JPH0454943B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, r-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. Fixed imaging devices are sometimes 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 exchange reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall characteristics. 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 time, fatigue accumulates due to repeated use, resulting in so-called ghost development, which causes afterimages. For example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member can be replaced with conventional inorganic photoconductive materials such as Se, CdS, ZnO, etc. Although it has many advantages compared to organic photoconductive materials such as PVCz and TNF,
Charging treatment for forming an electrostatic image on the photoconductive layer of an electrophotographic imaging member having a single-layer photoconductive layer made of a-Si that has been given properties for use as a conventional solar cell. However, the dark decay is extremely fast even when the electrophotographic method is applied, making it difficult to apply normal electrophotography, and in a humid atmosphere, the above tendency is remarkable, and in some cases, the electrostatic charges may be retained until the development time. It has been found that there are some points that can be resolved, such as cases in which it is almost impossible to hold. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may arise in the electrical, optical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, fixed imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] "a-Si(H,X)" is used as a generic notation for It not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. It is based on the findings that The electrical, optical, and photoconductive properties of the present invention are almost always stable without being controlled by the usage environment, and are extremely resistant to light fatigue, and do not cause deterioration even after repeated use. The main object of the present invention is to provide a photoconductive member which has excellent durability and has no or almost no residual potential 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 pressure resolution. Yet another object of the present invention is to provide a photoconductive member having high light sensitivity, high signal-to-noise ratio characteristics, and good electrical contact with the support. The photoconductive member of the present invention is composed of a support for the photoconductive member and an amorphous material containing silicon atoms as a matrix, and includes a first amorphous layer () exhibiting photoconductivity, silicon atoms and halogen atoms and their content
and a second amorphous layer () made of an amorphous material containing less than 40 atomic% carbon atoms as constituent atoms, the first amorphous layer () comprising:
A first layer region (O) containing oxygen atoms as constituent atoms and having a region whose distribution concentration gradually decreases in the layer thickness direction; having a layer region that does not substantially contain atoms, and a second layer region () containing atoms belonging to group of the periodic table in a continuous distribution state in the layer thickness direction as constituent atoms, The first layer region (0) and the second layer region () are provided in contact with the support and share at least a part of each other. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties and a usage environment. Show characteristics. In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio and is excellent in light fatigue resistance, repeated use characteristics, especially in a humid atmosphere, and is of high quality with high density, clear halftones, and high resolution. A visible image can be obtained. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic diagram schematically showing the layer structure of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 has a photoconductive layer made of a-Si (H, It has one amorphous layer ( ) 102 . The amorphous layer ( ) 102 includes a first layer region (O) 103 containing oxygen atoms as constituent atoms, and a second layer region (O) 103 containing atoms belonging to Group Group of the Periodic Table (Group atoms). 104, and a layer region 106 on the second layer region ( ) 104 that does not contain oxygen atoms or group atoms. The layer region 105 provided between the first layer region (O) 103 and the layer region 106 does not contain oxygen atoms, although group group atoms are contained therein. The oxygen atoms contained in the first layer region (O) 103 are continuously distributed in the layer thickness direction in the layer region (O) 103, and the distribution state is non-uniform; A continuous and substantially uniform distribution in a direction substantially parallel to the surface of body 101 is preferred. In the photoconductive member of the present invention, as shown in FIG.
It is necessary to have a layer region containing no oxygen atoms (corresponding to the layer region 106 shown in FIG. 1), but a layer region containing group atoms but no oxygen atoms (corresponding to the layer region 106 shown in FIG. Layer area 10 shown
5) does not necessarily need to be provided. That is, for example, the first layer region (O) and the second layer region () may be the same layer region, or
A second layer region (O) may be provided within the first layer region (O). The group atoms contained in the second layer region () are continuously distributed in the layer thickness direction in the layer region (), and even if the distribution state is non-uniform, it is substantially uniform. However, it is preferable that it is continuously and substantially uniformly distributed in a direction substantially parallel to the surface of the support. In the photoconductive member 100 shown in FIG. 1, the layer region 106 does not contain group atoms, but in the present invention, the layer region 106 may also contain group atoms. It is something. In the photoconductive member of the present invention, the first layer region (O) contains oxygen atoms to provide a high dark resistance and a bond with the support on which the amorphous layer () is directly provided. The focus is on improving the adhesion between the two. In particular, as in the photoconductive member 10 shown in FIG. A layer region (O) 104, a layer region 105 containing no oxygen atoms, and a layer region 106 containing no oxygen atoms or group atoms, the first layer region (O) 103 and the second layer region area()1
Better results are obtained in the case of a layer structure having a layer area shared with 04. Further, in the photoconductive member of the present invention, the distribution state of oxygen atoms contained in the first layer region (O) in the layer thickness direction in the layer region (O) is determined firstly by In order to improve adhesion and contact with the support or other layers on which the first layer region (O) is provided, the distribution concentration should be higher on the side of the bonding surface with the support or other layers. be done. Secondly, the oxygen atoms contained in the first layer region (O) generate electricity at the bonding interface with the layer region that does not contain oxygen atoms and is provided on the first layer region (O). In order to smooth the surface contact, the distribution concentration is gradually reduced in the layer region side where no oxygen atoms are contained, and at the bonding surface, the first concentration is reduced so that the distribution concentration becomes substantially zero. It is preferably contained in the layer region (O). This point also applies to the group atoms contained in the second amorphous layer ( ), and the group atoms in the layer region on the surface side of the amorphous layer ( ) are not contained. In the case of the above example, on the side of the layer region on the surface side, the distribution concentration of group atoms in the second layer region ( ) is gradually reduced in the direction of the bonding surface with the layer region on the surface side, It is preferable that the distribution state of the group atoms is formed such that . In the present invention, atoms belonging to group of the periodic table contained in the second layer region ( ) constituting the amorphous layer ( ) are B (boron),
These include Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. In the present invention, the content of group atoms contained in the second layer region (2) may be appropriately determined as desired so as to effectively achieve the object of the present invention. Usually 0.01 to 1000 atomic ppm, preferably 0.5 to 800 atomic ppm, optimally 1 to 800 atomic ppm, relative to the amount of silicon atoms constituting the layer.
It is desirable that the content be 500 atomic ppm. The amount of oxygen atoms contained in the first layer region (O) can be determined as desired depending on the properties required of the photoconductive member to be formed, but usually 0.001~ 20atomic%, preferably
0.002-10atomic%, optimally 0.003-5atomic%
It is desirable that this is the case. 2 to 10 each show typical examples of the distribution state of oxygen atoms and group atoms contained in the amorphous layer ( ) of the photoconductive member in the layer thickness direction in the present invention. . In FIGS. 2 to 10, the horizontal axis represents the concentration C of oxygen atoms or group atoms, the vertical axis represents the layer thickness direction of the amorphous layer exhibiting photoconductivity, and _tB represents the support t S indicates the position of the surface of the amorphous layer ( ) on the body side, and t _S indicates the position of the surface of the amorphous layer ( ) on the side opposite to the support side. The amorphous layer ( ) containing oxygen atoms and group group atoms grows from the t _B side toward the t _S side. Note that the scale of the vertical axis is different for oxygen atoms and group atoms. Further, A ₂ to _{A 10} represent the distribution concentration lines of oxygen atoms, and B ₂ to _{B 10} represent the distribution concentration lines of group atoms, respectively. FIG. 2 shows a first typical example of the distribution state of oxygen atoms and group atoms contained in the amorphous layer ( ) in the layer thickness direction. In the example shown in Fig. 2, an amorphous layer ()t _S , t _B (from t _S to
t _B ), from the support side, oxygen atoms have a distribution concentration C _(O)1 , and group atoms have a distribution concentration C ₍ 〓 ₎₁
, the layer regions t ₂ , t _B (layer region between t ₂ and t _B ) are substantially uniformly distributed in the layer thickness direction, and the distribution concentration of oxygen atoms is the distribution concentration C _(O)1 A layer region t ₁ in which the distribution concentration of group atoms gradually decreases linearly from C ₍ 〓 ₎₁ to substantially zero, t ₂ and layer regions t _S and t ₁ in which neither oxygen atoms nor group group atoms are substantially contained. As in the example shown in Fig. 2, the amorphous layer ()t _S , t _B is
When the layer region t ₂ , t _B has a contact surface with the support or another layer (corresponding to t _B ) and the distribution of oxygen atoms and group atoms is uniform, the distribution concentration C ₍ 〓 ₎₁ and C _(O)1 can be determined as desired in relation to the support or other layers, but
In the case of C ₍ 〓 ₎₁ , it is usually 0.1 for silicon atoms.
~10000 atomic ppm, preferably 1-4000 atomic
ppm, optimally 2 to 2000 atomic ppm, C _(O)1
For silicon atoms, typically 0.01~
It is desirable that the content be 30 atomic %, preferably 0.02 to 20 atomic %, most preferably 0.03 to 10 atomic %. The layer regions t ₁ , t ₂ are provided mainly to smooth electrical contact between the layer regions t _S , t ₁ and the layer regions t ₂ , t _B ; The layer thicknesses of ₁ and _t2 can be adjusted as desired in relation to the distribution concentration C _(O)1 of oxygen atoms and the distribution concentration C ₍ 〓 ₎₁ of group atoms, especially the distribution concentration C _(O)1. Therefore, it needs to be determined. The layer region t _S , t ₁ may contain group group atoms if necessary, but the layer region t ₁ does not contain oxygen atoms. If t _B is sufficiently protected from the atmosphere and if photocarriers are generated by light irradiation in the layer regions t _S , t ₁ , the irradiated light will be applied to the layer regions t _S , t 1 . It can be determined as desired so that sufficient absorption is achieved at _t1 . In the present invention, the layer thickness of the layer region that does not contain oxygen atoms provided on the surface side of the amorphous layer ( ) is usually 100 Å to 10 μ, preferably 200 μm.
It is desirable that the thickness be 500 Å to 3 μ, most preferably 500 Å to 3 μ. In a photoconductive member having a distribution state of oxygen atoms and group atoms as shown in Fig. 2, it is possible to achieve high photosensitivity and high dark resistance, while also achieving high adhesion with the support or other layers. and the amorphous layer from the support side ()
To further improve the ability to prevent charge injection into the
As shown by the dashed line a in FIG. 2, on the surface of the amorphous layer on the support side (corresponding to the position t _B ),
It is preferable to provide layer regions t ₃ and t _B in which the distribution concentration of oxygen atoms is higher than the distribution concentration C _(O)1 . Layer regions t ₃ , t _B where oxygen atoms are distributed at high concentration
The distribution concentration of oxygen atoms C _(O)2 in silicon atoms is normally desirably 30 atomic % or more, optimally 40 atomic % or more, and optimally 50 atomic % or more. . The distribution state of oxygen atoms in a layer region where oxygen atoms are distributed at a high concentration may be constant (uniform) in the layer thickness direction, as shown by the dashed line a in Fig. 2, or may be made uniform by direct bonding. In order to improve the electrical contact between the adjacent layer region, as shown by the dashed line b, from the support side, a constant value of C _(O)2 is applied up to a certain thickness, and then to C _(O)1. It may be made to gradually decrease continuously until it becomes. The distribution state of the group atoms contained in the second layer region () in the layer region () is such that the distribution state of the group atoms contained in the second layer region _{( )} is the layer region [layer _However , in order to more efficiently prevent charge injection from the support side to the _amorphous layer, the support side is provided with a It is desirable to provide layer regions t ₄ and t _B in which group group atoms are distributed at a high concentration, as indicated by the dashed line C. In the present invention, the layer regions t ₄ and t _B are located from the position t _B.
It is preferable that they be provided within 5μ. Layer area t ₄ , t _B
may be the entire layer region L _T up to a thickness of 5 μm from the position t _B or may be provided as a part of the layer region L _T . Whether the layer regions t ₄ and t _B are part or all of the layer region L _T is appropriately determined according to the characteristics required of the amorphous layer to be formed. The layer regions t ₄ and t _B are such that the maximum value Cmax of the content distribution value (distribution concentration value) of the group atoms is normally the distribution state of the group atoms contained therein in the layer thickness direction. It is desirable that the layer be formed in such a manner that a distribution state of 50 atomic ppm or more, preferably 80 atomic ppm or more, optimally 100 atomic ppm or more can be obtained. That is, in the present invention, the second layer region () containing group atoms has a maximum content Cmax within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ). Preferably, it is formed in such a way that it exists. In the present invention, the layer thicknesses of layer regions t ₃ and t _B in which oxygen atoms are distributed in high concentration and the layer thicknesses in layer regions t ₄ and t _B in which group group atoms are distributed in high concentration are as follows: It is determined as desired depending on the content and content distribution of oxygen atoms or group atoms contained in these layer regions, and is usually 30 Å to 5 μ, preferably
It is desirable that the thickness be 40 Å to 4 μ, most preferably 50 Å to 3 μ. The example shown in Fig. 3 is basically the same as the example shown in Fig. 2, but the difference is that in the case of the example shown in Fig. ₂ , the oxygen atom is Both the distribution concentration and the distribution concentration of group atoms begin to decrease,
On the other hand, in the case of the example in Figure ₃ , the distribution concentration of oxygen atoms decreases from position t ₃ to solid line B3, as shown by solid line A3. As shown, the distribution concentration of group atoms is from the position of t ₂ ,
Both begin to decrease, and at the position _t1 , both become substantially zero. That is, the first layer region (O)t ₁ , t _B containing oxygen atoms is separated from the layer region t ₃ , t _B in which the oxygen atoms are substantially uniformly distributed with a distribution concentration C _(O)1 , and the position Distribution concentration from t ₃
It consists of layer regions t ₁ and t ₃ that gradually decrease linearly from C _(O)1 to substantially zero. Second layer region containing group atoms ()
t ₁ , t _B are the layer regions t ₂ , t _B which are substantially uniformly distributed with the distribution concentration C ₍ 〓 ₎₁ , and the distribution concentration from the position t ₂
It consists of layer regions t ₁ and t ₂ that gradually decrease linearly from C ₍ 〓 ₎₁ to substantially zero. The layer regions t _S , t ₁ do not contain oxygen atoms or group atoms, similar to the layer regions t _S , t ₁ shown in FIG. The example _shown in FIG _. 4 is a modification of the example shown in _FIG . A layer region where group atoms are contained in a uniform distribution with a distribution concentration C ₍ 〓 ₎₁
This is the same as the case shown in FIG. ₃ , except that t 3 and t _B are provided. The example shown in FIG. 5 is a case in which there are two layer regions in which group atoms are contained in a uniform distribution at a constant distribution concentration. _The amorphous layer () in _the example _shown in FIG _. Consists of layer regions t ₁ and t ₃ that contain group group atoms but no oxygen atoms, and layer regions t _s and t ₁ that contain neither group group atoms nor oxygen atoms. has been done. Then, the layer region t ₃ containing oxygen atoms,
t _B is a layer region t ₅ , t _B that is substantially uniformly distributed in the layer thickness direction with a distributed concentration C _(O)1, and a layer region t 5 , t B that is substantially uniformly distributed in the layer thickness direction with a distributed concentration C _{(O)1, and a layer region t 5 , t B that is substantially uniformly distributed in the layer thickness direction with a distributed concentration C (O)1} . It is composed of layer regions t ₃ and t ₅ where the value reaches zero. The layer regions t ₁ , t _B are divided from the support side to the layer regions t ₄ , t _B in which group atoms are substantially uniformly distributed with a distribution concentration C ₍ 〓 ₎₁ , and from the distribution concentration C ₍ 〓 _)1. The layer region t 3 is distributed linearly and continuously decreasing up to the distribution concentration C ₍ 〓 _{) 3} ,
t ₄ , layer regions t ₂ , t ₃ that are substantially uniformly distributed with a distribution concentration C ₍ 〓 ₎ 3, and layer regions t that are distributed linearly and continuously decreasing from the distribution concentration C ₍ 〓 ₎₃ . ₁ and _t2 are laminated. FIG. 6 shows a modification of the example shown in FIG. In the case of the example shown in FIG. 6, layer regions t ₄ and t ₅ in which oxygen atoms and group group atoms are uniformly distributed with distribution concentrations C _(O)1 and C ₍ 〓 ₎₁ , respectively, and oxygen Atoms are distributed in concentration C _(O)1
Layer regions t _{4 , t 5} in which group group atoms are contained in a linearly decreasing distribution in layer regions t ₃ , t ₅ which are linearly gradually decreased from substantially zero to _zero ;
and layer regions t ₃ and t ₄ containing group atoms in a substantially uniform distribution state with a distribution concentration C ₍ 〓 _{) 3} . Layer regions t _S and t ₃ substantially free of oxygen atoms are provided above the layer regions t ₃ and t _B.
t _S , t ₃ are composed of layer regions ( ) t ₁ , t ₃ containing group atoms and layer regions t _S , t ₁ containing neither oxygen atoms nor group atoms. ing. In FIG. 7, group atoms are contained in the entire layer region of the amorphous layer ( ) [layer regions t _S , t _B ], and oxygen atoms are contained in the layer regions t _S , t ₁ on the surface side. An example is shown where this is not the case. The layer regions t ₁ and t _B containing oxygen atoms are indicated by the solid line A
As shown in 7, there is a layer region t ₃ , t _B in which oxygen atoms are contained in a uniform distribution with a distribution concentration C _(O)1 , and a distribution concentration C _(O)1 that gradually decreases to zero. It has layer regions (O) t ₁ and t ₃ containing oxygen atoms in a distributed state. The distribution of group atoms in the amorphous layer ( ) is shown by the solid line B7. That is, the layer regions t _S , t _B containing the group group atoms are the layer regions t ₂ , t B in which the group atoms are uniformly distributed with a distribution concentration C _(O)1 , and the layer regions t 2 , t _B in which the group atoms are uniformly distributed with a distribution concentration C ₍ 〓 _{) 2} , the distribution concentration C ₍ 〓 )1 and the distribution concentration C ₍ 〓 _{)2 are} formed between the layer region t _S and t ₁ in which group atoms are uniformly distributed.
In order to continuously change the distribution of group atoms between these distribution concentrations, the layer region t ₁ contains group atoms in a distribution state that continuously changes linearly between these distribution concentrations. t ₂ . FIG. 8 shows a variation of the example shown in FIG. 7. The entire layer area of the amorphous layer ( ) contains group atoms, as shown by the solid line B8, and the layer area
t ₁ and t _B contain oxygen atoms. layer area
At t ₃ , t _B , oxygen atoms have a distributed concentration C _(O)1 ,
Group atoms are contained in a uniform distribution state with a distribution concentration C ₍ 〓 ₎₁ , and in the layer regions t _S and t ₂ ,
Group atoms are contained in a uniform distribution with a distribution concentration C ₍ 〓 ₎₂ . Oxygen atoms are present in the layer region as shown by solid line A8.
At t ₁ and t ₃ , the concentration is gradually decreased linearly from the distribution concentration C _{(O) 1} from the support side to substantially zero at position t ₁ . In layer regions t ₂ and t ₃ , group atoms have a distribution concentration
It is contained in a distribution state that gradually decreases from C ₍ 〓 ₎₁ to distribution concentration C ₍ 〓 ₎₂ . Figure 9 shows that oxygen atoms are contained in a non-uniform distribution in the layer thickness direction, but group atoms are substantially uniform in the layer thickness direction in the layer region where they are continuously contained. An example is shown in which it is contained in a distribution state. In the example shown in FIG. 9, the first layer region (O) containing oxygen atoms and the second layer region () containing group atoms are substantially the same layer region. It has a layer region on the surface side that does not contain any oxygen atoms or group atoms. Oxygen atoms are contained in the layer regions t ₂ and t _B in a substantially uniform distribution with a distribution concentration C _(O)1 , and in the layer regions t ₁ and t ₂ the oxygen atoms are contained in a substantially uniform distribution state. It is contained in a distribution state that continuously decreases from C _(O)1 to C _(O)2 . In the example shown in FIG. 10, both oxygen atoms and group atoms are contained in a non-uniform distribution state in a continuously distributed layer region, and the layer region containing oxygen atoms is A layer region () is provided in which group group atoms are contained (O). In layer regions t ₃ and t _B , oxygen atoms have a distribution concentration C _(O)1 , group atoms have a distribution concentration C ₍ 〓 ₎₁ ,
Each of the oxygen atoms and group atoms are contained substantially uniformly at a constant distribution concentration, and in the layer regions t ₂ and t ₃ , the oxygen atoms and group atoms are respectively contained so that the distribution concentration gradually decreases as the layer grows, In the case of group atoms, the distribution concentration is assumed to be substantially zero at t ₂ . Oxygen atoms are contained so as to form a linearly decreasing distribution state even in the layer regions t ₁ and t ₂ where group group atoms are not contained, and the distribution state is substantially zero at t ₁ . It is said that The layer regions t _S , t ₁ contain no oxygen atoms or group atoms. Some typical examples of the distribution state of oxygen atoms and group atoms contained in the amorphous layer in the layer thickness direction have been explained above with reference to FIGS. 2 to 10.
In the cases shown in FIGS. 10 to 10, as explained in the case of _FIG . A layer region may be provided in which a distribution state of C is formed in a portion where C is considerably lower than that on the support side. Further, each of the distribution concentrations of oxygen atoms and group atoms may be decreased not only linearly but also curvilinearly. In the present invention, if necessary, an amorphous layer ()
Specific examples of the halogen atom (X) contained therein include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, the amorphous layer () composed of a-Si (H, done by. For example, by glow discharge method,
In order to form an amorphous layer composed of a-Si (H,
A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber. A layer made of a-Si(H,X) may be formed on the surface of the support.
In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. 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 ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention 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,
An amorphous layer made of a-Si:X can be formed on a predetermined support. When manufacturing an 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 ,
A gas such as He is introduced into a deposition chamber for forming an amorphous layer () at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. In particular, an amorphous layer () can be formed on a given support, but in order to introduce hydrogen atoms, a silicon compound gas containing hydrogen atoms may also be added to these gases. A layer may be formed by mixing quantitatively. In addition, 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 an amorphous layer () made 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. Law (EB Law)
This can be carried out by heating and evaporating the flying evaporated material by, for example, passing 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 blating 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 , SiH ₂
Halogen-substituted hydrogen silicon such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc., and halides that are one of the constituent elements of hydrogen atoms in a gaseous state or that can be gasified, are also effective non-halides. It can be mentioned as a starting material for the formation of a crystalline 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 when forming the amorphous layer. In the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the amorphous layer (), in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be done 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, an 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 amorphous layer () of the photoconductive member to be formed is a normal amount. case 1~40atomic%,
The preferred range is 5 to 30 atomic %. Hydrogen atoms (H) contained in the amorphous layer ()
Or/and to control the amount of halogen atoms (X), for example, the support temperature or/and hydrogen atoms (H)
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, a so-called rare gas, such as He,
Preferable examples include Ne, Ar, and the like. In order to introduce oxygen atoms and periodic table group atoms into the amorphous layer ( ) to form the first layer region (O) and the second layer region ( ), glow discharge method or reactive sputtering is used. When forming a layer by a method etc., a starting material for introducing a group atom or a starting material for introducing an oxygen atom, or both starting materials are used together with the above-mentioned starting material for forming an amorphous layer. This is achieved by containing it in a controlled amount in the layer. First layer region (O) constituting the amorphous layer ()
When using the glow discharge method to form
The starting material to be the raw material gas for forming the first layer region (O) is selected as desired from among the starting materials for forming the amorphous layer (O) mentioned above. Starting materials are added. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or halogen atoms (X) as necessary. A raw material gas is used by mixing it at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are oxygen atoms (O) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used in combination with a raw material gas having two constituent atoms. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (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 atoms (Si) and oxygen atoms (O)
and a hydrogen atom (H) as constituent atoms, for example,
Disiloxane H ₃ SiOSiH ₃ , Trisiloxane H ₃
Examples include lower siloxanes such as SiOSiH ₂ OSiH ₃ and the like. To form the first layer region containing oxygen atoms by the sputtering method, single-crystal or polycrystalline Si wafers or SiO ₂ wafers, or Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
In order to introduce halogen atoms, the raw material gas is diluted with a diluent gas as necessary and introduced into a sputtering deposition chamber, and a gas plasma of these gases is formed to sputter the Si wafer. Good. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. Second layer region () constituting the amorphous layer ()
In order to form the above-mentioned amorphous layer (2), together with the raw material gas for forming the above-mentioned amorphous layer (2), a gaseous or gasifiable starting material for introducing group atoms is added. It is sufficient to introduce the substance in a gaseous state into a vacuum deposition chamber for forming an amorphous layer. The content of group atoms introduced into the second layer region (2) is determined by controlling the gas flow rate, gas flow rate ratio, discharge power, etc. of the starting material for introducing group atoms introduced into the deposition chamber. Therefore, it can be controlled arbitrarily. In the present invention, starting materials for introducing group atoms that are effectively used for introducing boron atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H, ₁₁ ,B ₆
Boron hydride such as H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ etc. can also be mentioned. In the present invention, the formation of a transition layer region (a layer region in which the distribution concentration of either oxygen atoms or group atoms changes in the layer thickness direction) is achieved by controlling the flow rate of a gas containing a component whose distribution concentration is to be changed. This is achieved by making appropriate changes. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve. When creating an amorphous layer, there is no effect on the properties of the film even if the plasma state is maintained or interrupted at the boundary between the transition layer region and other layer regions, but it is best to perform it continuously. It is also preferable from a management perspective. In the present invention, the layer thickness of the amorphous layer ( ) is appropriately determined depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 100 ml.
The thickness is desirably 100μ, preferably 1 to 80μ, optimally 2 to 50μ. In the photoconductive member of the present invention, the second layer region () provided on the first amorphous layer () is
Amorphous material [a-(Si _X C _1-X ) _y ( H,
X) _1-y , but since it is formed with 0<x, y<1], the amorphous material constituting the first amorphous layer () and the second amorphous layer () Since each of them has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. The formation of the second amorphous layer () composed of a-(Si _x C _1-x )y(H,X) _{1-y can} be performed by glow discharge method, sputtering method, ion implantation method,
This is done by 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 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, a glow discharge method and a sputtering method may be used together in the same apparatus system to form the second amorphous layer (). In order to form the second amorphous layer ( ) by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y (H,X) _1-y is added as necessary. The gas is mixed with a diluted gas 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 then the support is converted into gas plasma. a-(Si _x C _1-x )y(H,X) _1-y may be deposited on the first amorphous layer ( ) already formed on the body. In the present invention, a-(Si _x C _1-x )y(H,X) _1-
As the raw material gas for forming _y , most gaseous substances containing at least one of Si, C, and X as a 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 Alternatively, 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. or with a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, F, Cl, Br, and I are preferable as the halogen atoms (X) contained in the second amorphous layer ( ), with F and Cl being particularly preferable. In the present invention, hydrogen atoms can be contained in the second amorphous layer (2) if necessary. The inclusion of hydrogen atoms in the second amorphous layer () is
This is advantageous in terms of production costs because it is possible to share some of the raw material gas types when forming a continuous layer with the first amorphous layer (2). 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 the substance for forming the second amorphous layer include saturated carbon hydrogen having 1 to 4 carbon atoms, ethylene hydrocarbon 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 ( _{C2H4 )} as an ethylene _hydrocarbon
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 ), and halogen alone:
Halogen gases such as fluorine, chlorine, bromine, and iodine, and 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 , halogen-substituted hydrogen silicon includes SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ ,
Examples of silicon hydride include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄
Silanes such as H ₁₀ , etc. can be mentioned. In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃
Halogen-substituted paraffinic hydrocarbons such as F, CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Si( Alkyl silicides such as C ₂ 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 optionally hydrogen atoms in a predetermined composition ratio in the second amorphous layer () to be formed. It is selected and used as desired when forming the second amorphous layer (2) 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 SiHCI can contain halogen atoms (X). ₃ , _SiCl4 , _{SiH2
A- _}
A second amorphous layer ( ) consisting of (Si _x C _1-x )y(Cl+H) _1-y can be formed. To form the second amorphous layer by sputtering, target a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C. This can 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 , and then sputtering the Si wafer. Alternatively, Si and C can be sputtered in a gas atmosphere containing at least halogen atoms, by using separate targets or by using a mixed target of Si and C. will be accomplished. As the material gas for introducing C, X, and H if necessary, the material for forming the second amorphous layer () shown in the glow discharge example described above is also effective in the sputtering method. It can be used as a substance. In the present invention, so-called rare gases such as He, Ne, Ar, etc. are suitable as the diluting gas used when forming the second amorphous layer () by the glow discharge method or the sputtering method. It can be mentioned as such. 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 have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrically from conductivity to amorphous. In the present invention, a that exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive properties, has the desired properties depending on the purpose. −(Si _x
The preparation conditions are strictly selected according to desire so that C _1-x )y(H,X) _1-y is formed. For example, to provide the second amorphous layer () with the main purpose of improving pressure resistance, a-(Si _x C _1-x )y(H,
X) _1-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use. In addition, 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
(H,X) _1-y is created. a-(Si _x C _1-x ) on the surface of the first amorphous layer ()
When forming the second amorphous layer () consisting of y( _H, Therefore, in the present invention, the temperature of the support at the time of layer formation is adjusted so that a-(Si _x C _1-x )y(H,X) _1-y having the desired properties can be formed as desired. It is desirable that the 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 30-400
℃, preferably 100 to 300℃. 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 discharge method during layer formation should be power is created a-
(Si _x C _1-x )y(H,X) This is one of the important factors that influences the characteristics of _1-y . As a discharge power condition for effectively producing a-(Si _x C _1-x )y(H,X) _1-y with good productivity, is usually 10 to 300W, preferably 20 to 200W. It is desirable that the gas pressure in the deposition chamber is usually 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 creating the second amorphous layer () include the values in the above ranges,
These layer creation factors are not determined independently and separately, but rather the desired properties a-(Si _x
The optimum value of each layer formation factor is determined based on the mutual organic relationship so that the second amorphous layer ( ) consisting of C _1-x )y(H,X) _1-y is formed. is desirable. 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 first amorphous layer (2), 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 atomic% or more and less than 40 atomic%, preferably 1 atomic% or more.
Less than 40 atomic%, optimally more than 10 atomic%
It is desirable that it be less than 40 atomic%.
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 in this range 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. In other words, if we use the x,y representation of a-(Si _x C _1-x )y(H,X) _1-y , then normally 0.47≦x<
0.99999, preferably 0.5≦x≦0.99, optimally 0.5≦
It is desirable that x≦0.9 and y usually satisfy 0.8≦y≦0.99, preferably 0.82≦y≦0.99, and optimally 0.85≦y≦0.98. 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 layer thickness of the second amorphous layer ( ) has an organic relationship with the layer thickness of the first layer region 103 according to the characteristics required for each layer region. It is necessary to decide as appropriate under the following. In addition, it is desirable to consider the economical aspects including 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, Pd, and alloys thereof. As the electrically insulating support, synthetic resin films or sheets such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness is determined within a range that allows the support to function sufficiently. If inside, it will be made as thin as possible. However, in such cases, the thickness is usually 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, 1103, and 1104 in the figure are sealed with raw material gases for forming the respective layers of the present invention. As an example, 1102 is SiH ₄ gas (purity
99.999%, hereinafter abbreviated as SiH ₄ /He. ) cylinder, 11
03 is B ₂ H ₆ gas diluted with He (purity 99.999
%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 1104
is C ₂ H ₄ gas (99.999% purity) cylinder, 1105
is NO gas (99.999% purity) cylinder, 1106 is
_SiF4 gas diluted with He (purity 99.999% or less)
Abbreviated as SiF ₄ /He. ) It is a cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
Check that the leak valves 2 to 1126 and the leak valve 1135 are closed, and also check that the inflow valve 111
2 to 1116, outflow valves 1117 to 1121,
After confirming that the auxiliary valves 1132 and 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 valves 1117 to 1121 are closed. Thereafter, a desired gas is introduced into the reaction chamber 1101 by operating the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 1101 as prescribed. Next, an outline will be given of an example in which a photoconductive member having an amorphous layer (2) having a layer structure similar to that shown in FIG. SiH ₄ /He gas is supplied from the gas cylinder 1102, B ₂ H ₆ /He gas is supplied from the gas cylinder 1103, and NO gas is supplied from the gas cylinder 1105.
2, 1123, 1125 open and outlet pressure gauge 1
Adjust the pressure of 127, 1128, 1130 to 1Kg/cm ² , and inflow valves 1112, 1113, 1115.
Gradually open the mass flow controller 110.
7,1108,1110. 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, B ₂ H ₆ /He gas flow rate, and NO gas flow rate becomes the desired value, and the pressure inside the reaction chamber 1101 is adjusted. While checking the reading on the vacuum gauge 1136, adjust the main valve 11 to obtain the desired value.
Adjust the aperture of 34. The temperature of the cylindrical base 1137 is then controlled by the heater 1138.
After confirming that the temperature is set in the range of 50 to 400°C, the power source 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101,
At the same time, according to the pre-designed rate of change curve
B ₂ H ₆ B contained in a layer formed by gradually changing the flow rate of He gas and NO gas by operating valves 1118 and 1120 manually or by using an externally driven motor, etc. Controlling the concentration of group group atoms and oxygen atoms such as
Layer regions t ₁ and t _B are formed. At the time when the layer regions t ₁ and t _B are formed, the valves 1118 and 1120 are completely closed, so that the subsequent layer formation is performed using SiH ₄ /
This is done only with the use of He gas, resulting in a layered area
Layer regions t _S , t ₁ are formed on t ₁ , t _B with desired layer thicknesses, and the formation of the first amorphous layer ( ) is completed. As described above, after the amorphous layer () has been formed to a desired layer thickness with a desired depth profile of group atoms and oxygen atoms contained therein, the outflow valve 1117 is once completely closed. It is closed and the discharge is also interrupted. In addition to SiH ₄ gas, Si ₂ H ₆ gas is particularly effective as the raw material gas used in forming the amorphous layer (2) in order to improve the layer formation rate. When containing halogen atoms in the first amorphous layer (2), the above gas may contain, for example, SiF ₄ /He.
is further added and sent into the reaction chamber 1101. To form the second amorphous layer ( ) on the first amorphous layer ( ), for example, the cylinder 1102
SiH ₄ /He gas filled inside and cylinder 1
Using the SiF ₄ /He gas filled in the cylinder 105 and the C ₂ H ₄ gas filled in the cylinder 1106, perform the same procedure as in the case of the amorphous layer () described above. I can do it. Among the layers constituting the photoconductive member of the present invention, when a layer that can be formed by a sputtering method is created using the apparatus shown in FIG. 11, for example, in the case of an amorphous layer ( conduct. A target consisting of high-purity graphite 1142-2 arranged at a desired area ratio on a high-purity silicon wafer 1142-1 is set on an electrode 1141 that is firmly fixed to a fixing member 1139 of a base 1137 and also serves as a support. do. An amorphous layer ( ) is previously formed on the base 1137 as described above. After evacuating the inside of the reaction chamber 1101 to a predetermined degree of vacuum by operating the valves at predetermined locations, the shutter 1142 which also serves as an electrode is opened to make the target and the substrate 1137 face each other, and the heater 1138 is opened.
The support is heated to a desired temperature to prepare it for sputtering. SiF ₄ /He gas from a cylinder 1106 and Ar gas from a cylinder 1104 filled with Ar gas instead of C ₂ H ₄ gas are introduced into the reaction chamber 1101 by operating the respective valves at predetermined locations. It flows in at the desired flow rate ratio to achieve the desired degree of vacuum during sputtering. After the inside of the reaction chamber 1101 reaches a desired degree of vacuum and its internal pressure becomes stable, the power source 1140 is turned on to start sputtering and continue for a desired time. At this time, a second amorphous layer ( ) having a desired layer thickness is formed on the first amorphous layer ( ). In addition, when forming each layer, the gas used to form the previous layer flows into the reaction chamber 1101 and the outflow valve 111.
In order to avoid remaining in the piping leading from 7 to 1121 into the reaction chamber 1101, the outflow valve 11
17 to 1121 are closed and auxiliary valves 1132 and 11 are closed.
33 and fully open the main valve 1134 to temporarily evacuate the system to a high vacuum, as necessary. Example 1 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 3 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 1 below. Distribution concentration of oxygen C _(O)1 ……3.5 atomic% Distribution concentration of boron C ₍ 〓 ₎₁ ……80 atomic ppm The electrophotographic image forming member created has a series of electrophotographic processes from charging to image exposure to development to transfer. The image visualized on the transfer paper through the process was comprehensively evaluated based on its quality, such as density, resolution, and gradation reproducibility.

[Table] Example 2 When forming an amorphous layer (), the flow rate ratio of (SiH ₄ + SiF ₄ ) gas and C ₂ H ₄ gas was changed to form an amorphous layer ().
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. As a result, the results shown in Table 2 were obtained.

[Table] ○ = Very good △ = Slight image defects Example 3 An image forming member was prepared in exactly the same manner as in Example 1 except that the layer thickness of the amorphous layer ( ) was changed. The steps of image formation, development, and cleaning as described in Example 1 were repeated to obtain the following results.

[Table] Example 4 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 4 was formed on an Al cylinder.
The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 4 below. Oxygen distribution concentration C _(O)1 ...7 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...30 atomic ppm Using the obtained electrophotographic image forming member, the electrophotographic process was applied in the same manner as in Example 1. When a toner image was repeatedly formed on the transfer paper, a stable and high quality toner transfer image could be obtained.

[Table] Example 5 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 5 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 5 below. Distribution concentration of oxygen C _(O)1 ...7 atomic% Distribution concentration of boron C ₍ 〓 ₎₁ ...10 atomic ppm 〃 C ₍ 〓 ₎₈ ...5 atomic% Example using the obtained electrophotographic image forming member 1
When toner images were repeatedly formed on transfer paper using the same electronic process as described above, it was possible to obtain stable, high-quality toner transfer images.

[Table] Example 6 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 6 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer () and the conditions for creating the amorphous layer () are shown in Table 6 below. Distribution concentration of oxygen C _(O)1 ...1 atomic% Distribution concentration of boron C ₍ 〓 ₎₁ ...100 atomic ppm 〃 C ₍ 〓 ₎₈ ...10 atomic% Example 1 was carried out using the obtained electrophotographic image forming member.
When we repeatedly formed toner images on transfer paper using the same electrophotographic process, we were able to obtain stable, high-quality toner images.

[Table] Example 7 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer having the layer structure shown in FIG. 7 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 7 below. Oxygen distribution concentration C _(O)1 ...2 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...30 atomic ppm 〃 C ₍ 〓 ₎₃ ...5 atomic% Conducted using the obtained electrophotographic image forming member When a toner image was repeatedly formed on a transfer paper using the electrophotographic process in the same manner as in Example 1, a stable and high quality toner image could be obtained.

【table】

[Table] Example 8 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 8 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 8 below. Oxygen distribution concentration C _(O)1 ...2 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...200 atomic ppm 〃 C ₍ 〓 ₎₃ ...5 atomic% Conducted using the obtained electrophotographic image forming member When a toner image was repeatedly formed on a transfer paper using the electrophotographic process in the same manner as in Example 1, a stable and high quality toner image could be obtained.

【table】

[Table] Example 9 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 9 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 9 below. Oxygen distribution concentration C _(O)1 ...5 atomic% 〃 C _(O)3 ...2 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...50 atomic ppm Conducted using the obtained electrophotographic image forming member When toner images were repeatedly formed on transfer paper by applying the electrophotographic process in the same manner as in Example 1, stable and high-quality toner images could be obtained.

[Table] Example 10 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 2 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 10 below. Distribution concentration of oxygen C _(O)1 ...3.5 atomic% Distribution concentration of boron C ₍ 〓 ₎₁ ...80 atomic ppm 〃 C ₍ 〓 ₎₂ ...500 atomic ppm Conducted using the obtained electrophotographic image forming member When toner images were repeatedly formed on transfer paper by applying the electrophotographic process in the same manner as in Example 1, stable and high-quality toner transfer images could be obtained.

[Table] Example 11 Using the manufacturing apparatus shown in FIG. 11, an electrophotographic image forming member having an amorphous layer ( ) having the layer structure shown in FIG. 3 was formed on an Al cylinder. The respective layer regions constituting the amorphous layer ( ) and the conditions for creating the amorphous layer ( ) are shown in Table 11 below. Oxygen distribution concentration C _(O)1 ...3.5 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...50 atomic ppm Using the obtained electrophotographic image forming member, the electrophotographic process was applied in the same manner as in Example 1. When a toner image was repeatedly formed on the transfer paper, a stable and high quality toner transfer image could be obtained.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram for explaining one preferred example of the structure of the photoconductive member of the present invention, and FIGS. FIG. 11 is a schematic explanatory diagram illustrating the layer structure of the photoconductive member of the present invention. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 103...First layer region (O), 104...Second layer region (),
105... layer area, 106... layer area, 107...
...Second amorphous layer (), 108...Free surface.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, a first amorphous layer that is composed of an amorphous material having silicon atoms as a matrix and exhibits photoconductivity, and a support for a photoconductive member; , and a second amorphous layer made of an amorphous material containing carbon atoms with a content of less than 40 atomic % as constituent atoms, and the first amorphous layer has carbon atoms as constituent atoms. a first layer region having a region containing oxygen atoms and whose distribution concentration gradually decreases in the layer thickness direction; and a layer region provided on the first layer region and containing substantially no oxygen atoms as constituent atoms. , a second layer region containing atoms belonging to group of the periodic table in a continuous distribution state in the layer thickness direction as constituent atoms, and the first layer region and the second layer A photoconductive member characterized in that the regions are provided in contact with the support and share at least a portion of each other. 2. The photoconductive member according to claim 1, wherein the second layer region has a uniform distribution of atoms belonging to Group 3 of the periodic table in the layer thickness direction. 3. The photoconductive member according to claim 1, wherein the second layer region has a uniform distribution of atoms belonging to Group 3 of the periodic table in the layer thickness direction. 4. The photoconductive member according to claim 1, wherein the first layer region and the second layer region are substantially the same layer region. 5. The photoconductive member according to claim 1, wherein the first layer region constitutes a part of the second layer region. 6. The photoconductive member according to claim 1, wherein the second layer region constitutes a part of the first layer region.