly excellent properties as a photoconductive member for electrophotography. The electrical, optical, and photoconductive properties of the present invention are almost unaffected by the usage environment, are always stable, are extremely resistant to light fatigue, do not deteriorate even after repeated use, are highly durable, and have excellent durability. The main object of the present invention is to provide a photoconductive member for electrophotography (hereinafter referred to as "photoconductive member") in which no or almost no potential is observed. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied very effectively. An object of the present invention is to provide a photoconductive member having 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. 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 and high voltage resistance. The photoconductive member of the present invention comprises a support for a photoconductive member for electrophotography and an amorphous material having silicon atoms as a matrix, and has a photoconductive layer thickness of 1 to 1.
100μ first amorphous layer, silicon atoms and 1×
a second amorphous layer having a layer thickness of 0.003 to 30μ and made of an amorphous material containing 10 ^-3 to 90 atomic% of carbon atoms and halogen atoms, and the first amorphous layer is
A first layer region having a layer thickness of 0.001μ or more containing 0.001 to 50 atomic% of oxygen atoms as constituent atoms, and a distribution state of atoms belonging to group of the periodic table as constituent atoms, such that the distribution concentration thereof is on the support side.
a second layer region that is continuous in the layer thickness direction and has a portion with a high concentration of 50 atomic ppm or more and a portion that is considerably lower on the interface side than on the support side, and the first layer region is , is characterized in that it is present on the support side of the first amorphous layer. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has a-Si (H,
A first amorphous layer 10 having photoconductivity consisting of
2 and a second amorphous layer 106, the first amorphous layer 102 is continuous in the layer thickness direction with the first layer region O103 containing oxygen atoms as constituent atoms, and It has a layer structure configured to have a second layer region 104 containing group atoms as constituent atoms in a distribution state in which it is distributed more toward the support 101 . In the example shown in Figure 1, the second
The layer region 104 occupies the entire layer region of the first amorphous layer 102, has a layer structure in which the first layer region O103 constitutes a part of the second layer region 104, O103 exists below the surface of the first amorphous layer 102. The upper layer region 105 of the first amorphous layer 102 does not contain oxygen atoms;
It is contained only in the layer region O103. In the first layer region O103, by containing oxygen atoms, the dark resistance is intensively increased and the adhesion between the support 101 and the first amorphous layer 102 is improved, and the upper layer region 105 Efforts have been made to increase sensitivity without containing oxygen atoms. First layer region O103
The oxygen atoms contained in the layer are continuously and substantially uniformly distributed in the layer thickness direction, and in a plane parallel to the interface between the support 101 and the first amorphous layer 102, the oxygen atoms are substantially uniformly distributed in the layer thickness direction. is contained in the first layer region O103 in a uniformly distributed state. In the present invention, the second layer region 10 constituting the first amorphous layer 102 and containing group atoms
Group atoms contained in 4 include B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc. B, It is Ga. In the present invention, the distribution state of group atoms contained in the second layer region 104 is as described above in the layer thickness direction, and the distribution state of the group atoms contained in the second layer region 104 is as described above.
In a plane parallel to the surface of 01, the distribution is substantially uniform. The layer thickness of the first layer region O103 and the upper layer region 105 is one of the important factors for effectively achieving the object of the present invention, so that the formed photoconductive member has sufficient desired characteristics. As given, due care must be taken in the design of the photoconductive member. In the present invention, the layer thickness of the first layer region O103
The lower limit of T ₀ is usually 0.001μ or more, preferably 0.002μ or more, and optimally 0.003μ or more. Further, the lower limit of the layer thickness T ₀ of the upper layer region 105 is usually 0.02μ or more, preferably
It is desirable that the thickness be 0.03μ or more, most preferably 0.05μ or more. The lower limit of the layer thickness T ₀ of the first layer region O103 and the upper limit of the layer thickness T of the upper layer region 105 are based on the characteristics required for both layer regions and the first amorphous layer 102.
It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the properties required for the second amorphous layer 106 as a whole and for each of the second amorphous layers 106. In the photoconductive member of the present invention, as shown in FIG. In addition to this, the first layer region O and the second layer region can be made into the same layer region without containing group atoms in the upper layer region 105. The photoconductive member according to the embodiment in which the upper layer region 105 does not contain group atoms exhibits even more remarkable effects when used repeatedly in a humid atmosphere, and can be used for a long period of time in the atmosphere. Demonstrates sufficient durability for use. Further, the case where the second layer region is formed within the first layer region O can also be cited as one of the preferred embodiments. The amount of oxygen atoms contained in the first layer region O is determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001 to 50 atomic%, preferably 0.001 to 50 atomic%. is 0.002~
It is desirable that it be 40 atomic%, optimally 0.003 to 30 atomic%. If the layer thickness T ₀ of the first layer region O is sufficiently thick or the ratio of the first amorphous layer to the total layer thickness (T ₀ +T) exceeds two-fifths or more, the first The upper limit of the amount of oxygen atoms contained in the layer region O is usually 30 atomic% or less, preferably,
It is desirable that it be 20 atomic % or less, optimally 10 atomic % or less. FIGS. 2 to 10 show the layer thickness direction of group group atoms contained in the layer region containing group group atoms constituting the first amorphous layer of the photoconductive member of the present invention. A typical example of the distribution state is shown. In the examples shown in FIGS. 2 to 10, the layer region O containing oxygen atoms may be the same layer region as the layer region, include the layer region, or be part of the layer region. Therefore, in the following explanation, the layer region O containing oxygen atoms will not be mentioned unless a particular explanation is required. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of group atoms, and the vertical axis represents the layer region that constitutes the first amorphous layer exhibiting photoconductivity and contains group atoms. Indicates the layer thickness t, _tB indicates the position of the interface on the support side, and _tT indicates the position of the interface on the opposite side to the support side. That is, the layer region containing group atoms is
Layer formation occurs from the _tB side toward the _tT side. In the present invention, the layer region containing group atoms is a-Si(H,X) constituting the photoconductive member.
It may occupy the entire layer area of the first amorphous layer exhibiting photoconductivity, or may occupy a part thereof. In the present invention, when the layer region occupies a part of the layer region of the first amorphous layer, as shown in the example of FIG. Preferably, it is provided in the lower layer region of layer 102. FIG. 2 shows a first typical example of the distribution state of group atoms contained in the layer region in the layer thickness direction. In the example shown in FIG. 2, the content concentration of group atoms is from the interface position t _B to the position t ₁ where the surface where the layer region containing group atoms is formed and the surface of the layer region contact. C is contained in the layer region where group group atoms are formed while taking a constant value of _C1 , and the distributed concentration C gradually and continuously decreases from _C2 from position _t1 to the interface position _tT . ing. At the interface position _tT , the distribution concentration C of group atoms is _C3 . In the example shown in Figure 3, the distribution concentration C of the group atoms contained gradually and continuously decreases from C ₄ from position t _B to position t _T , and reaches C ₅ at position t _T. It forms a similar distribution state. In the case of Figure 4, the distribution concentration C of group atoms is constant at _C6 from position _tB to position _t2 , and gradually and continuously between position _t2 and position _tT . is reduced to substantially zero at position _tT . In the case of Fig. 5, the distribution concentration C of group atoms gradually decreases continuously from 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 group atoms is a constant value of C ₉ between the position t _B and the position t ₃ , and is set to C ₁₀ at the position t _T. Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of _C11 from position _tB to position _t4 , and
From t ₄ to position t _T, the distribution state decreases linearly from C ₁₂ to C ₁₃ . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of group atoms decreases linearly from C ₁₄ to zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C of group atoms decreases linearly from C ₁₅ to C ₁₆ , and between position t ₅ and t _T An example is shown in which C ₁₆ is a constant value. In the example shown in FIG. 10, the distribution concentration C of group atoms is C 17 at position t _B and C ₁₇ at position t ₆
At first, the value is gradually decreased from C ₁₇ until it reaches t 6 , and then it is rapidly decreased to C ₁₈ at position _{t 6 .} Between position t ₆ and position t ₇ , the distribution concentration C
is decreased rapidly at first, and then slowly and gradually decreased to C ₁₉ at position t ₇ , and between positions t ₇ and t ₈ , it is decreased very gradually and gradually to position t ₈ . reaches C ₂₀ . Between the position t ₈ and the position t _T , the distribution concentration C is decreased from C ₂₀ 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 group atoms contained in the layer region in the layer thickness direction, in the present invention, on the support side, Distribution concentration C of group atoms
On the interface _tT side, the layer region in which the distribution state of group atoms is formed has a part where the distribution concentration C is considerably lower than that on the support side, and the layer region is the first amorphous layer. It is provided in layers. In the present invention, the layer region containing group atoms constituting the first amorphous layer is a localized region containing group atoms at a relatively high concentration toward the support side, as described above. It has A. If the localized region A is explained using the symbols shown in FIGS. 2 to 10, it is preferable that the localized region A be provided within 5 μm from the interface position t _B. In the present invention, the localized region A may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region A is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the first amorphous layer to be formed. In the localized region A, the maximum value Cmax of group atoms contained therein in the layer thickness direction is usually 50 atomic ppm.
or more, preferably 80 atomic ppm or more, optimally
It is desirable to form a layer so that a distribution state of 100 atomic ppm or more can be obtained. That is, in the present invention, the layer region containing group atoms has the maximum value of the distribution concentration C within 5μ of the layer thickness from the support side (layer region of 5μ thickness from t _B ).
It is desirable that the structure be formed so that Cmax exists. In the present invention, the content of group atoms contained in the layer region containing group atoms may be determined as desired so as to effectively achieve the object of the present invention. , usually 0.01~5
×10 ⁴ atomic ppm, preferably 0.5 to 1×
10 ⁴ atomic ppm, optimally 1-5×10 ³ atomic
It is preferable to set it in ppm. In the present invention, the thickness of the first amorphous layer is usually 1 to 100 μm, preferably 1 to 80 μm, and most preferably It is desirable that the thickness be 2 to 50μ. In the present invention, the first amorphous layer composed of a-Si (H, It is done by law. For example, in order to form the first amorphous layer composed of a-Si (H, Along with the raw material gas of
A raw material gas for introducing hydrogen atoms H and/or for introducing halogen atoms A layer made of a-Si(H,X) may be formed on the supporting surface of the substrate. In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms H or / and a gas for introducing halogen atoms X may be introduced into the deposition chamber for sputtering. In the present invention, specific examples of the halogen atom X contained in the first amorphous layer as necessary include fluorine, chlorine, bromine, and iodine,
Particularly preferred are fluorine and chlorine. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. 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 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 ₂ , 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 by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
A first amorphous layer made of a-Si containing halogen atoms can be formed on a predetermined support. When forming the first amorphous layer containing halogen atoms according to the glow discharge method, basically Si
Silicon halide gas, which is the raw material gas for supply, and
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber for forming the first amorphous layer at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to remove these gases. By forming a plasma atmosphere, a first amorphous layer can be formed on a predetermined support, but these gases may also contain hydrogen atoms in order to introduce hydrogen atoms. A layer may also be formed by mixing a silicon compound gas in a predetermined amount. 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. To form the first amorphous layer of a-Si(H, This is sputtered in a predetermined gas plasma atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam. This can be done by heating and evaporating the flying evaporates using a method such as the EB method and passing them through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it. 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 , etc., and halides that have a hydrogen atom as one of their constituents in a gaseous state or can be gasified are also used. It can be mentioned as an effective starting material for forming the first amorphous layer. These 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 during the formation of the first amorphous layer. is used as a suitable raw material gas for introducing halogen atoms in the present invention. In order to structurally introduce hydrogen atoms into the first amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be achieved by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, a first amorphous layer made of a-Si(H,X) is formed on the substrate. Furthermore, a gas such as B ₂ H ₆ can also be introduced for doping with impurities. In the present invention, the amount of hydrogen atoms H, the amount of halogen atoms X, or the sum of the amounts of hydrogen atoms and halogen atoms contained in the first amorphous layer of the photoconductive member to be formed is usually 1 to 1. It is desirable that the content be 40 atomic %, preferably 5 to 30 atomic %. To control the amount of hydrogen atoms H and/or halogen atoms X contained in the first amorphous layer, for example, the support temperature or/and the amount used to contain hydrogen atoms H or halogen atoms The amount of starting material to be introduced into the deposition system, the discharge force, etc. may be controlled. In order to provide the layer region containing group atoms and the layer region O containing oxygen atoms in the first amorphous layer, the first amorphous layer is formed by a glow discharge method, a reactive sputtering method, etc. In this case, a starting material for introducing group atoms and a starting material for introducing oxygen atoms are used together with the above-mentioned starting material for forming the first amorphous layer to control their amount in the formed layer. However, this can be achieved by containing it. When using the glow discharge method to form the layer region O containing oxygen atoms and the layer region O containing group atoms constituting the first amorphous layer, the raw material gas for forming each layer region As the starting material, a starting material for introducing oxygen atoms and/or a starting material for introducing group atoms is selected as desired from among the starting materials for forming the first amorphous layer described above. Substances are added. Such starting materials for introducing oxygen atoms or starting materials for introducing group atoms include gaseous substances or gasified substances whose constituent atoms are at least oxygen atoms or group atoms. Most can be used. For example, if layer region O is to be formed, raw material gas containing silicon atoms Si and oxygen atoms O
A raw material gas having a constituent atom of , and a raw material gas having a hydrogen atom H or/and a halogen atom Either a raw material gas containing atoms and a raw material gas containing oxygen atoms O and hydrogen atoms H are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms Si as constituent atoms, A raw material gas having three constituent atoms: silicon atom Si, oxygen atom O, and hydrogen atom H can be mixed and used. Alternatively, a raw material gas containing silicon atoms Si and hydrogen atoms H as constituent atoms may be mixed with a raw material gas containing oxygen atoms O as constituent atoms. Specifically, starting materials for introducing oxygen atoms include, for example, oxygen O ₂ , ozone O ₃ , and nitrogen monoxide.
NO, nitrogen dioxide N ₂ O, nitrogen monodioxide N ₂ O, nitrogen sesquioxide N ₂ O ₃ , nitrogen tetraoxide N ₂ O ₄ , nitrogen pentoxide N ₂ O ₅ , nitrogen trioxide NO ₃ , silicon atom Si and oxygen For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), which have an atom O and a hydrogen atom H as constituent atoms, can be mentioned. When a layer region is formed using a glow discharge method, B ₂ H ₆ and B ₄ H ₁₀ are effectively used in the present invention as starting materials for introducing group group atoms. , 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 . The content of group atoms introduced into the layer region containing group atoms is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, the support temperature, It can be arbitrarily controlled by controlling the pressure in the deposition chamber, etc. To form the layer region O containing oxygen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or SiO ₂ , wafer or Si
The sputtering may be carried out by targeting wafers containing a mixture of 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 to form a gas plasma of these gases to sputter the Si wafer. All you have to do is tutter. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms H and/or halogen atoms X as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example mentioned above is
It can also be used as an effective gas in sputtering. In the present invention, the dilution gas used when forming the first amorphous layer by the glow discharge method or the sputtering gas used when forming the first amorphous layer by the sputtering method is a so-called rare gas. gas,
For example, He, Ne, Ar, etc. can be cited as suitable examples. In the photoconductive member 100 shown in FIG. It is provided in order to achieve the purpose of the present invention in terms of usage characteristics, pressure resistance, usage environment characteristics, and durability. In addition, in the present invention, since each of the amorphous materials constituting the first amorphous layer and the second amorphous layer has a common constituent element of silicon atoms, the lamination is possible. Chemical stability is sufficiently ensured at the interface. The second amorphous layer is an amorphous material [a
−(Si _x C _1-x ) _y X _1-y , where 0<x, y<1]. The formation of the second amorphous layer composed of a-(Si _x C _1-x ) _y X _1-y is performed using a glow discharge method, a sputtering method,
This is done by ion implantation method, ion plating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having a photoconductive member, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second amorphous layer to be manufactured. Due to their advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second amorphous layer may be formed by using a glow discharge method and a sputtering method in the same apparatus system. To form the second amorphous layer by the glow discharge method, _the raw material gas for forming a-(Si _x C _1-x ) _y The mixture is mixed at a mixing ratio of 1, and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by causing a glow discharge method to form a gas already formed on the support. a on the first amorphous layer
−(Si _x C _1-x ) _y X _1-y may be deposited. In the present invention, as the raw material gas for forming a-(Si _x C _1-x ) _y X _1-y , at least one of silicon atom Si, carbon atom C, and halogen atom Most gaseous substances or gasified substances that can be gasified can be used. When using a raw material gas containing Si as one of Si, C, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing A raw material gas containing Si as a constituent atom and a raw material gas containing C and X as constituent atoms may be mixed at a desired mixing ratio. Mix or
Alternatively, a raw material gas containing Si as a constituent atom and Si, C
and a raw material gas having three constituent atoms of X can be used in combination. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, preferred halogen atoms X contained in the second amorphous layer are F, Cl,
Br and I, with F and Cl being particularly preferred. In the present invention, the second amorphous layer is a-
Although it is composed of (Si _x C _1-x ) _y X _1-y , it can further contain a hydrogen atom. The inclusion of hydrogen atoms in the second amorphous layer makes it possible to share some of the raw material gas types when forming a continuous layer with the first amorphous layer, which reduces production costs. It's convenient. In the present invention, raw material gases that can be effectively used to form the second amorphous layer include those in a gaseous state at room temperature and pressure, or substances that can be easily gasified. I can list them. Such substances for forming the second amorphous layer include, for example, saturated hydrocarbons having 1 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, Examples include simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF ₃ , ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr,
Silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
SiCl ₃ Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ ,
Examples of halogen-substituted silicon hydride include SiH ₂ F ₂ ,
SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ ,
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₈ ,
Silanes such as Si ₄ H ₁₀ , etc. can be mentioned. In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ Cl, CH ₃ Br, CH ₃ I, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si(C ₅ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ can also be mentioned as effective. These second amorphous layer forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second amorphous layer formed. They are selected and used as desired during the formation of the second amorphous layer. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiCl can contain halogen atoms. _{A- ( Si _ x} C _1-x ) _y
A second amorphous layer consisting of (Cl+H) _1-y can be formed. To form the second amorphous layer by the sputtering method, target a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and optionally hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing C and The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least halogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. C and X, H as necessary
As the material serving as the raw material gas for introduction, the material for forming the second amorphous layer shown in the glow discharge example described above can also be used as an effective material in the sputtering method. In the present invention, the diluent gas used when forming the second amorphous layer by a glow discharge method or a sputtering method is a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. The second amorphous layer in the present invention is carefully formed to provide the desired properties. In other words, substances whose constituent atoms are Si, C, X, and optionally H have a structure ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductivity to semiconductor. In the present invention, a- (Si _x
The preparation conditions are strictly selected according to the desired conditions so that C _1-x ) _y X _1-y is formed. For example, to provide the second amorphous layer with the main purpose of improving voltage resistance, _a- (Si _x C _1-x ) _y It is created as an amorphous material. In addition, when a second amorphous layer is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. A-(Si _x C _1-x ) _y X _1-y is created as a sensitive amorphous material. a-(Si _x C _1-x ) _y X _1-y on the surface of the first amorphous layer
The temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. a-(Si _x C _1-x ) _y X _1-y which has the property of
It is desirable that the temperature of the support during formation of the layer be tightly controlled so that the layer can be formed as desired. In the present invention, the formation of the second amorphous layer is carried out by selecting an optimal range as appropriate in accordance with the method of forming the second amorphous layer in order to effectively achieve the desired purpose. However, in normal cases, the temperature is preferably 50 to 350°C, preferably 100 to 250°C. The glow discharge method is used to form the second amorphous layer because it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. However, when forming the second amorphous layer using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, is advantageous. Created a−(Si _x C _1-x ) _y
It is one of the important factors that influences the characteristics of X _1-y . _The discharge power condition for effectively producing a-(Si _x C _1-x ) _y
300W, preferably 20-200W. It is desirable that the gas pressure in the deposition chamber is normally about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the support temperature and discharge power for forming the second amorphous layer are preferably in the above-mentioned ranges, but these layer forming factors can be determined independently. The desired characteristics a-(Si _x C _1-x ) _y X _1-y are not determined separately.
It is preferable that the optimum values of each layer forming factor be determined based on mutual organic relationships such that a second amorphous layer consisting of . The amounts of carbon atoms and halogen atoms contained in the second amorphous layer in the photoconductive member of the present invention are as follows:
The conditions for forming the second amorphous layer are also important factors in forming the second amorphous layer that provides the desired properties to achieve the objectives of the present invention. The amount of carbon atoms contained in the second amorphous layer in the present invention is usually 1×10 ^-3 to 90 atomic%, preferably 1 to 90 atomic%, and optimally 10 to 80 atomic%.
% is preferable. The content of halogen atoms is usually 1 to
It is desirable that the halogen atom content be 20 atomic%, preferably 1 to 18 atomic%, and optimally 2 to 15 atomic%, and photoconductive members produced when the halogen atom content is within these ranges can be sufficiently applied in practice. It is possible to do so. The content of hydrogen atoms, which may be included as necessary, is usually 19 atomic %, preferably 13 atomic % or less. That is, if expressed in the x and y representation of a-(Si _x C _1-x ) _y X _1-y , x is usually 0.1 to 0.99999, preferably 0.1 to
It is desirable that y is 0.99, optimally 0.15 to 0.9, and y usually 0.8 to 0.99, preferably 0.82 to 0.99, and optimally 0.85 to 0.98. When both a halogen atom and a hydrogen atom are included, a-(Si _x C _1-x ) _y (H+X) ₁ as before
If you display _-y, the numerical range of x and y in this case is a
-(Si _x C _1-x ) _y X _1-y It is almost the same as the case. The numerical range of the layer thickness of the second amorphous layer in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. Furthermore, the layer thickness of the second amorphous layer is determined based on organic relationships according to the characteristics required for each layer region, even in relation to the layer thickness of the first layer region O103. It needs to be determined appropriately according to the desired results. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The thickness of the second amorphous layer in the present invention is as follows:
Usually 0.003-30μ, preferably 0.004-20μ, optimally
It is desirable that the thickness be 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pb, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and as desired,
Although its shape is determined, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying. . The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range.
However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, a method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming each layer region of the present invention is sealed, and as an example, 11
02 is a SiH ₄ (purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder diluted with He, and 1103 is a B ₂ H ₆ gas diluted with He (purity 99.999%, below).
Abbreviated as B ₂ H ₆ /He. ) cylinder, 1104 is Si ₂ H ₆ gas diluted with He (purity 99.99%, hereinafter Si ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is NO gas (purity
99.999%) cylinder, 1106 diluted with He
It is a SiF ₄ gas (purity 99.999%, hereinafter abbreviated as SiF ₄ /He) cylinder. In order to cause these gases to flow into the reaction chamber 1101, the valves of gas cylinders 1102 to 1106, 11
22 to 1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112
~1116, confirming that the outflow valves 1117~1121 and auxiliary valves 1132, 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and gas piping. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valve 1
Close 117-1121. Next, to give _an example of forming a photoconductive _member having _the layer structure shown in FIG.
5 to NO gas through valves 1122 and 112, respectively.
3,1125 open and outlet pressure gauge 1127,1
Adjust the pressure of 128 and 1130 to 1Kg/cm ² respectively,
Gradually open the inflow valves 1112, 1113, and 1115, respectively, and the mass flow controllers 1107,
1108 and 1110, respectively. Subsequently, the outflow valves 1117, 1118, 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, 1118, and 1120 are adjusted so that the ratio of the SiH ₄ /He gas flow rate to the B ₂ H ₆ /He gas flow rate and NO gas flow rate becomes the desired value, and the pressure inside the reaction chamber is adjusted to the desired value. Vacuum gauge 11 to get the value
Adjust the opening of the main valve 1134 while checking the reading of 36. After confirming that the temperature of the base cylinder 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. and at the same time B ₂ H ₆ /He according to the pre-designed rate of change curve.
The distribution concentration of boron atoms contained in the formed layer in the layer thickness direction is controlled by gradually changing the gas flow rate manually or by using an externally driven motor or the like by operating the valve 1118. As described above, when layer regions B and O containing boron atoms and oxygen atoms are formed to a desired layer thickness, the outflow valve 1120 is closed and the reaction chamber 1101 is closed.
By continuing layer formation under the same conditions except for blocking the inflow of NO gas into layer region B, which contains no oxygen atoms but contains boron atoms, layer region B and O Form the desired layer thickness on top. In this way, a first amorphous layer with desired characteristics can be formed on the substrate. The layer region containing boron atoms is formed by cutting off the flow of B ₂ H ₆ /He gas into the reaction chamber 1101 at an appropriate point in the process of forming the first amorphous layer. It can be formed to have a desired layer thickness, and the layer region can either occupy the entire layer region of the first amorphous layer or a part thereof. For example, in the above example, when the layer region B is formed to a desired layer thickness, the flow of B ₂ H ₆ /He gas into the reaction chamber 1101 is stopped by completely closing the outflow valve 1118. By continuing layer formation under the same conditions except for cutting, a layer region containing neither boron atoms nor oxygen atoms is formed on layer region B as part of the first amorphous layer. I can do it. Further, when forming a layer region that does not contain boron atoms but contains oxygen atoms, the layer may be formed using, for example, NO gas and SiH ₄ /He gas. When containing halogen atoms in the first amorphous layer, for example, SiF ₄ /He is added to the above gas,
Further, it is added and sent into the reaction chamber 1101. Depending on the selection of gas species during the formation of the amorphous layer,
The layer formation speed can be further increased. for example
If layer formation is performed using Si ₂ H ₆ gas instead of SiH ₄ gas, the productivity can be increased several times. Forming the second amorphous layer on the first amorphous layer is performed, for example, as follows. First, open shutter 1142. All gas supply valves are once closed, and the reaction chamber 1101 is
34 is fully opened to exhaust the air. A target is provided on the electrode 1141 to which high-voltage power is applied, in which a high-purity silicon wafer 1142-1 and a high-purity graphite wafer 1142-2 are placed in advance at a desired area ratio.
SiF ₄ /He gas is introduced into the reaction chamber 1101 from the gas cylinder 1106, and the internal pressure of the reaction chamber 1101 is increased.
Adjust the main valve 1134 to 0.05 to 1 Torr. A second amorphous layer can be formed on the first amorphous layer by turning on the high voltage power supply and sputtering the target. Another method for forming the second amorphous layer is to use, for example, SiH ₄ gas, SiF ₄ gas,
This is achieved by diluting each of the C ₂ H ₄ gases with a diluent gas such as He as necessary and flowing them into the reaction chamber 1101 at a desired flow rate ratio to generate a glow discharge according to desired conditions. Ru. Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 1101. Valve 1
In order to avoid gas remaining in the gas piping leading from 117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, and the auxiliary valve 11
32 and fully open the main valve 1134 to temporarily evacuate the system to a high vacuum, as necessary. The amount of carbon atoms contained in the second amorphous layer is, for example, in the reaction chamber 11 of SiH ₄ gas and C ₂ H ₄ gas.
The flow rate ratio introduced into the 01 is changed as desired, or when forming a layer by sputtering, the sputtering area ratio of the silicon wafer and graphite wafer is changed when forming the target, or the sputtering area ratio of the silicon wafer and the graphite wafer is changed. It can be controlled as desired by changing the mixing ratio of powder and graphite powder and molding the target. The amount of halogen atoms X contained in the second amorphous layer can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF ₄ gas, is introduced into the reaction chamber 1101. will be accomplished. Example 1 Using the manufacturing apparatus shown in FIG. 11, an image forming member having a concentration distribution of B and O as shown in FIG. 12 in the amorphous layer was produced under the conditions shown in Table 1. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5 KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux.sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 2 Using the manufacturing apparatus shown in FIG. 11, an image forming member having the concentration distribution of B and O as shown in FIG. 13 in the amorphous layer was prepared under the conditions shown in Table 2. Created. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux.sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

【table】

[Table] Example 3 Using the manufacturing apparatus shown in FIG. 11, an image forming member having the concentration distribution of B and O as shown in FIG. 14 in the amorphous layer was prepared under the conditions shown in Table 3. Created. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux.sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 4 By changing the flow rate of B ₂ H ₆ , the first
Image forming members having boron concentration distributions as shown in FIGS. 5 to 20 were prepared. Other conditions and evaluation methods were carried out in exactly the same manner as in Example 1, and the results shown in the table below were obtained.

[Table] ◎ High image quality with no image defects ○ No image defects and very good adhesion Example 5 Exactly the same as Example 1 except that the NO flow rate was changed to change the oxygen content in the amorphous layer. An image forming member was formed by the method described above and evaluated in the same manner as in Example 1, and the results shown in the table below were obtained.

[Table] ◎ Very good
○ Good Example 6 An image forming member was prepared in exactly the same manner as in Example 2, except that the thickness of the amorphous layer was 20μ and the thickness of the first layer region was changed, and the same evaluation was performed. The results shown in the table below were obtained.

[Table] ◎: Very good ○: Good example 7 When forming the amorphous layer, the flow rate ratio of SiH ₄ gas, SiF ₄ gas, and C ₂ H ₄ gas was changed to An image forming member was prepared in exactly the same manner as in Example 1, except that the content ratio of silicon atoms to carbon atoms in the sample was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 about 50,000 times for the image forming member thus obtained, image evaluation was performed and the results shown in Table 7 were obtained.

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Example that causes some image defects 8 The method was exactly the same as in Example 1 except that the layer thickness of the amorphous layer was changed. An imaging member was thus formed. The steps of image formation, development, and cleaning as described in Example 1 were repeated to obtain the following results.

[Table] Example 9 Layer formation was performed in the same manner as in Example 1 except that the method for forming the amorphous layer was changed as shown in the table below, and good results were obtained when evaluated.

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 respectively show layer regions containing group atoms constituting the amorphous layer. FIG. 11 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 12 to 20 are diagrams for explaining the distribution state of group atoms in the present invention. FIG. 2 is an explanatory diagram showing the distribution state of boron atoms and oxygen atoms. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer, 103...First layer region O, 104...Second layer region, 105...
Upper layer region, 106...Second amorphous layer, 10
7...Free surface.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a first amorphous layer having photoconductivity and having a thickness of 1 to 100 μm, which is composed of an amorphous material having silicon atoms as a matrix. a second amorphous layer having a layer thickness of 0.003 to 30μ and made of an amorphous material containing silicon atoms and 1 × 10 ^-3 to 90 atomic% of carbon atoms and halogen atoms,
The first amorphous layer has constituent atoms of 0.001 to
A first layer region having a layer thickness of 0.001μ or more containing 50 atomic% oxygen atoms, and a portion with a high distribution concentration of 50 atomic ppm or more on the support side, where the distribution state of atoms belonging to group 3 of the periodic table as constituent atoms is 50 atomic % or more. a second layer region that is continuous in the layer thickness direction and has a portion that is considerably lower on the interface side than on the support side, and the first layer region is A photoconductive member for electrophotography, characterized in that a crystalline layer is present on the support side. 2. The photoconductive member for electrophotography according to claim 1, wherein the first layer region and the second layer region share at least a portion thereof. 3. The photoconductive member for electrophotography according to claim 1, wherein the second layer region occupies substantially the entire layer region of the first amorphous layer.