JPH0454942B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having 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, such as the need to improve overall characteristics in terms of usage environment characteristics and stability over time. 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. 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. , has many advantages over organic photoconductive materials such as PVCz and TNF, but has a single-layer photoconductive layer made of a-Si that has properties that make it suitable for use in conventional solar cells. Even if the photoconductive layer of the electrophotographic image forming member is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply normal electrophotography methods, and in a humid atmosphere. In some cases, the above-mentioned tendency is remarkable, and in some cases, it has been found that there are problems that can be solved, such as in some cases being unable to retain almost any electrical charge until the development time. . Furthermore, when forming a photoconductive layer with an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boric acid 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, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least one of hydrogen atoms (H) or halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [ "a-Si(H,X)" will be used hereafter as a generic term for these. The conductive material not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. It is based on the findings that the The present invention is an all-environment type in which the electrical, optical, and photoconductive properties are almost always stable without being controlled by the usage environment, and it is extremely resistant to light fatigue and does 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 resolution. Yet another object of the present invention is high photosensitivity,
It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. The photoconductive member of the present invention 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 hydrogen Atom, content 30atomic%
a second amorphous layer () made of an amorphous material containing less than or equal to carbon atoms as constituent atoms;
The first amorphous layer () has, as constituent atoms,
a first layer region (O) having a region containing oxygen atoms and whose distribution concentration gradually decreases in the layer thickness direction; and a second layer region () containing atoms belonging to Group 3 of the periodic table in a continuous distribution state in the layer thickness direction as constituent atoms, Layer area (O)
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 configuration diagram schematically shown to explain the layer configuration 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 a first 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 contains group group atoms but does not contain oxygen atoms. 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; Preferably, it is continuously and substantially uniformly distributed in a direction substantially parallel to the surface of body 101. 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 Although it may be uniform, it is preferably distributed continuously and substantially uniformly 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;
In the present invention, the layer region 106 may also contain group group atoms. 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, like the photoconductive member 100 shown in FIG.
The amorphous layer ( ) 102 includes a first layer region (O) 103 containing oxygen atoms, a second layer region (O) 104 containing group group atoms, a layer region 105 containing no oxygen atoms, and a layer region 106 containing no oxygen atoms or group atoms,
First layer region (O) 103 and second layer region ()
Better results are obtained with a layer structure having a layer area shared with 104. 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) have an electric potential 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 layer region ( ), and in the example in which the group atoms are not contained in the layer region on the surface side of the amorphous layer ( ). In this case, on the side of the layer region on the surface side, the distribution concentration of group atoms in the second layer region ( ) is gradually decreased in the direction of the interface with the layer region on the surface side; It is preferable that the distribution state of the group atoms is formed such that the number of atoms is substantially zero. 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
It is desirable to set it to ~10 atomic%, optimally 0.003 to 5 atomic%. Each of FIGS. 2 to 10 shows typical examples of the distribution state of oxygen atoms and group atoms contained in the amorphous layer () of the photoconductive member in the present invention in the layer thickness direction. . ° In FIGS. 2 to 10, the horizontal axis indicates the concentration C of oxygen atoms or group atoms, the vertical axis indicates the layer thickness direction of the amorphous layer exhibiting photoconductivity, and t _B is t S indicates the position of the surface of the amorphous layer ( ) on the support side, and t _S indicates the position of the surface of the amorphous layer ( ) on the opposite side 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. Also, A ₂ ~A ₁₀ is B ₂ ~ of oxygen atom
B ₁₀ represents the distribution concentration line 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 Figure 2, the amorphous layer () (t _S , t _B ) (total thickness region from t _S to t _B ) that is made of a-Si (H, X) and exhibits photoconductivity is , from the support side, _{a layer region (t 2 , t B} ) (layer area between t ₂ and t _B )
, the distribution concentration of oxygen atoms gradually decreases linearly from the distribution concentration C(o) ₁ to substantially zero, and the distribution concentration of group atoms decreases from the distribution concentration C() ₁ ) to substantially zero. a layer region ₍ t ₁ , t ₂ ) that gradually decreases linearly until
t ₁ ). As in the example shown in Figure 2, the amorphous layer () (t _S , t _B )
has a contact surface with the support or another layer (corresponding to t _B ) and a layer region (t ₂ , t _B ) in which the distribution of oxygen atoms and group atoms is uniform, then the distribution The concentrations C() ₁ and C(o) ₁ are appropriately determined depending on the relationship with the support or other layers, but in the case of C() ₁ , for silicon atoms,
Usually 0.1 to 10000 atomic ppm, preferably 1
~4000atomic ppm, optimally 2-2000atomic
ppm, and in the case of C(o) ₁ , it is usually 0.01-30 atomic% with respect to silicon atoms, preferably 0.02-30 atomic%.
It is desirable that the content be 20 atomic%, most preferably 0.03 to 10 atomic%. Layer area (t ₁ , t ₂ )
is provided mainly to smooth the electrical contact between the layer region (t _S , t ₁ ) and _the layer region (t ₂ , t _B ); The layer thickness of t ₂ ) is determined 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 . It needs to be decided. The layer thickness of the layer region (t S , t 1 ) that may contain group group atoms but does not contain oxygen atoms is determined by the thickness of the layer region (t _S , t ₁ ) that contains oxygen atoms, including durability against repeated use. t ₁ , t _B ) are sufficiently protected from the atmosphere, and the layer area (t _S , t B ) is
If a photocarrier is generated by light irradiation in t ₁ ), the irradiated light will reach the layer region (t _S ,
It is determined as desired so that sufficient absorption is achieved at t ₁ ). 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 molecules 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 a layer region (t ₃ , t _B ) in which the distribution concentration of oxygen atoms is higher than the distribution concentration C(o) ₁ . Layer region where oxygen atoms are distributed in high concentration (t ₃ ,
As the distribution concentration C _(O)2 of oxygen atoms at t _B ),
Usually 30 atomic% or more for silicon atoms,
Preferably 40 atomic% or more, optimally 50 atomic%
The above is desirable. 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 reaches. The distribution state of the group atoms contained in the second layer region () in the layer region () is such that on the support side, the layer region [layer region] maintains a constant value at a distribution concentration C() ₁ (t ₂ , t _B )], but in order to more efficiently prevent charge injection from the support side to the amorphous layer, a second layer is added to the support side. It is desirable to provide a layer region (t ₄ , t _B ) in which group group atoms are distributed at a high concentration, as shown by the dashed line C in the figure. In the present invention, the layer region (t ₄ , t _B ) is located at the position t _B
It is more preferable to provide the distance within 5μ. The layer region (t ₄ , t _B ) may be the entire layer region L _T up to 5 μm thick from the position t _B , or may be provided as a part of the layer region L _T. Whether the layer region (t ₄ , t _B ) is a part or all of the layer region L _T is appropriately determined according to the characteristics required of the amorphous layer ( ) to be formed. In the layer region (t ₄ , t _B ), the maximum Cmax of the content distribution value (distribution concentration value) of group atoms is the distribution state of the group atoms contained therein in the layer thickness direction, which is normal for silicon atoms. is 50 atomic ppm or more, preferably 80 atomic ppm or more, optimally 100 atomic ppm
It is desirable to form a layer in such a way that a distribution state of ppm or more can be achieved. That is, in the present invention, the second layer region () containing group atoms has the maximum value Cmax of the content distribution within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ). It is preferable that it be formed so that In the present invention, the layer thickness of the layer region (t ₃ , t _B ) in which oxygen atoms are distributed in high concentration and the layer region (t ₄ , t _B ) in which group group atoms are distributed in high concentration are The layer thickness is
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,
The preferred thickness is 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 the layer region (t ₃ , t _B ) in which oxygen atoms are substantially uniformly distributed with a distribution concentration C _(O)1 . ) and a layer region (t ₁ , t ₃ ) in which the distribution concentration C _(O)1 linearly gradually decreases from position t ₃ to substantially zero. Second layer region containing group atoms ()
(t ₁ , t _B ) is a layer region (t ₂ , t B ) that is substantially uniformly distributed with a distribution concentration C ₍ 〓 ₎₁ , and a layer region (t 2 , t _B ) that is substantially uniformly distributed with a distribution concentration C ₍ 〓 ₎₁ from the position t ₂ . The layer region (t ₁ , t ₂ ) gradually decreases linearly until it reaches zero. The layer region (t _S , t ₁ ) contains neither oxygen atoms nor group atoms, similar to the layer region (t _S , t ₁ ) shown in FIG. The example _shown in FIG _. 4 is a modification of the example shown in _FIG. , is the same as the case shown in FIG. 3, except that there is provided a layer region (t ₃ , t _B ) in which group atoms are uniformly distributed at a distribution concentration C ₍ 〓 ₎₁ . 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 _. , _tB )
There are layer regions (t 1 , t 3 ) containing group group atoms but no oxygen atoms (t ₁ , t ₃ ) and layer regions (t _S , t ₁ ) containing neither group group atoms nor oxygen atoms. ). The layer region (t ₃ , t _B ) containing oxygen atoms is the layer region (t ₅ , t B ) in which oxygen atoms are substantially uniformly distributed in the layer thickness direction with a distribution concentration _{C (O)1} . and a layer region (t ₃ , t ₅ ) in which the distribution concentration C _(O)1 gradually decreases linearly and reaches substantially zero. The layer region (t ₁ , t _B ) includes, from the support side, a layer region (t 4 , t B ) in which group group atoms are substantially uniformly distributed with a distribution concentration C ₍ 〓 ₎₁ , a layer region (t ₄ , t _B ), a distribution concentration C ₍ 〓 ₎₁ to distribution concentration
The layer region ₍ t ₃ , t 4 ) is distributed linearly and continuously decreasing up to C ( 〓 )3, and the layer region (t ₂ , t ₄ ) is distributed substantially uniformly at _the distribution concentration C ₍ 〓 _{)3. 3} ), and layer regions (t ₁ , t ₂ ) distributed in a linearly continuously decreasing manner from the distribution concentration C ₍ 〓 _{) 3} are stacked. FIG. 6 shows a modification of the example shown in FIG. In _{the case} of _the example shown in _FIG . is the distribution concentration
A layer containing group atoms in a linearly decreasing distribution in the layer region (t ₃ , t ₅ ) which is linearly decreasing gradually from C _(O)1 to substantially zero. The layer region (t ₄ , t ₅ ) and the layer region (t 3 , t 5 ) in which group atoms are contained in a substantially uniform distribution state with a distribution concentration C ₍ 〓 _{) 3
t4} ) is provided. A layer region (t _S , t ₃ ) substantially free of oxygen atoms is provided on the layer region (t ₃ , t _B ),
The layer region (t _S , t ₃ ) is divided into a layer region ( ) ( ) (t ₁ , t ₃ ) containing group group atoms and a layer region (t _S , _t1 )
It is made up of. FIG. 7 shows an amorphous layer () [layer region (t _S , t _B )]
An example is shown in which group group atoms are contained in the entire layer region, and oxygen atoms are not contained in the layer region (t _S , t ₁ ) on the surface side. The layer region (t ₁ , t _B ) containing _oxygen atoms is the layer region (t ₃ , t _B )
and a layer region _(O) (t ₁ , t ₃ ) in which oxygen atoms are contained in a distribution state that is gradually decreased from the distribution concentration C (O)1 to reach the example. The distribution of group atoms in the amorphous layer ( ) is shown by the solid line B7. In other words, the layer region containing group atoms (t _S , t _B ) is the layer region (t ₂ , t _B ) in which group atoms are uniformly distributed with a distribution concentration C ₍ 〓 _)1.
and the layer region ₍ t _S , t ₁ ) in which the group atoms are uniformly distributed with the distribution concentration C ( 〓 ) ₂ , and the distribution concentration C ₍ 〓 ₎₁ and the distribution concentration C ₍ 〓 ₎₂ . In order to continuously change the distribution of group atoms between these distribution concentrations, the layer region (t ₁ , t ₂ ). FIG. 8 shows a modification of the example shown in FIG. 7. The entire layer region of the amorphous layer ( ) contains group atoms, as shown by the solid line B8, and the layer region (t ₁ , t _B ) contains oxygen atoms. In the layer region (t ₃ , t _B ), oxygen atoms have a distributed concentration
In C _(O)1 , group atoms are contained in a uniform distribution state with a distribution concentration C ₍ 〓 ₎₁ , and the layer area (t _S , t ₂ )
In , group atoms are contained in a uniformly distributed state with a distribution concentration C ₍ 〓 ₎₂ . As shown by the solid line A8, in the layer region (t ₁ , t ₃ ), oxygen atoms gradually decrease linearly from the distribution concentration C _{(O) 1} from the support side to a substantial concentration at position t ₁ . It is contained so that it becomes zero. In the layer region (t ₂ , t ₃ ), group group atoms are contained in a distribution state that gradually decreases from the distribution concentration C ₍ 〓 ₎₁ to the 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. In the layer region (t ₂ , t _B ), oxygen atoms are contained in a substantially uniform distribution state with a distribution concentration C _{(O)1, and} in the layer region (t ₁ , t ₂ ), the oxygen atoms are contained in a substantially uniform distribution state. distribution concentration
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 the layer region (t ₃ , t _B ), oxygen atoms have a distributed concentration C _(O)1 , and group atoms have a distributed concentration C ₍ 〓 ₎₁
In the layer region (t ₂ , t ₃ ), oxygen atoms and group atoms are each contained substantially uniformly with a constant distribution concentration, and the distribution concentration of oxygen atoms and group atoms each gradually decreases as the layer grows. In the case of group atoms, the distribution concentration is said to be substantially zero at _t2 . Oxygen atoms are contained so as to form a linearly decreasing distribution state even in layer regions (t ₁ , t ₂ ) where no group group atoms are contained, and at t ₁ the distribution state becomes substantially It is said to be zero. The layer region (t _S , t ₁ ) contains 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 in a curved manner. 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 reduced in 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 method,
For example, for introducing hydrogen atoms (H) and/or halogen atoms (X) when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. The gas 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 these, 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 in which an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. Although it is possible to form an amorphous layer ( ) on a predetermined support by
In order to introduce hydrogen atoms, a layer may be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms with these gases. 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 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 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 , SiH ₂
I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other halogen-substituted silicon hydrides, etc., in a gaseous state or can be gasified. Halides containing hydrogen atoms as one of their constituent elements can also be cited as effective starting materials for forming the 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 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 usually In the case of 1 to 40 atomic%,
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 and Ar. 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. Formed by using a starting material for introducing group atoms, a starting material for introducing oxygen atoms, or both starting materials together with the above-mentioned starting material for forming an amorphous layer when forming a layer by a method etc. 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. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) are used. are also mixed 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) are mixed. It can be used in combination with a raw material gas having 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 tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H Examples include lower siloxanes such as ₃ SiOSiH ₂ OSiH ₃ ). To form the first layer region (O) containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer,
Alternatively, the sputtering may be carried out by targeting a wafer containing a mixture of Si and SiO ₂ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a 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 oxidizing 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 , _{B6H10 ,}
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as BBr ₃ . Other examples include AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ and TlCl ₃ . In the present invention, 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 performed by appropriately controlling the flow rate of a gas containing a component whose distribution concentration is to be changed. This is achieved by making changes. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed using any commonly used method such as a main drive or an external drive 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 standpoint. In the present invention, the thickness of the amorphous layer (2) is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 1.
It is desirable that the thickness be 100μ, preferably 1 to 80μ, optimally 2 to 50μ. In the photoconductive member of the present invention, a second amorphous layer () provided on the first amorphous layer () is provided.
is an amorphous material [a-(Si _x C _1-x ) _y H _1-y , where 0
<x,y<1], so it is an amorphous layer ()
Since each of the amorphous materials forming the first amorphous layer ( ) and the second amorphous layer ( ) having a common constituent element of silicon atoms,
Chemical safety is sufficiently ensured at the laminated interface. The second amorphous layer ( ) composed of a-(Si _x C _1-x ) _y H _1-y is formed by glow discharge method, sputtering method, ion implantation method, ion plating method. 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, it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms into the second amorphous layer (2), etc. 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. 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 _1-y is mixed with a diluent 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, which is already formed on the support. a-(Si _x C _1-x ) _y H _1-y may be deposited on the first amorphous layer ( ). In the present invention, at least one of Si, C, and H is used as the raw material gas for forming a-(Si _x C _1-x ) _y H _1-y.
Most gaseous substances or gasified substances having two constituent atoms can be used. When using a raw material gas with Si as a constituent atom as one of Si, C, and H, for example, a raw material gas with Si as a constituent atom, a raw material gas with C as a constituent atom, and a raw material gas with H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing C and H 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
It is possible to use a mixture of a raw material gas having three constituent atoms: and H. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, Si and H are effectively used as raw material gases for forming the second amorphous layer ().
The constituent atoms are Si ₂ H ₆ , Si ₃ H ₈ , SiH ₄ , Si ₄
Silicon hydride gas such as silanes such as H ₁₀ , whose constituent atoms are C and H, for example, carbon number 1
-4 saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (CH 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 ), poutine (C ₄ H ₆ ), and the like. Examples of the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these raw material gases, H
Of course, H ₂ is also effectively used as the raw material gas for introduction. 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. For example, if a Si wafer is used as a target, the raw material gases for introducing C and H are diluted with diluent gas as necessary, and introduced into the sputtering deposition chamber. The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least hydrogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. As the raw material gas for introducing C or H, the raw material gas 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, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluting gas when forming the second amorphous layer () by a glow discharge method or a 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, materials whose constituent atoms are Si, C, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. and the properties between photoconductive and non-photoconductive properties,
Accordingly, in the present invention, the preparation conditions are strictly selected according to the needs so that a-Si _x C _1-x having the desired characteristics depending on the purpose is formed. . For example, in order to provide the second amorphous layer () with the main purpose of improving pressure resistance, a-(Si _x C _1-x ) _y
H _1-y is produced as an amorphous material with pronounced electrically insulating behavior under conditions of use. In addition, if a second amorphous layer () is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to some extent, and it will be more effective against the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y
H _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 H _1-y , the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. 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 H _1-y can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer () is determined as appropriate in accordance with the method of forming the second amorphous layer (). The formation of the second amorphous layer () is carried out with an optimal range selected, typically between 100 °C and
Desirably, the temperature is 300°C, preferably 150°C to 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 forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. The discharge power and gas pressure are one of the important factors that influence the characteristics of the a-(Si _x C _1-x ) _y H _1-y that is created. The discharge power conditions for effectively producing a-(Si _x C _1-x ) _y H _1-y with high productivity, which has the characteristics to achieve the purpose of the present invention, are usually 10 ~
It is desirable that the power be 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-mentioned ranges,
These layer creation factors are not determined independently and separately, but rather the desired properties a-(Si _x
It is desirable that the optimum value of each layer formation factor be determined based on the mutual organic relationship so that a second amorphous layer ( ) consisting of C _1-x ) _y H _1-y is formed. The amounts of carbon atoms and hydrogen atoms contained in the second amorphous layer () in the photoconductive member of the present invention are as follows:
The conditions for forming the second amorphous layer ( ) are also important factors in forming the second amorphous layer ( ) that provides the desired properties to achieve the objects 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 30 atomic%, preferably
1 atomic% or more and less than 30 atomic%, optimally
It is desirable that the content be 10 atomic % or more and less than 30 atomic %. The hydrogen atom content is usually 1 to 40 atomic%, preferably 2 atomic%.
It is desirable that the hydrogen content be ~35 atomic%, optimally 5 to 30 atomic%, and photoconductive members formed when the hydrogen content is in this range are considered to be excellent in practice. It's something you get. That is, if expressed as a-(Si _x C _1-x ) _y H _1-y , x is usually 0.5<x≦0.99999, preferably 0.5
<x≦0.99, optimally 0.5<x≦0.9, y usually 0.6≦y≦0.99, preferably 0.65≦y≦0.98, optimally 0.7≦y≦0.95. 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. The numerical range of the layer thickness of the second amorphous layer ( ) in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the purpose of the present invention. In addition, the layer thickness of the second amorphous layer () is determined by the amount of carbon atoms and hydrogen atoms contained in the layer (),
The relationship with the layer thickness of the first amorphous layer () also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. There is. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The layer thickness of the second amorphous layer ( ) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ,
The optimum value is 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, 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 above metal. This imparts conductivity to the surface. The shape of the support body is cylindrical,
The photoconductive member 100 shown in FIG. 1 may be used as an image forming member for electrophotography, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member. In the case of copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such 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. In the gas cylinders 1102, 1103, and ₁₁₀₄ in the figure, raw material gases for forming the respective layers of the present invention are sealed.
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 CH ₄ gas (99.99% purity) cylinder, 1105 is
NO gas (99.999% purity) cylinder, 1106 is He
SiF ₄ gas diluted with (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, we will outline an example of creating a photoconductive member having an amorphous layer () with a layer structure similar to that shown in FIG. 2, and an amorphous layer () on the layer (). . SiH ₄ /He gas is supplied from the gas cylinder 1102, B ₂ H ₄ /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 /He is contained in a layer formed by gradually changing the flow rate of He gas and the flow rate of NO gas by operating the valves 1118 and 1120 manually or using an externally driven motor, respectively. B
The layer regions (t ₁ , t _B ) are formed by controlling the concentration of group group atoms such as and oxygen atoms. At the time when the layer region (t ₁ , t _B ) is formed, the valves 1118 and 1120 are completely closed, so that the subsequent layer formation is as follows.
It is carried out using only SiH ₄ /He gas, resulting in
A layer region (t _S , t ₁ ) is formed on the layer region (t ₁ , t _B ) with a desired layer thickness, and the formation of the first amorphous layer ( ) is completed. As described above, after the amorphous layer () is formed to have a desired depth profile of group atoms and oxygen atoms and a desired layer thickness, the outflow valve 317 is once completely closed. closed,
Discharge is also interrupted. In addition to SiH ₄ gas, Si ₂ H ₆ gas is particularly effective as the raw material gas used for 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 an amorphous layer () on an amorphous layer (), use the B ₂ H ₆ /
Layer formation is performed using CH ₄ gas instead of He gas and NO gas. It goes without saying that all outflow valves for gases other than those required for forming each layer are closed, and
When forming each layer, the gas used to form the previous layer is released into the reaction chamber 1101 and the outflow valves 1117 to 1.
121 to the inside of the reaction chamber 1101, the outflow valves 1117 to
1121 is closed, auxiliary valves 1132 and 1133 are opened, and main valve 1134 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. During layer formation, the base 1137 is rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Example 1 Using the manufacturing apparatus shown in FIG. 11, 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. Oxygen distribution concentration C _(O)1 ……3.5 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ……80 atomic ppm The electrophotographic image forming member produced was subjected to a series of electrophotographic processes including charging, image exposure, development, and 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】

[Table] Example 2 When forming the amorphous layer (), the content ratio of silicon atoms and carbon atoms in the amorphous layer () was determined by changing the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas An image forming member was produced in exactly the same manner as in Example 1, except that . As a result, the results shown in Table 2 were obtained.

[Table] ○ = Very good △ = Easy to cause image defects Example 3 An image forming member was prepared in exactly the same manner as in Example 1 except that the 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 toner images were repeatedly formed on transfer paper using this method, stable and high quality toner transfer images 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. Oxygen distribution concentration C _(O)1 ...7 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...10 atomic ppm 〃 C ₍ 〓 ₎₃ ...5 atomic% Examples using the obtained electrophotographic image forming member When toner images were repeatedly formed on transfer paper using the same electrophotographic process as in Example 1, stable high-quality toner transfer images could be obtained.

【table】

[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. Oxygen distribution concentration C _(O)1 ...7 atomic% Boron distribution concentration C ₍ 〓 ₎₁ ...100 atomic ppm 〃 C ₍ 〓 ₎₃ ...10 atomic% Examples using the obtained electrophotographic image forming member When toner images were repeatedly formed on transfer paper using the same electrophotographic process as in Example 1, stable high-quality toner images could be obtained.

【table】

[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 toner images were repeatedly formed on transfer paper using the same electrophotographic process as in Example 1, stable, high-quality toner images could be obtained.

[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 toner images were repeatedly formed on transfer paper using the same electrophotographic process as in Example 1, stable, high-quality toner images could be obtained.

[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 using the same electrophotographic process as in Example 1, stable, high-quality toner images could be obtained.

【table】

[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 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】

[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 ...80 atomic ppm Using the obtained electrophotographic image forming member, an electrophotographic process was carried out in the same manner as in Example 1. When this method was applied to repeatedly form toner images on transfer paper, stable, high-quality toner transfer images could be obtained.

【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 crystalline layer ( ), and is a schematic explanatory diagram of the apparatus used for producing 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 silicon atoms and hydrogen atoms. and a second amorphous layer () made of an amorphous material containing carbon atoms with a content of less than 30 atomic% as constituent atoms, and the first amorphous layer () has a , 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; and the first layer region (O)
a layer region provided thereon which does not substantially contain oxygen atoms as constituent atoms; and a second layer containing atoms belonging to group 3 of the periodic table in a continuous distribution state in the layer thickness direction as constituent atoms. region (), and the first layer region (O) and the second layer region () are provided in contact with the support and share at least a part of each other. A photoconductive member. 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 non-uniform distribution of atoms belonging to Group 3 of the periodic table in the layer thickness direction. 4 Claim 1, wherein the first layer region (O) and the second layer region (O) are substantially the same layer region
The photoconductive member described in . 5. The photoconductive member according to claim 1, wherein the first layer region (O) 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 (O).