JPH0220102B2 - - 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,
It must have a high signal-to-noise ratio [photocurrent (I _p )/dark current (I _d )], have absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use, and being able to easily dispose of 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, and 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, and this type of photoconductive member 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. When the photoconductive layer is made 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 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 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. 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 and hydrogen atoms (H ) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "a- A photoconductive member designed and produced with a photoconductive layer composed of a photoconductive layer composed of Si (H, Not only does it exhibit extremely excellent properties, but it also surpasses conventional photoconductive members in every respect, and in particular, it has extremely excellent properties as a photoconductive member for electrophotography. It is based on the point that was found. 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, and are highly durable. The main object of the present invention is to provide a photoconductive member for electrophotography (hereinafter referred to as a "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 extremely 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 includes a support for the photoconductive member and a first amorphous layer having photoconductivity and having a layer thickness of 1 to 100 μm, which is composed of an amorphous material containing silicon atoms as a matrix. and silicon atoms and 1×10 ^-3 ~
and a second amorphous layer with a layer thickness of 0.003 to 30 μ made of an amorphous material containing 90 atomic % of carbon atoms and halogen atoms, and the first amorphous layer is
A first layer region containing 0.001 to 50 atomic % of oxygen atoms as constituent atoms and in contact with the support and occupying a part of the first amorphous layer;
a second layer region having a layer thickness of 50μ or less containing atoms belonging to Group Group of the Periodic Table in a substantially uniform distribution state in the layer thickness direction in a range of 0.001 to 5×10 ⁴ atomic ppm; The distribution state of oxygen atoms on the support side is 500 atomic ppm.
It is characterized by having a non-uniform and continuous distribution state in the layer thickness direction, which has the above-mentioned high portion and has a portion lower on the second amorphous layer side than on the support side. 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 with photoconductivity consisting of ()
102 and a second amorphous layer ( ) 106 made of an amorphous material containing silicon atoms, carbon atoms, and halogen atoms. The first amorphous layer () 102 is a first layer region (O) containing oxygen atoms as constituent atoms, which is continuous in the layer thickness direction and distributed more toward the support 101. 103 and a second layer region ( ) 104 containing a group atom as a constituent atom. In the example shown in FIG. 1, the first layer region (O) 103
occupies a part of the second layer region (V) 104, and the first layer region (O) 103 and the second layer region (V) 104 occupy a part of the first amorphous layer ( )10
They are unevenly distributed on the support body 101 side of No. 2. The upper layer region 105 of the first amorphous layer 102 does not substantially contain oxygen atoms and group atoms, and the oxygen atoms are present in the first layer region (O) 103.
Group atoms are contained in the second layer region (V) 104. Of course, the first layer region (O) 103 also contains group atoms. In the present invention, the above-mentioned layer structure is adopted because the first layer region (O) 103 contains oxygen atoms to achieve high dark resistance and the support 101 and the first amorphous layer. An emphasis is placed on improving the adhesion between the upper layer region 102 and the upper layer region 105, and an emphasis is placed on increasing the sensitivity by not containing oxygen atoms in the upper layer region 105. The oxygen atoms contained in the first layer region (O) 103 are continuously and non-uniformly distributed in the layer thickness direction,
and a support 101 and a first amorphous layer ( ) 102
In the plane parallel to the interface with the first layer region (O) 103, the first layer region (O) 103 has a substantially uniform distribution. In the present invention, the first amorphous layer ( ) 102
The group atoms contained in the second layer region (V) 104 containing group atoms are:
P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and particularly preferably used are P,
It is As. In the present invention, the second layer region (V) 104
The group atoms contained therein are distributed substantially uniformly in the layer thickness direction and in a plane parallel to the surface of the support 101. First layer region (O) 103 and upper layer region 105
Since the layer thickness of the photoconductive member is one of the important factors for effectively achieving the object of the present invention, the design of the photoconductive member should be carefully selected so that the formed photoconductive member has sufficient desired characteristics. Sufficient care must be taken when doing so. In the present invention, the upper limit of the layer thickness T _B of the second layer region (V) 104 is usually 50 μm.
The thickness is preferably 30μ or less, most preferably 10μ or less. Further, the lower limit of the layer thickness T of the upper layer region 105 is usually 0.5μ or more, preferably 1μ or more, and optimally 3μ or more. The lower limit of the layer thickness T _B of the second layer region (V) 104 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 (V).
It is appropriately determined as desired when designing the layers of the photoconductive member, based on the mutual organic relationship with the properties required for the entire layer 102. In the present invention, the above layer thickness T _B and layer thickness T
Generally, appropriate numerical values are selected for each when the relationship T _B /T≦1 is satisfied. In selecting the numerical values of layer thickness T _B and layer thickness T, more preferably T _B /T≦0.9, optimally T _B /T≦
Layer thickness T _B and layer thickness T so that the relationship 0.8 is satisfied
It is desirable that the value of . In the photoconductive member of the present invention shown in FIG.
Second layer region (V) containing group atoms
Although the first layer region (O) 103 is formed within 104, the first layer region (O) and the second layer region (V) can also be made into the same layer region. Further, a case where the second layer region (V) 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 characteristics required of the photoconductive member to be formed, but is usually 0.001 to 50 atomic %. , preferably 0.002~
It is desirable that it be 40 atomic %, optimally 0.003 to 30 atomic %. Is the layer thickness T _O of the first layer region (O) sufficiently thick?
Or, if the ratio of the first amorphous layer () to the total layer thickness exceeds two-fifths or more, the upper limit of the amount of oxygen atoms contained in the first layer region (O) is typically 30 atomic % or less, preferably 20 atomic % or less, optimally 10 atomic %
The following is desirable. In the present invention, the thickness of the first amorphous layer ( ) is usually 1 to 100 μm, preferably 1 to 100 μm, from the viewpoint of obtaining desired electrophotographic properties and economical efficiency. It is desirable that the thickness be 80μ, and optimally 2 to 50μ. 2 to 10 show the distribution in the layer thickness direction of oxygen atoms contained in the first layer region (O) constituting the first amorphous layer ( ) of the photoconductive member in the present invention. Typical examples of conditions are shown. In the examples shown in FIGS. 2 to 10, the layer region (V) containing group atoms does not include the layer region (O) even if it is the same layer region as the layer region (O). However, in the following explanation, the layer region (V) containing group atoms will not be particularly referred to. Do not mention unless an explanation is required. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of oxygen atoms, and the vertical axis represents the layer region (O) constituting the amorphous layer exhibiting photoconductivity and containing oxygen atoms.
indicates the layer thickness T _O , and t _B is the position of the interface on the support side,
t _T indicates the position of the interface on the opposite side to the support side. That is, in the layer region (O) containing oxygen atoms, the layer is formed from the t _B side toward the t _T side. In the present invention, the layer region (O) containing oxygen atoms is a-Si (H,
X) and occupies a part of the first amorphous layer () exhibiting photoconductivity. In the present invention, the layer region (O) is the support 10 of the first amorphous layer ( ) as shown in the example of FIG.
a first amorphous layer ( ) 102 including the surface of one side;
It is preferable that it be provided in the lower layer region of. FIG. 2 shows a first typical example of the distribution state of oxygen atoms contained in the layer region (O) in the layer thickness direction. In the example shown in FIG. 2, from the interface position _tB where the surface where the layer region (O) containing oxygen atoms is formed and the surface of _the layer region (O) contact, the oxygen A layer region (O) where oxygen atoms are formed while the atomic distribution concentration C takes a constant value of _C1 .
The distribution concentration C is contained in the interface position t _T from position t ₁ .
It is gradually and continuously decreased from C ₂ up to . At the interface position _tT , the distribution concentration of oxygen atoms C
is assumed to be C ₃ . In the example shown in FIG. 3, the distribution concentration C of the contained oxygen atoms gradually and continuously decreases from C ₄ to position t _T from position t _B to position t _T.
A distribution state such as C ₅ is formed. In the case of Fig. 4, the distribution concentration C of oxygen atoms is constant at _C6 from position t _B to position t ₂ , and at position t ₂
It is gradually and continuously decreased between and the position _tT , and becomes substantially zero at the position _tT . In the case of Figure 5, the oxygen atom is located at a position lower than position t _B.
Until t _T , the distribution concentration C is gradually decreased continuously from C ₈ and becomes substantially zero at the position t _T . In the example shown in FIG. 6, the distribution concentration C of oxygen atoms is a constant value of _C9 between position _tB and position _t3 , and _C10 at position _tT . 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 oxygen atoms decreases linearly from C ₁₄ to zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C of oxygen atoms decreases linearly from C ₁₅ to C ₁₆ , and between position t ₅ and t _T. , C ₁₆ are shown as constant values. In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is C ₁₇ at position t _B , and from this C 17 it gradually decreases until reaching position t ₆ , and then the distribution concentration C of oxygen atoms decreases slowly from this C ₁₇ until reaching position t ₆ . , 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 . , reaching C ₂₀ . position t ₈ and position t _T
In between, the distribution concentration C is reduced 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 oxygen atoms contained in the layer region (O) in the layer thickness direction, in the present invention, on the support side , a layer region containing oxygen atoms in a distributed state, which has a portion where the distribution concentration C of oxygen atoms is high, and has a portion where the distribution concentration C is relatively lower on the interface _tT side than on the support side. (O) is provided in the first amorphous layer (). In the present invention, the layer region (O) containing oxygen atoms constituting the first amorphous layer () contains oxygen atoms at a relatively high concentration toward the support side, as described above. It is desirable to provide the support with localized regions (A), and in this case, the adhesion between the support and the first amorphous layer () can be further improved. If the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable 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 5μ thick from the interface position t _B , or may be a part of the layer region L _T. be. Whether the localized region (A) is a part or all of the layer region L _T is appropriately determined according to the characteristics required of the first amorphous layer (I) to be formed. The localized region (A) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of oxygen atoms is usually 500 atomic ppm or more, preferably 800 atomic ppm or more, and most preferably 800 atomic ppm or more.
It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be achieved. That is, in the present invention, the layer region (O) containing oxygen atoms has the maximum value of the distribution concentration C within 5 μm in layer thickness from the support side (layer region 5 μ thick 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 (V) containing group atoms is appropriately determined as desired so that the object of the present invention is effectively achieved. However, usually 0.01~5×
10 ⁴ atomic ppm, preferably 0.5 to 1×10 ⁴ atomic
ppm, preferably 1 to 5×10 ³ atomic ppm. In the photoconductive member of the present invention, the second layer region (V) forming a part of the first amorphous layer (V)
When the photoconductive member is subjected to charging treatment, the second layer region is mainly charged with the function of preventing charge injection from the support side to the first amorphous layer (). In the relationship between the content of group atoms contained in (V) and the layer thickness and characteristics of the layer region provided directly on the second layer region (V), the second layer region ( It is desirable that the layer thickness of V) is appropriately determined as desired so that the above-mentioned functions can be sufficiently performed. In the present invention, when the above points are mainly considered, the layer thickness of the second layer region (V) is usually 30
Å~5μ, preferably 40Å~4μ, optimally 50Å~3μ
It is desirable that this is the case. 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 first amorphous layer ( ) composed of a-Si(H,X). It is made by vacuum deposition method. For example, to form the first amorphous layer ( ) composed of a-Si (H, Together with the supply source gas, a source gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. , a layer made of a-Si (H, In addition, when forming by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms ( A gas for introducing H) or/and 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 (X) as necessary include fluorine, chlorine, bromine, and iodine, particularly fluorine. , chlorine can be mentioned as suitable. 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 silicon halide gas, which is a raw material gas for supplying Si, and Ar, H ₂ , He, etc. Introducing gases and the like into a deposition chamber for forming the first amorphous layer () at a predetermined mixing ratio and gas flow rate, and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to introduce hydrogen atoms, a silicon compound gas containing hydrogen atoms is added to these gases. A predetermined amount of these materials may also be mixed 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. To form the first amorphous layer () made of a-Si(H, Then, this is sputtered in a predetermined gas plasma atmosphere, and in the case of ion plating method, polycrystalline silicon or single crystal silicon is accommodated in the evaporation port as an evaporation source, and this silicon evaporation source is used by resistance heating method or This can be done by heating and evaporating the flying evaporates using an electron beam method (EB method) or the like 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 a 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 hydrogen silicon 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 effective. It can be mentioned as a 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. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen atoms. In order to structurally introduce hydrogen atoms into the first amorphous layer (), in addition to the above, H ₂ or SiH ₄ ,
Silicon hydride gas such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ etc.
This can also be done by causing a discharge by coexisting in a deposition chamber with a silicon compound for supplying Si. 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 support. Furthermore, a gas such as B ₂ H ₆ can also be introduced for doping with impurities. In the present invention, hydrogen atoms (H) contained in the first amorphous layer () of the photoconductive member to be formed
The amount of , the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms is usually 1 to
It is desirable that it be 40 atomic %, preferably 5 to 30 atomic %. In order 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 of hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain the atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In order to provide the layer region (V) containing Group Group atoms and the layer region (O) containing oxygen atoms in the first amorphous layer (2), the first method is performed using a glow discharge method, a reactive sputtering method, etc. When forming the amorphous layer (), 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 (), respectively. , by controlling the amount and containing it in the formed layer. When a glow discharge method is used to form the layer region (O) containing oxygen atoms and the layer region (V) containing group atoms, which constitute the first amorphous layer (I), each layer The starting material that becomes the raw material gas for forming the region is the first amorphous layer () described above.
The starting materials for the introduction of oxygen atoms and/or the starting materials for the introduction of group atoms are added to those selected as desired among the starting materials for the formation. 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 a layer region (O) is to be formed, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or and a raw material gas whose constituent atoms are halogen atoms (X) at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen. A raw material gas containing atoms (H) as constituent atoms is also mixed at a desired mixing ratio, or
Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si) and oxygen atoms (O)
and a raw material gas containing three hydrogen atoms (H) as constituent atoms can be used in combination. 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 ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monooxide (N ₂ O ), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si) and oxygen atoms (O )
and a hydrogen atom (H) as constituent atoms, for example,
Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). When forming the layer region (V) using a glow discharge method, the starting materials for introducing group group atoms that are effectively used in the present invention are PH ₆ and P ₂ H for introducing phosphorus atoms. Phosphorus hydride such as ₄ , PH ₄ I,
Examples include phosphorus halides such as PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , PI ₃ and the like. In addition, AsH ₃ ,
AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ ,
SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. The content of group atoms introduced into the layer region (V) 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 It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. To form the layer region (O) containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or a SiO ₂ wafer, or a Si and
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 diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. 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, 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 include: So-called rare gases, such as He, Ne, Ar, etc., can be mentioned as suitable gases. In the photoconductive member of the present invention, a layer region (B) not containing group atoms is provided on the layer region (V) containing group atoms (corresponding to layer region 105 in FIG. 1). The layer region (B) contains a substance that controls conduction properties.
The conduction properties of can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-
P gives P-type conduction characteristics to Si(H,X)
Type impurities, specifically atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium),
Examples include Tl (thallium), among which B and Ga are particularly preferably used. In the present invention, the content of the substance that controls the conductive properties contained in the layer region (B) is determined by the conductive properties required for the layer region (B) or the substance that is in direct contact with the layer region (B). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided as well as the characteristics of the contact interface with the other layer regions. In the present invention, the content of the substance controlling conduction properties contained in the layer region (B) is usually 0.001 to 1000 atomic ppm, preferably 0.05 atomic ppm.
~500atomic ppm, optimally 0.1~200atomic
It is preferable to set it in ppm. In order to structurally introduce substances that control the conduction properties, for example group atoms, into the layer region (B), the starting material for introducing group atoms is introduced in a gaseous state into the deposition chamber during layer formation. It may be introduced together with other starting materials for forming one 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 ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as BBr ₃ . Other examples include AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ and TlCl ₃ . In the photoconductive member 100 shown in FIG. 1, the second amorphous layer ( ) 106 formed on the first amorphous layer ( ) 102 has a free surface 107 and is primarily moisture resistant. properties, continuous repeated use characteristics, pressure resistance,
This is provided in order to achieve the objectives of the present invention in terms of usage environment characteristics and durability. Further, in the present invention, the first amorphous layer ()
Since each of the amorphous materials constituting the and the second amorphous layer () has a common constituent element of silicon atoms, chemical stability can be sufficiently ensured at the laminated interface. has been done. The second amorphous layer () is an amorphous material [a-(Si _x C _1-x ) _y X _1-y , where 0 <x, y<
1]. The second amorphous layer () composed of a-( _{Si x} C _1-x ) _y This is done by the 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 silicon atoms, and carbon atoms and halogen atoms can be easily introduced into the second amorphous layer (2) to be manufactured. Due to these 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 X _1-y is mixed with a diluting gas as necessary. The mixture is mixed at a predetermined mixing ratio 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 generating a glow discharge, and the gas is already deposited on the support. The first amorphous layer formed ()
It is sufficient to deposit a-(Si _x C _1-x ) _y X _1-y thereon. In the present invention, the raw material gas for forming a-(Si _x C _1-x ) _y X _1-y includes at least one of silicon atoms (Si), carbon atoms (C), and halogen atoms (X). Most gaseous substances having one constituent atom 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. Among the constituent atoms, F, Cl, Br, and I are preferable as the halogen atom (X) contained in the second amorphous layer (2), with F and Cl being particularly preferable. In the present invention, the second amorphous layer (a)
-(Si _x C _1-x ) _y X _1-y , but it is possible to further contain a hydrogen atom. The inclusion of hydrogen atoms in the second amorphous layer (2) makes it possible to share some of the raw material gas types when forming a continuous layer with the first amorphous layer (2), which reduces production costs. It is convenient for the above. 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 those that can be easily gasified. Can list substances. Examples of substances for forming such a second amorphous layer include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 3 carbon atoms.
acetylenic hydrocarbons, elemental halogens, hydrogen halides, interhalogen compounds, silicon halides,
Examples include halogen-substituted silicon hydride and silicon hydride. 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 , silicon hydride includes SiH ₄ , Si ₂ H ₄ ,
Examples include silanes such as Si ₄ H ₁₀ , etc. 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 and SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ 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 ₅ CH ₈ can also be mentioned as effective examples. 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 () to be formed. When forming the second amorphous layer, it is selected and used as desired so that it contains atoms. 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 contain halogen atoms. ₄ , SiH ₂ Cl ₂ , or SiH ₃ Cl, etc. at a predetermined mixing ratio and introducing it in a gaseous state into the apparatus for forming the second amorphous layer () to generate a glow discharge. −(Si _x
A second amorphous layer ( ) consisting of C _1-x ) _y (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; These may be performed by sputtering in various gas atmospheres containing halogen atoms and, if necessary, 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 containing Si and C. It is accomplished by doing so. In the case of the sputtering method, the material for forming the second amorphous layer () shown in the glow discharge example mentioned above is used as the raw material gas for introducing C, X, and H if necessary. can also be used as effective substances. In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluting gas when forming the second amorphous layer () by the glow discharge method or the sputtering method. It can be mentioned as a suitable one. The second amorphous layer ( ) in the present invention is carefully formed so as to provide the desired properties. In other words, substances whose constituent atoms are Si, C, X, and optionally H can have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrically conductive to semiconductive. , exhibiting properties ranging from insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so 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 Created as a distinctly 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 degree of electrical insulation described above is relaxed to some extent, and it becomes more resistant to the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y X _1-y
is created. a−(Si _x C _1-x ) _y on the surface of the first amorphous layer ()
When forming the _second amorphous layer () consisting of In this case, a-(Si _x
It is desirable that the temperature of the support during layer formation be strictly controlled so that C _1-x ) _y X _1-y can be formed as desired. In the present invention, the second amorphous layer () is formed 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. formation is performed, but typically 50~
The temperature is desirably 350°C, preferably 100-250°C. In order to form the second amorphous layer (2018), we use a glow method, as it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. It is advantageous to adopt the discharge method or the sputtering method, but when forming the second amorphous layer () using these layer formation methods, the temperature during layer formation as well as the support temperature described above must be adjusted. The discharge power is one of the important factors that influences the characteristics of a-(Si _x C _1-x ) _y X _1-y created. _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 preferable numerical ranges of the support temperature and discharge power for forming the second amorphous layer ( ) include the values in the above ranges, but these layer forming factors are independent of each other. The desired characteristics a−(Si _x C _1-x ) _y
It is desirable that the optimum value of each layer formation factor be determined based on the mutual organic relationship so that the second amorphous layer ( ) consisting of X _1-y is formed. The amounts of carbon atoms and halogen atoms contained in the second amorphous layer () in the photoconductive member of the present invention are the same as the conditions for producing the second amorphous layer ().
This is an important factor in the formation of the second amorphous layer (), which 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 1-90 atomic%, optimally 10-90 atomic%
It is preferable to set it to 80 atomic.
The content of halogen atoms is usually 1
~20 atomic %, preferably 1-18 atomic %,
The optimum content is preferably 2 to 15 atomic %, and photoconductive members prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms that are included as necessary is usually 19 atomic.
%, preferably 13 atomic % or less. That is, the previous a-(Si _x C _1-x ) _y X _1-y
If x and y are displayed, x is usually 0.1 to 0.99999,
Preferably 0.1 to 0.99, optimally 0.15 to 0.9, y usually 0.8 to 0.99, preferably 0.82 to 0.99, optimally 0.85
~0.98 is desirable. When both a halogen atom and a hydrogen atom are included, the same a-(Si _x
C _1-x ) _y (H+X) _1-y , the numerical range of x and y in this case is a-(Si _x C _{1 -x} ) _y
Almost the same. 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. In addition, the thickness of the second amorphous layer () has an organic relationship with the thickness of the first amorphous layer depending on the characteristics required for each layer region. It needs to be determined appropriately depending on the nature and desire. 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 usually 0.003 to 30 μm, preferably 0.004 to 20 μm, and most preferably 0.005 to 10 μm. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined as appropriate so that the photoconductive member is formed as desired, but if flexibility is required for the photoconductive member, the thickness is determined within a range that allows the support to function adequately. If inside, it will be made as thin as possible. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming each layer region of the present invention is sealed, for example, 110
2 is SiH ₄ diluted with He (purity 99.999% or less)
Abbreviated as SiH ₄ /He. ) cylinder, 1103 is PH ₃ gas diluted with He (purity 99.999%, hereinafter PH ₃ /
Abbreviated as He. ) cylinder, 1104 is C ₂ H ₄ gas (purity 99.99%) cylinder, 1105 is NO gas (purity
99.99%) cylinder, 1106 diluted with He
It is a SiF ₄ gas (purity 99.999%, hereinafter abbreviated as SiF ₄ /He) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2 to 1126, confirm that the leak valves 1135 are closed, and also check that the inflow valves 1112 to 1126 are closed.
1116, check that the outflow valves 1117 to 1121 and the auxiliary valve 1132 are open, and first open the main valve 1134 to drain the reaction chamber 110.
1. Evacuate the inside of the gas pipe. Next, the vacuum gauge 1136
When the reading reaches approximately 5×10 ⁻⁶ torr, the auxiliary valve 1132 and the outflow valves 1117 to 1121 are closed. Next, an example will be given in which a photoconductive member having the layer structure shown in FIG. 1 is formed on the base 1137. SiH ₄ /He gas from gas cylinder 1102, PH ₃ /He gas from gas cylinder 1103, gas cylinder 11
From 05, NO gas is supplied from 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. Subsequently, the outflow valves 1117, 1118, 1120 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. SiH ₄ /He at this time
Outflow valve 1117, so that the ratio of gas flow rate, PH ₃ /He gas flow rate, and NO gas flow rate becomes a desired value.
1118 and 1120, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure in the reaction chamber reaches the desired value. 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 heating heater 1138, the power supply 11
40 to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the NO gas flow rate is controlled manually or by an externally driven motor or the like in accordance with a pre-designed rate of change curve.
120 is performed to control the distribution concentration of oxygen atoms contained in the formed layer in the layer thickness direction. As described above, when the layer region (P, O) containing phosphorus atoms and oxygen atoms is formed to the desired layer thickness, the outflow valves 1118 and 1120 are closed, and the PH ₃ / By continuing layer formation under the same conditions except for blocking the inflow of He gas and NO gas, a layer region containing no oxygen atoms and phosphorus atoms is formed on the layer region (P, O) as desired. Form thickly. In this way, the first amorphous layer ( ) having desired characteristics can be formed on the substrate 1137. The layer region (V) containing phosphorus atoms is formed at an appropriate point in the formation process of the first amorphous layer ().
By cutting off the flow of PH ₃ /He gas into the reaction chamber 1101, it is possible to form a layer with a desired thickness. Any of the cases where it occupies a part can be realized. For example, in the above example, the layer region (P,
When NO) is formed to a desired thickness, the outflow valve 1120 controls the inflow of NO gas into the reaction chamber 1101.
The layer region (P,
A layer region containing phosphorus atoms but no oxygen atoms on O) can be formed as part of the first amorphous layer (). Further, when forming a layer region that does not contain phosphorus 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 (I), for example, SiF ₄ /He is added to the above gas.
is further added and sent into the reaction chamber 1101. Depending on the selection of gas species during the formation of the first amorphous layer (2), the layer formation rate 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. To form the second amorphous layer ( ) on the first amorphous layer ( ), for example, the following procedure is performed. First, open shutter 1142. All gas supply valves are once closed, and the reaction chamber 1101 is evacuated by fully opening the main valve 1134. 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. By turning on the high-voltage power supply and sputtering the target, the second amorphous layer () can be formed on the first amorphous layer (). 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 glow discharge according to desired conditions. . Needless to say, all the 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 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 ( ) can be determined, for example, by changing the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas introduced into the reaction chamber 1101 as desired; Alternatively, when forming a layer by sputtering, the target may be formed by changing the sputter area ratio of the silicon wafer and graphite wafer, or by changing the mixing ratio of silicon powder and graphite powder. can be controlled as desired. The amount of halogen atoms (X) contained in the second amorphous layer () is determined by the raw material gas for introducing halogen atoms,
For example, this can be done by adjusting the flow rate when SiF ₄ gas is introduced into the reaction chamber 1101. Example 1 Using the manufacturing apparatus shown in FIG.
An imaging member having an oxygen concentration distribution within the layer as shown in FIG. 12 was prepared under the conditions shown in Table 1. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 1.5 lux·sec was irradiated through 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. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 2 Using the manufacturing apparatus shown in Fig. 11, the first and second
An imaging member having an oxygen distribution concentration in the layer as shown in FIG. 13 was prepared under the conditions shown in Table 2. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 3 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen distribution concentration as shown in FIG. 14 in the first layer was produced under the conditions shown in Table 3. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 When forming the amorphous layer (), SiH ₄ gas,
The method was exactly the same as in Example 1, except that the flow rate ratio of SiF ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the amorphous layer (). An image forming member was then prepared. 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 4 were obtained. Example 5 An imaging member was prepared in exactly the same manner as in Example 1 except that the thickness of the amorphous layer ( ) was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 5. Example 6 Layers were formed in the same manner as in Example 1, except that the method of forming the first and second layers was changed as shown in Table 6, and the image quality was evaluated in the same manner as in Example 1. Good results were obtained as shown in .

【table】

【table】

【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Some image defects occur

【table】

[Table] Example 7 The conditions and procedures shown in Examples 1 and 2 were followed, except that when creating the second layer region in Examples 1 and 3, the layer creation conditions were set to the conditions shown in Table 7. Accordingly, electrophotographic image forming members were produced and evaluated in the same manner as in Example 1. As a result, good results were obtained for each of them, particularly in terms of image quality and durability.

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 are layer regions containing oxygen atoms (O ), FIG. 11 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 12 to 14 are diagrams for explaining the distribution state of oxygen atoms in the present invention. FIG. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 103...First
layer region (O), 104... second layer region (V),
105... Upper layer region, 106... Second amorphous layer (), 107... Free surface.

Claims (1)

[Claims] 1. A support for a photoconductive member for electrophotography, a first amorphous layer having photoconductivity and having a layer thickness of 1 to 100 μm and made of an amorphous material having silicon atoms as a matrix, and silicon atoms. and a second amorphous layer with a layer thickness of 0.003 to 30 μ made of an amorphous material containing 1 × 10 ^-3 to 90 atomic% of carbon atoms and halogen atoms, and the first amorphous layer layers as constituent atoms
A first layer region containing 0.001 to 50 atomic% of oxygen atoms and occupying a part of the first amorphous layer in contact with the support;
a second layer region having a layer thickness of 50 μm or less containing atoms belonging to Group Group of the Periodic Table of 10 ⁴ atomic ppm in a substantially uniform distribution state in the layer thickness direction; The layer is non-uniform and continuous in the layer thickness direction, having a portion where the distribution concentration of oxygen atoms is high at 500 atomic ppm or more on the support side, and a portion where the distribution concentration of oxygen atoms is lower than that on the support side on the second amorphous layer side. A photoconductive member for electrophotography, characterized in that it has a distribution state.