JPS58159544A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain an all-environment type photoconductive material superior in optical fatigue resistance and durability, by forming the specified first amorphous layer and the second amorphous layer contg. Si, C, and H. CONSTITUTION:A photoconductive material 100 is obtained by forming on a substrate 101 the first photoconductive amorphous layer 102 contg. Si as a main component, and H or halogen, and the second amorphous layer 107 contg. Si, C, and H. The layer 102 comprises the first layer region 103 contg. O as a component, a layer region 104 contg. an element of group V of the periodic table in a distribution of concn. C held at a constant concn. C1 as shown in the graph, in the graph, in the range of tB-t1, where tB is an interface position in contact with the side of the substrate 101 and gradually decreasing from a concn. C2 to a concn. C3 in the range of the second layer region 105 of t1-tT, where tT is an interface position in contact with a layer region 106, and this region 106 contg. neither O nor said element.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoconductive material that is sensitive to electromagnetic waves such as light (in a broad sense, ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). Regarding members ○ As a photoconductive material that forms a light guide layer in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices, it is highly sensitive, has a high signal-to-noise ratio [photocurrent (Ip
)/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time. Especially,
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 this point, there is amorphous silicon (hereinafter referred to as a-8t) as a light guide material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional a-8i has excellent electrical and optical binary conductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of photoconductive member When used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon, which causes an afterimage. According to experiments, a-
Although 8T has many advantages compared to conventional inorganic photoconductive materials such as Se, CdS, and ZnO or organic photoconductive materials such as B PVCz + TNF, it has some characteristics that make it unsuitable for use in conventional solar cells. Even if the photoconductive layer of an electrophotographic imaging member having a single-layer photoconductive layer made of a-8i is subjected to charging treatment for electrostatic image formation, dark decay is significant. However, it is difficult to apply ordinary electrophotographic methods, and in a humid atmosphere, the above-mentioned tendency is significant, and in some cases, the magnetic charge may hardly be retained until the development time. It has been found that there are points that can be obtained.

Furthermore, when forming a photoconductive layer using an a-Si material, hydrogen atoms, fluorine atoms, chlorine atoms, etc., and electrical Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the conductivity type, or other atoms are included in order to improve other properties, but the manner in which these constituent atoms are contained is determined. In some cases, problems may arise with the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation is not sufficient, or the injection of organic substances from the support side in a dark area is not sufficiently prevented. This often occurs.

Therefore, while the characteristics of the a-8t material itself are being improved, when designing photoconductive members, it is difficult to achieve the desired properties as described above.
It is necessary to devise ways to obtain uniform, optical, and photoconductive properties.

The present invention has been made in view of the above points, and the applicability and application of A-8T as a photoconductive member used in image forming members for single-child photography, solid-state imaging devices, reading devices, etc. As a result of comprehensive and intensive research and consideration from the viewpoint of the properties of , so-called hydrogenated amorphous silicon, halogenated amorphous silicon.

Alternatively, specify the layer structure of a photoconductive member having a photoconductive layer composed of halogen-containing hydrogenated amorphous 7-licon [hereinafter, a-5t(H,X)J will be used as a generic notation]. The photoconductive members designed and produced in this way not only show extremely superior properties in practical use, but also surpass in all respects compared to conventional photoconductive members, especially when used in electrophotography. This is based on the discovery that it has extremely excellent properties as a conductive member.

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, the present invention has sufficient charge retention ability during charging treatment for electrostatic image formation, and ordinary electrophotographic methods can be applied very effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

Yet another object of the present invention is high photosensitivity.

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 includes a support for the photoconductive member, and an amorphous material having silicon atoms as a matrix and preferably containing at least one of hydrogen atoms ([I) or halogen atoms + X] as constituent atoms. Material (a-8i (H,X)
), a first amorphous layer having photoconductivity;
a second amorphous layer made of an amorphous material containing silicon atoms, carbon atoms, and hydrogen atoms (-1) the first amorphous layer contains oxygen atoms as constituent atoms; , atoms belonging to group V of the periodic table as constituent atoms, continuous in the layer thickness direction with the first layer region unevenly distributed toward the support side, and distributed in large numbers toward the support side; It is characterized by having a second layer region containing.

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 and optical properties.

Indicates photoconductive properties and usage environment properties.

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 structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention.

The photoconductive member 100 shown in FIG. 1 is made of a-8t(H,X) on a support 101 for the photoconductive member,
A first amorphous layer (1) 102 exhibiting photoconductivity and an amorphous material composed of silicon atoms and carbon atoms provided on the first amorphous layer (1) 102. It has a second amorphous layer (■) 1o7.

Amorphous layer (1) 102 includes a first layer region +01103 containing oxygen atoms as constituent atoms, and a second layer region (V
) 104, and a layer region 106 containing no oxygen atoms or group V atoms on the second layer region (V) 104.

The first layer region (layer region 105K provided between Olloa and layer region 106) contains group V atoms but no oxygen atoms.

The group V atoms contained in the second layer region (V) 104 are continuously and non-uniformly distributed in the layer thickness direction, and
It is continuously and substantially uniformly distributed in a plane substantially parallel to the surface of 01.

In the present invention, the oxygen atoms contained in the first layer region to) 103 are distributed in a substantially uniform manner in the layer thickness direction and in a plane parallel to the surface of the support 101. ,
Contained in the entire layer area of the first layer area + o) 1o, a.

In the present invention, the focus is on improving the adhesion between the first amorphous layer (1) and the support directly provided by containing oxygen atoms in the first layer region +01. It is planned.

In the photoconductive member of the present invention such as the example shown in FIG. 1, the surface side portion of the amorphous layer (I) 102 has a layer region ( A layer region (corresponding to layer region 106 shown in FIG. 1) that contains Group V atoms but does not contain oxygen atoms (layer region 105 shown in FIG. 1) is not necessarily provided. does not require

That is, for example, in FIG. 1, the first layer region +0110
3 and the second layer region (V) 104 may be the same layer region, or the second layer region (V) 104 may be provided in the first layer region +01103. It is.

In the photoconductive member of the present invention, the first layer region (0) that constitutes a part of the amorphous layer (1) and contains oxygen atoms is 1
For the purpose of improving the adhesion of the amorphous layer (1) to the support, there is also a The second layer region M is formed, in part, because when the free surface side of the amorphous layer (■) is subjected to charging treatment, charges are injected into the inside of the amorphous layer (1) from the support side. For the purpose of preventing this, the support and the amorphous layer (1) are provided as part of the amorphous layer (1) in a structure in which they share at least a part of each other as a bonding layer region.

In addition, in order to more effectively improve the adhesion between the support of the second layer region (to) or the layer region provided directly on the second layer region (a), , the first layer region (0) is provided so as to include the second layer region (g) from the contact interface with the support; The first layer region 10) is covered with an amorphous layer (1) so as to form a layered structure penetrating the second region M up to the top.
It is preferable to provide it inside.

The Group Ⅰ atoms contained in the layer region (G) are continuous in the layer thickness direction and on the side opposite to the side on which the support is provided (in FIG. 1, on the second side) Amorphous layer (II) 1 of
It is contained in the middle of the layer region so that it is distributed more on the support side than on the 07 side).

In the present invention, P (phosphorus) is used as the atom belonging to Group V of the periodic table contained in the second layer region (g) constituting the amorphous layer (1).

As (tilt element), sb (antimony), Bi (bismuth), etc., and P is particularly preferably used.

It is As.

In the present invention, the distribution state of group (III) atoms contained in the layer region (b) is as described above in the layer thickness direction, and substantially in the direction parallel to the surface of the support. It is assumed that the distribution is uniform.

2 to 10 show the distribution in the layer thickness direction of Group V atoms contained in the layer region (V) constituting the first amorphous layer (1) of the photoconductive member of the present invention. Typical examples of conditions are shown.

In the case of the present invention, oxygen atoms are uniformly contained in the entire layer region of the first layer region (0) in the above-mentioned distribution state, so the following description will be made in the examples of FIGS. 2 to 10. Here, the layer region (0) containing oxygen atoms will not be mentioned unless a particular explanation is required.

42 to 10, the horizontal axis represents the cap C containing group V atoms, and the vertical axis represents the first amorphous layer (1) exhibiting photoconductivity.
tB indicates the position of the interface on the support side, and tT indicates the position of the interface on the opposite side to the support side. That is, the layer region (V) containing Group (1) atoms is formed as a layer toward the 1T side rather than the tB side.

In the present invention, the layer region (G) containing group V atoms is a-8t (H) constituting the photoconductive member.

X) and is unevenly distributed on the support side of the first amorphous layer (1) exhibiting photoconductivity.

FIG. 2 shows a layer region (
A first typical example of the distribution state of Group V atoms contained in g) in the layer thickness direction is shown.

In the example shown in FIG. 2, the surface (support 10 in FIG.
1) from the interface position tB where the surface of layer region (V) contacts the surface of layer region (V). No place li! Up to , the distribution concentration C of group Ⅰ atoms takes a constant value C, and is contained in the layer region (b) where group Ⅰ atoms are formed, and at position 1. The distribution concentration is gradually and continuously reduced from the distribution concentration C1 to the boundary surface position tT. At the interface position tiitr, the distribution concentration C of Group V atoms is C3.

In the example shown in FIG. 3, the distributed concentration C of the contained group V atoms gradually and continuously decreases from the distributed concentration C4 from the position tB to the position tT, and reaches the concentration C1 at the position tT. It forms a distribution state.

In the case of FIG. 4, position 1. From position t to - is Vth
The distribution concentration C of the group atoms is a constant value with the concentration C6, and the n1 position t
2 and position tT, the distribution density C is gradually and continuously decreased, and at position tT, the distribution density C is substantially zero.

In the case of FIG. 5, the group V atom is located at position tT from position tB.
The distribution density C is gradually and continuously decreased until it reaches , and becomes substantially zero at the position tq=.

In the example shown in FIG. 6, the distribution concentration C of the vi-th atom is a constant value of the distribution concentration C1l between the positions tn and t1, and is the distribution concentration CIG at the position tT. Position t, and position t! , the distribution density C is linearly decreased up to position t, and then to position 1.

In the example shown in FIG. 7, position t, tilt position lft
Up to 4, the distribution concentration CI+ takes a constant value, and from position t to positions t and r, the distribution concentration CI! The distribution state is such that the distribution concentration decreases in a linear function up to the distribution concentration C1m.

In the example shown in FIG. 8, from the position to to the position tT, the distribution concentration C of group (I) atoms decreases linearly from the concentration 014 to zero.

In FIG. 9, from position tn to position t, the distribution concentration C of Group Ⅰ atoms decreases in a linear function from distribution concentration Cl1l to distribution concentration Cl11, and between position t and position tT. An example is shown in which the distribution density C□ is set to a constant value.

In the example shown in FIG. 10, the distribution concentration C of group (III) atoms is the distribution concentration crt at the position ta, and the distribution concentration Crt at the position t
, this distribution concentration CI? At first, it decreases slowly, and near the position t, it decreases rapidly and becomes the distribution concentration C1l at the position t6.

Between the positions Wit, te and t, the distribution concentration is first rapidly decreased, and then gradually decreased to become the distribution concentration Cl11 at the position t, and the distribution concentration Cl11 at the position t, and the position t,
between Mt and Mt.
At s, the distribution density Coo is reached. Between position tijtta and position tT, the distribution concentration CIO is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 2 to 10, some of the typical examples of the distribution state of group (I) atoms contained in the layer region (V') in the layer thickness direction, in the present invention, On the support side, there is a part where the distribution concentration C of Group V atoms is high, and on the interface tT side, there is a part where the distribution concentration C is lower than on the support side, and the Group A contained layer region (7) is provided in the amorphous layer.

In the present invention, the layer region M in which the group (III) atoms that constitute the amorphous layer are completely contained is preferably a localized area where the group (III) atoms are contained in a high concentration toward the support side, as described above. area IA).

The localized region IA) is provided within 5 μm from the interface position tn, if explained using the symbols shown in FIGS. 2 to 7M10.

In the present invention, the localized region fA) is the interface position it
In some cases, the entire layer region L is up to 5 μ thick from tn, and in other cases, it is a part of the layer region LT.

Whether the localized region tAJ is to be a part or all of the layer region LT is determined as appropriate depending on the characteristics required of the amorphous layer to be formed.

The localized region +AJ is a distribution state of group V atoms contained therein in the layer thickness direction, and the maximum value Cmax of the content distribution value (distribution concentration value) of group V atoms is usually 100 with respect to silicon atoms. Atomic PIG or higher, preferably 150
Atomic I- or higher, optimally 20 Oatomic
It is desirable that the layers be formed in such a way that a distribution state of c-order or higher can be obtained.

That is, in the present invention, in the layer region (t) containing group V atoms, the maximum value Cmax of the distribution concentration exists within 5 μm in layer thickness from the support side (layer region 5 μ thick from ts). It is formed like this.

As described above, by providing the localized region IAJ containing a high concentration of group IV atoms on the support side in the layer region M, charge injection from the support side into the amorphous layer becomes more effective. can be prevented.

In the present invention, the content of group V atoms contained in the layer region (g) containing group generally 30 to 5 X 10' atoms
tc IIMI, preferably 50 to 1×4 10 atomic IIF! , optimally 100-5
X 103 atomic pPIll is preferable. The amount of oxygen atoms contained in the first layer region (0) is determined as desired depending on the characteristics required of the photoconductive member formed, but in normal cases, it is from 0.001 to 50 atomic%, preferably
0.002-40 atomic % optimally 0.00
It is desirable that the content be 3 to 30 atomic%.

In the photoconductive member of the present invention, the layer thickness tB of the layer region (V) containing group V atoms (layer region 10 in FIG.
30 layer thickness), and the layer region (B) which is provided on the layer region (G) and does not contain group Ⅰ atoms, that is, the part excluding the layer region (G) (Fig. 1 The layer thickness T of the layer region 106) is appropriately determined according to the purpose at the time of layer formation so that the first amorphous layer (1) with desired characteristics is formed on the support.

In the present invention, the layer region (b) containing group (ii) atoms
The layer thickness tB is usually 30λ to 5μ, preferably 40
λ~4μ, optimally 50λ~3μ, layer area 1Bl
The O layer thickness T is usually 0.2 to 95 μm, preferably 0.2 μm to 95 μm.
It is desirable that the thickness be 5 to 76μ, most preferably 1 to 47μ.

Further, the sum (T+tB) of the layer thickness T and the layer thickness tB is usually 1 to 100 μm, preferably 1 to 80 μm, and most preferably 2 to 50 μm.

The layer thickness t of the layer region to) containing oxygen atoms. Finally, a layer region (V) that shares at least a part of the layer region
It is desirable that the thickness be appropriately determined in accordance with the desired purpose in relation to the layer thickness tB. In other words, if the purpose is to strengthen the adhesion between the layer region (G) and the support that is in direct contact with the core layer region (To), the layer region (0) is the layer region (To). Since it is sufficient that it is provided at least in the support side end layer region, the layer thickness t0 of the layer region tO) is at most the layer region (
It is sufficient to have a layer thickness tB of V).

In addition, if it is intended to strengthen the adhesion between the layer region M and a layer region provided directly on the layer region (b) (corresponding to the layer region 106 in FIG. 1), the layer region (0) should be provided at least in the end layer region opposite to the side where the support is provided in the layer region M, so the layer thickness t of the layer region (0)
. For closing, it is sufficient to have at most the layer thickness tB of the layer region (b).

Furthermore, considering the case where the above two points are satisfied, the layer thickness t of the layer region (0). Finally, at least the layer region (V)
In this case, it is necessary to have a layer structure in which a layer region (g) is provided in a layer region ((2)).

In order to achieve more effective adhesion between the layer region (G) and the layer region provided directly on the layer region (7), the layer region (
0) above between the layer regions (in the opposite direction from the side with the support)
It is preferable to extend it to .

In the present invention, the amorphous layer (11) of the amorphous layer (1)
A portion containing no oxygen atoms is provided in the side edge layer region,
Since it is necessary to locally unevenly distribute the layer region (0) on the support side of the amorphous layer (1), the layer thickness t of the layer region (0) is determined.

The final step is usually 10λ to 10μ, preferably 2
It is desirable that the thickness be 0λ to 8μ, optimally 30λ to 5μ.

1 In the present invention, in order to form the amorphous layer (1) composed of a-8i (H9X), a vacuum method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method is used. It is done by a deposition method. For example, in order to form the amorphous layer (I) composed of a-3t (H, with gas,
or/and halogen atom (X) for introducing hydrogen atom (H)
A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a St.
A layer consisting of (H+X) may be formed. In addition, when forming by sputtering method, for example, Ar,
When sputtering a target composed of St in an atmosphere of an inert gas containing He% or a mixed gas based on these gases, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is used. It may be introduced into a deposition chamber for sputtering.

2 In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer (1) if necessary include fluorine, chlorine, bromine, and iodine. It can be mentioned as a suitable one.

The raw material gas for Si supply used in the present invention is 5IH4+ 5ItHa + 5lsT(a +
Silicon hydride (silanes) in a gaseous state or that can be gasified such as 814'H+o can be effectively used, especially in terms of ease of handling in layer creation work and good Si supply efficiency. SiL + 5itHa is preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogenides, interhalogen compounds, halogen-substituted silane derivatives, etc. Gaseous or gasifiable halogen compounds are preferably mentioned.

Furthermore, 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.

The halogen compounds preferably used in the present invention to be obtained from 1 to 1 include halogen gases such as fluorine, chlorine, bromine, and iodine, and BrF + ClF r ClF5 + Br
F,, , BrF5, IFs + IFy +
Examples include interhalogen compounds such as Icz and IBr.

...A silicon compound containing a halogen atom, so-called a halogen atom-substituted silane derivative, specifically, for example, 5IF4 + St2Fg l 5IC44H5IBr
Silicon halides such as No. 4 are preferred.

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 not used as a raw material gas capable of supplying Si. In both cases, ZIG is produced which forms an amorphous layer (1) of aS+ containing halogen atoms on a predetermined support.

When forming the 9 amorphous layer (I) 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,
, He, etc. are introduced into the deposition chamber where the amorphous layer ([) is to be formed, with a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. By this, an amorphous layer (I) can be formed on a predetermined 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.

Further, each gas may be used alone or in a mixture of multiple types at a predetermined mixing ratio.

In order to form amorphous Jm (1) made of a-8i (H9X) by a reactive sputtering method or an ion blating method, for example, in the case of a sputtering method, St
This is sputtered in a predetermined gas plasma atmosphere using a target consisting of This can be done by heating and evaporating a silicon evaporation source using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material 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 blasting method, the gas of the above-mentioned halogen compound or the above-mentioned silicon compound containing halogen atoms is introduced into the deposition chamber. The gas may be introduced into the atmosphere to form a plasma atmosphere of the gas.

Further, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, gas or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms.
In addition, hydrogen halides such as Hlli'', HC47 HEr, HI, S i H
++Ft + St HJt rSiHtCt, ,
Halogen-substituted silicon hydrides such as 5iHC4, StH, Brt + 5iT-TBr, etc., and halogen compounds that have hydrogen atoms as one of their constituents in a gaseous state or can be gasified, are also effective as an amorphous layer (for forming D). It can be mentioned as a starting material.

These halides containing hydrogen atoms form an amorphous layer (1
) During formation, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer. be done.

To structurally introduce hydrogen atoms into the amorphous layer (1),
In addition to the above, H, or SiH4, 5itHa +S
This can also be carried out by causing a discharge by causing a silicon hydride gas such as i sHs + S 14 t(+) to coexist with a silicon compound for supplying St in the deposition chamber.

For example, in the case of reactive sputtering method, St metal
A plasma atmosphere is formed by introducing a gas for introducing halogen atoms and a T gas, including inert gases such as He and Ar as necessary, into the deposition chamber, using a By sputtering the metal, an amorphous layer (1) consisting of a-8t ('H,X) is formed on the support.

Furthermore, a gas such as BtHa can also be introduced for doping with impurities.

In the present invention, the amorphous layer (1
), the amount of hydrogen atoms (H) or the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+
X) is usually 1 to 4° atomic%, preferably 5 to 30 atomic%.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer (D), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (
The amount of the starting material used to contain X) introduced into the deposition system, the discharge force, etc. can be controlled.

A layer region (V) containing group (I) atoms in the amorphous layer (1)
In order to establish the layer region (0) containing oxygen atoms at λ, when forming the amorphous layer (1) by a glow discharge method, a reactive sputtering method, etc., a starting material for introducing group and using the starting materials for introducing oxygen atoms together with the starting materials for forming the amorphous layer (1) described above in 1-2,
The layer region (0) containing oxygen atoms and the inclusion of group (Ⅰ) atoms constituting the amorphous layer (1) are achieved by controlling the amount of the oxygen atoms contained in the layer to be formed. When a glow discharge method is used to form each of the layer regions (V), the starting materials for forming the amorphous layer (1) listed above may be used as the starting materials for forming the amorphous layer (1). A starting material for the introduction of one group of oxygen and/or a starting material for the introduction of a group (I) group is added to those selected according to preference. As a starting material for introducing an oxygen atom or a starting material for introducing a group Ⅰ atom, a gaseous substance containing at least an oxygen atom or a group Ⅰ atom or a gasified substance that can be gasified is used. Most of them can be used.

hmm? For example, if a layer region (O) is to be formed, a log '81 gas containing silicon atoms (St2) as constituent atoms, a raw material gas containing oxygen atoms (0), and hydrogen atoms as necessary. (H) and/or a raw material gas whose constituent atoms are halogen atoms (X) are mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and oxygen atoms are used. (0) and a raw material gas whose constituent atoms are hydrogen atoms ()I) are also mixed at a desired mixing ratio, or alternatively, a raw material gas whose constituent atoms are silicon atoms (Si) and a silicon atom (S i) + oxygen atom (0
) and hydrogen atoms (H) can be mixed and used.

Also, separately, silicon atoms (St) and hydrogen atoms (T
You may mix and use the raw material gas which has an oxygen atom (0) as a constituent atom with the raw material gas whose constituent atoms are ().

Specifically, starting materials for introducing oxygen 1f molecules include, for example, oxygen (02), ozone (O3), -nitrogen oxide (NO), nitrogen dioxide (NO2), -nitric oxide S/ element (N2o). , nitrogen sesquioxide (N,,0.,), trinitric oxide (N204), nitrogen sesquioxide (N20.), nitrogen trioxide (NO,).

Silicon atom (St), oxygen atom (0) and hydrogen atom (1
1) as constituent atoms, for example, disiloxa 7 (H
s S i O8i HB)H)
Examples include lower siloxanes such as HaSi (f3iH, 08iH9, etc.).

When the layer region (■) is formed using the glow discharge method, PHs is effectively used in the present invention as a starting material '14 for introducing group (III) atoms.
, the hydrogen ratio next to P2H4, etc., PH,I.

PF3 HPF6 HPC4s + PO2+ PBr
Examples include 710 genated phosphorus such as s I PBr= l PI3. In addition, AsTTm + AsF5! A
sC4+ AsBr3 + AsF5 l 5bHx
+ 5bFs + SbF', l 5bC4+5bC
4+ BiHs + B1C4+ B1Br5 and the like can also be mentioned in 17 as effective starting materials for the introduction of Group Ⅰ atoms.

The content of Group ■ atoms introduced into the layer region (■) containing Group ■ atoms is determined by the gas flow rate of the starting material for introducing Group ■ atoms flowing into the deposition chamber, the gas flow rate ratio, It can be arbitrarily controlled by controlling discharge power, support temperature, pressure inside the deposition chamber, etc.

In order to form the layer region (0) containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer, a 5iOz wafer, or a wafer containing a mixture of St and Stow is used as a target. etc., by sputtering in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is diluted with a diluent gas as necessary to create a deposition chamber for sputtering. The Si wafer may be sputtered by introducing the gas into the Si wafer and forming a gas plasma of these gases.

Alternatively, by using Si and SiOx as separate targets or by using a single mixed target of Si and 5iOz, at least hydrogen atoms can be mixed in an atmosphere of dilution gas as a sputtering gas or (n)
Alternatively, sputtering may be performed in a gas atmosphere containing halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, a so-called rare gas, e.g. He, Ne, Ar
etc. can be mentioned as suitable ones.

In the photoconductive member of the present invention, the layer region (B) (in FIG. By containing a substance that controls the conduction characteristics in the layer region (corresponding to layer region 106), the conduction characteristics of the layer region (B) can be arbitrarily controlled as desired.

j These various substances include so-called impurities in the semiconductor field, and in the present invention, a St (H+
On the other hand, a P-type impurity that gives P-type conductivity characteristics, specifically, an atom belonging to Group Ⅰ of the periodic table (Group Ⅰ atom), for example, B (boron).

At (aluminum), Ga (galium A)
, In (indium), T7=(lambda)%, and B1Ga is particularly preferably used.

In the present invention, the content of the substance controlling the conductive properties contained in the layer region CB) is determined by the conductive properties required for the layer region (3) or the substance that directly contacts the layer region (B). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided as a layer and the characteristics of the contact interface between the layer and the layer region.

In the present invention, the content of the substance controlling the conductive properties contained in the layer region (B) is usually 0.0
01-1001000ato ppm, preferably 0.
05-50Datomic 1)T)m + Optimally 01-200atomic, ? It is desirable to set the value to tl PI'1m.

Substance 2 controlling the conduction properties in the layer region (B), e.g.
In order to structurally introduce group atoms, they may be introduced together with a layered starting material. Possible starting materials for the introduction of Group Ⅰ atoms include:
It is desirable to use a material that can be easily gasified at least under layer forming conditions. Specifically, as a starting material for introducing a group Ⅰ atom, for introducing a boron atom, R
tHa * B4H1゜, BaT(, Bat(n,
BaH+o, BaH+t.

Boron hydride such as B6H14, BFs + BCI-s
+ Boron halides such as BBrs and the like can be mentioned. This pond, A, t.

GaC4, Ga(CHs)x + InCl21 TL
C4 etc. can also be mentioned.

In the photoconductive member of the present invention, as explained in the example shown in FIG.
0) is locally unevenly distributed toward the support side in the amorphous layer (1)? ! Although this is a preferred embodiment, the present invention is not limited thereto. The amorphous layer (I) may also be formed on the surface of the substrate.

In this case, since the amorphous layer (1) must be made to exhibit photoconductivity, the upper limit of the amount of oxygen atoms contained in the layer region (0) is usually 30 ato
mic%, preferably 10 atomia%.

Optimally, it is desirable to set it to 5 atomic%. In this case as well, the lower limit is of course set to the above value.

In the photoconductive member 100 shown in FIG. It is provided in order to achieve the objectives of the present invention mainly in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability.

Further, in the present invention, a first amorphous layer (1) 102 and a second amorphous layer (1) 107 constituting the amorphous layer (1) it;)2 are formed. Since each of the amorphous materials has a common constituent: silicon atoms.

Chemical stability is sufficiently ensured at the laminated interface.

The second amorphous layer (1) is made of an amorphous material (a-(S I xc
l −x)yH+ −y, where O< x 1 y
< 1).

The second amorphous layer (1) composed of a-(SixC+-x)yH+-y can be formed by a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, an electron beam method, etc. Therefore, it is accomplished. These manufacturing methods are manufacturing conditions.

It is selected and adopted as appropriate depending on factors such as the level of equipment capital investment and the desired characteristics of the photoconductive member to be manufactured. Control is relatively easy. A glow discharge method or a sputtering method is preferably employed because of the advantages of easy implementation, such as introduction of carbon atoms and hydrogen atoms together with silicon atoms into the second amorphous layer.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to form the second amorphous #(1).
may be formed.

In order to form the second amorphous layer (1) by the glow discharge method, the raw material gas for forming a-(5ixC+-x)yH+-y is mixed with a dilution gas as necessary at a predetermined mixing ratio. The mixed gas is introduced into a deposition chamber for vacuum deposition where the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge to remove the particles already formed on the support 101. ? 2- on the amorphous layer (1) of a-(SiXC,-x), H,
-, it is sufficient to deposit .

In the present invention, a (5ixC+ -x)yH+
As the raw material gas for forming -y, most of the gaseous substances containing at least one of 8i, C, and H 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 H, 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 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. Alternatively, a raw material gas having 8i as a constituent atom and a raw material gas having three constituent atoms, Si, C, and H, can be mixed and used.

Separately, C is added to the raw material gas containing 8i and H as constituent atoms.
It is also possible to use a mixture of raw material gases having constituent atoms.

In the present invention, gases that are effectively used as raw material gases for forming the second amorphous layer (1) include SiH, Si, H, Si, H8, whose constituent atoms are Si and H. ,5i4H
Silicon hydride gas such as silanes (8ilane) such as 1°, saturated hydrocarbons containing C and H as constituent atoms, e.g. having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, carbon atoms Examples include 2 to 3 acetylene hydrocarbons.

Specifically, as a saturated hydrocarbon, methane (CH4)
, xriy (CtH,), 7'l:lhough (C
H3), n-butane (n-Cd(1o) r-pentane (CIIHn), and the ethylene hydrocarbons include ethylene ((4H4).

Propylene (CsHe), butene-1 (C4H3
), butene-2 (C4H8) p-isobutylene (
CaHs) rpentene (CaH+.), acetylene hydrocarbons include acetylene (CtHt)
, methylacetylene (C3H4), butyne (C4H
6) etc.

As a raw material gas containing Si, C, and H as constituent atoms, 5
Examples include alkyl silicides such as i(CH3), 5i(C, horse)4, and the like. In addition to these raw material gases, H2 is of course also used as an effective raw material gas for introduction.

To form the second amorphous layer (1) by the sputtering method, a single crystal or polycrystalline Si wafer or a C
The target is a 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 diluting gas as necessary and introduced into the deposition chamber for sputtering. The Si wafer may be sputtered by forming plasma.

Alternatively, sputtering can be performed in a gas atmosphere containing at least hydrogen atoms by using Si and C as separate targets or by using a single mixed target of f3i and C.

As the raw material gas for introducing II/C or (1), the raw material gases shown in the glow discharge example described above can also be used as effective gases in the case of sputtering.

In the present invention, the diluent gas used when forming the second amorphous layer (1) by the glow discharge method or the spuckling method is a so-called conditional gas, such as He, Ne,
Ar4 can be cited as suitable.

The second amorphous layer (If) in the present invention is carefully formed so that its required properties are provided as desired.

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. of.

Also, the properties between photoconductive properties and non-photoconductive properties are
Therefore, in the present invention, in order to form a-(SixC,-x)yH,-, which has the desired properties according to the purpose, the manufacturing conditions must be strictly selected according to the desired conditions. be accomplished.

For example, to provide the second amorphous layer (1) with the main purpose of improving pressure resistance, a-(SiXC,-x), H,-.

is prepared as an amorphous material with pronounced electrically insulating behavior under conditions of use.

In addition, when the second amorphous 1m(1) is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the open environment, the above-mentioned degree of electrical insulation may be reduced to a certain extent, and the irradiation may be a-(8ixC1-x)yH, -y is created as an amorphous material that has a certain degree of sensitivity to light.

On the surface of the first amorphous layer (1), a-(”1 xCl −
When forming the second amorphous material 111 (1) consisting of , in the present invention, a(SixC+-
x) It is desirable that the temperature of the support during the formation of the y layer is tightly controlled so that yH4 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 (I) is determined by the method of forming the second amorphous layer (1). In addition, the second amorphous layer (II) is formed by appropriately selecting the optimum range, but in general, the temperature is 50°C to 350°C, preferably 1
It is desirable that the temperature is between 00°C and 250°C. In forming the second amorphous layer (1), delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. It is advantageous to employ the glow discharge method or the sputtering method, but when forming the second amorphous layer (seal) 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 generated a (5txC1-X)yHl-y.

a- having the characteristics for achieving the object of the present invention;
(5ixC1-x)yH+-y is normally created as a discharge power condition of 10 to 3
00W, preferably 20 to 200W. It is desirable that the gas pressure in the deposition chamber is normally about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr.

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second amorphous layer (seal) include the values in the above ranges, but these layer creation factors are as follows: They are not determined independently and separately, but are mutually organically related so that a second amorphous layer (seal) consisting of a-(Sixc, -x), H,-, with desired characteristics is formed. It is desirable that the optimal value of each layer creation factor be determined based on the properties of the layers.

The amounts of carbon atoms and hydrogen atoms contained in the second amorphous layer (1) in the photoconductive member of the present invention are the same as the conditions for producing the second amorphous layer (seal). The formation of the second amorphous layer is an important factor in achieving the desired properties.

The amount of carbon atoms contained in the second amorphous layer (1) in the present invention is usually I x 10-3 to 90 atomic
%, preferably 1 to 90 atomic %, most preferably 10 to 8 Q atomic %. The content of hydrogen atoms, and the normal content of hydrogen atoms, 1 to 40 atomic%, preferably 2 to 35 a
atomic%, preferably 5 to 30 atomic%, and when the hydrogen content is in this range, the photoconductive member formed is well suited for practical applications. It's something you get.

That is, if it is done using the above bounds a -(SixC1-x), )(, -y, it is usually 0.1 to 0.99999, preferably O1 to 0.99, optimally 0.15. -0.9.7 is usually 0.6-0.99°, preferably 0.65-0.98
, the optimum value is 07 to 0.95.

The numerical range of the layer thickness of the second amorphous layer (1) 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 # (11) 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 (seal) is determined by the amount of carbon atoms and hydrogen atoms contained in the layer (1), the first amorphous layer #(■
) should be appropriately determined as desired based on the organic relationship depending on the characteristics required for each latch layer region. 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 (It) in the present invention is usually 0.003 to 30 μm, preferably 0.004 to 20 μm.
It is desirable that μ is optimally set to 0.005 to 10 μ.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr and stainless steel.

kl, Cr, Mo, Au, Nb,
Ta, V, Tj, Pt.

Examples include metals such as Pd or alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose.

Acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polyurethane, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. These adhesives 7 It is preferable that at least one surface of the electrically insulating support is subjected to a conductive treatment, and another layer is provided on the conductive treated surface side.

For example, if it is glass, NiCr is applied to its surface.

AJ, Cr, Mo, Au, Ir, Nb, Ta, V, Ti
.

Pt, Pd, In2O3, 8nO,, ITO (
Conductivity can be imparted by providing a thin film made of In2O3+ 8nO, ), etc., or if it is a synthetic resin film such as a polyester film, NiCr, Al
, Ag, Pb.

Zn, Ni, Au, Cr, Mo,
Ir, Nb, Ta, V.

Conductivity is imparted to the surface by providing a thin film of metal such as Ti or Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the interface with the metal. 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. 1 is used as an electrophotographic image forming member. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape. The thickness of the support is appropriately determined so that the desired photoconductive member is formed.
When flexibility is required as a photoconductive member, it is made as thin as possible within a range that allows it to fully function as a support. In such cases, the thickness is usually set to 10 μ 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 to 1106 in the figure, raw material gases for forming each layer of the present invention are sealed.
As an example, 1102 is 8iH gas diluted with He (99.999% purity).

Hereinafter abbreviated as 8 iH,/He. ) cylinder, 1103 is BtHa gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as B and H6/He. ) cylinder, 1104 is a PH3 gas diluted with He (purity 99.99%, hereinafter abbreviated as PH,/He) cylinder, 1105 is a C2H gas (purity 99.999%) cylinder, 1106 is No gas (99.99% purity) It is a cylinder.

In order to flow these gases into the reaction chamber 1101, pulps 1122 to 1126 of gas cylinders 1102 to 1106 are used.
, confirm that the leak pulp 1135 is closed, and also check that the inflow pulp 1112 to 1116° and the outflow pulp 11
17 to 11211 After confirming that the auxiliary pulp 1132 is open, the main pulp 1134 is first opened to exhaust the inside of the reaction chamber 1101s gas pipe. Next, vacuum gauge 11
When the reading of 36 becomes approximately 5 x 10'torr, the auxiliary pulp 1132.

Close outflow pulps 1117-1121.

To give an example of the case where the first amorphous layer (+) is formed on the base 1137, the gas cylinder 1102 and SiH4
/He gas, from gas cylinder 1104 to PHs/HeJ gas, from gas cylinder 1106) No gas to pulp 1122
, 1124 , 1126 and outlet pressure gauge 1127
, 1129 , 1130 to 1%, and gradually open the inflow pulps 1112 , 1114 , 1116 to mass flow controllers 1107 , 1109 .

1111 respectively. Subsequently, outflow pulp 1
117, 1119, 1121, auxiliary valve 113
2.2 is gradually opened to allow each gas to flow into the reaction chamber 1101. SiH4/He gas flow rate and PH at this time,
/) Adjust the outflow valves 1117, 1119 and 1121 respectively so that the ratio of Ie gas flow rate to NO gas flow rate becomes the desired value, and adjust the vacuum gauge so that the pressure inside the reaction chamber 1101 becomes the desired value. Adjust the opening of the main valve 1134 while watching the Y & M of 1136. He then confirmed that the temperature of the base 1137 was set to a temperature in the range of 50 to 400°C by the heating beater 1138.
140 to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the flow rate of the PH,/He gas is gradually adjusted manually or by an externally driven motor or the like by controlling the valve 1118 according to a pre-designed rate of change curve. The distribution concentration of phosphorus atoms (P) contained in the layer formed by performing a changing operation is controlled. As described above, layer regions (p, o) containing phosphorus atoms and oxygen atoms are first formed on the base 1137.

t/ At this time, PH, /He gas or NO gas reaction chamber 1
By blocking the introduction into the gas introduction tube 101 by closing the valve of each corresponding gas introduction pipe, the layer thickness of the layer region containing phosphorus atoms or the layer region containing oxygen atoms can be arbitrarily adjusted depending on the situation. It can be controlled.

A layer region (P) containing phosphorus atoms and oxygen atoms, respectively.

After 0) is formed to a desired layer thickness as described above, each of the outflow valves 1119 and 1121 is closed and glow discharge is continued for a desired time to form a layer region containing phosphorus atoms and oxygen atoms, respectively. A layer region containing no phosphorus atoms and oxygen atoms is formed on (p 2 , o) to a desired layer thickness, and the formation of the first amorphous layer (1) is completed.

In the case where the first amorphous layer (1) contains NO-logon atoms, for example, Si F4 /He is further added to the above gas and the mixture is fed into the reaction chamber 1101.

In order to form the second amorphous layer (1) on the first amorphous layer (1) formed on the substrate 1137 by the above-described operation, the first amorphous layer ( For example, SiH by the same valve operation as in step 1).

Gas, C, H, and gas are each diluted with a diluent gas such as He as necessary, and flowed into the reaction chamber 1101 at a desired flow rate ratio, and glow discharge is generated according to desired conditions. be done.

The total number of carbon atoms contained in the second amorphous layer (1) is:
For example, by adjusting the flow rate ratio of SiH gas and C, H gas as desired, it is possible to arbitrarily control the flow rate as desired.

It goes without saying that all the outflowing pulp other than the gas necessary for forming each layer is closed, and when forming each layer, the gas used for forming the previous layer is discharged from the reaction chamber 1101.
Inside, from the outflow pulp 1117 to 1121 to the reaction chamber 1101
In order to prevent the pulp from remaining in the piping leading to the system, the outflow pulp 1117 to 1121 is closed, the auxiliary valve 1132 is opened, and the main valve 1134 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. .

Example 1 A layer was formed on an aluminum substrate using the manufacturing apparatus shown in FIG. 11 under the conditions shown in No. 13 below.

The electrophotographic image forming member thus obtained was placed in a copying machine and corona charged at 05KV for 0.2 seconds.
A light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0/ux, sec. The latent image was developed with a charged developer (containing +/- toner and carrier) and transferred to ordinary paper, which was then cleaned by a membrane blade and transferred to the next copying process. Even when such a process was repeated over 150,000 times, no deterioration of the image was observed.0 Example 2 Using the manufacturing equipment shown in Figure 11, parameters for the content of phosphorus (P) in the layer were determined. As, amorphous layer (1) on A2 substrate
The procedure was the same as in Example 1 except that layer formation was performed. The common manufacturing conditions for each sample at this time are as shown in Table 2-1. Table 2-2 shows the distribution concentration of phosphorus atoms contained in the first amorphous layer (I) at each position in the layer thickness direction from the substrate surface and the electrophotographic properties of the obtained sample. The evaluation results are shown.

The numbers in the left column of the table indicate sample numbers.

Each of the produced electrophotographic image forming members undergoes a series of electrophotographic processes including charging, image exposure, development, and transfer to improve the [density], resolution, and tone reproduction of images visualized on transfer paper. Comprehensive evaluation of 1-/1 with poor quality of 1a.

1\tl 7 The values in Table 2-2 are the distribution concentration of phosphorus (atm, I)T)m)
shows.

◎; Excellent ○; Good △: Sufficient for practical use Example 3 A layer was formed on the M substrate under the conditions shown in Table 3 below using the manufacturing apparatus shown in FIG.

Corona charging was performed at 12.05 KV for 0.2 secC, and a light image was irradiated (~.The light source was a tungsten lamp, and the light intensity was 1.071 ux, sec.The latent image was created using a charged developer ( The transferred image is developed with a toner (containing toner and carrier) and transferred to regular paper, but the transferred image is cleaned by the decoder and moved on to the next copying process. Even if this process is repeated over 100,000 times, the image does not deteriorate. was not seen.

Example 4 Using the apparatus shown in FIG. 11, a layer was formed on an Al substrate under the conditions shown in Table 4 below.

Other conditions were the same as in Example 1.

The electrophotographic image forming member thus obtained was placed in a copying machine and corona charged at 05KV for 0.2 seconds.
A light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 Aux, sec. The latent image is developed with a charged developer (containing toner and carrier),
The - is transferred to regular paper, but is cleaned by a rubber blade and transferred to the next copying process. Even after repeating this process more than 150,000 times, no deterioration of the image was observed.

ゝゝゝゝゝゝゝ7ゝゝゝ＼8, 6/Example 5 When forming the amorphous layer (II), SiH4 gas and C2H4
An image forming member was prepared in the same manner as in Example 4, except that the gas flow ratio was changed to change the content ratio of silicon atoms to carbon atoms in the amorphous layer (II).

After repeating the steps up to transfer about 50,000 times using the method described in Example 1 for the image forming member obtained in steps 1 to 1,
When the image was evaluated, the results shown in Table 5 were obtained.

1, 2) Example 6 Each of the image forming members was prepared in exactly the same manner as in Example 1, except that the layer thickness of the second amorphous layer (IT) was changed as shown in Table 6 below. The evaluation results are shown in Table 6 below.

\ \ t See Table 6. Example 7 Layer formation was performed and evaluated in the same manner as in Example 1, except that the method for forming the first amorphous layer (1) was changed as shown in Table 7 below. However, good results were obtained.

7.2 Example 8 Layer formation was performed in the same manner as in Example 1, except that the method for forming the first amorphous layer (1) was changed as shown in Table 8 below, and when evaluated, good results were obtained. 0 2A Example 9 The Φ conditions shown in Example 3 and the conditions shown in Table 9 below were used, except that the layer creation conditions in the second and third layer creation stages of Example 3 were set to the conditions shown in Table 9 below. According to the procedure, each of the electrophotographic image forming members was fabricated and evaluated in the same manner as in Example 1.
Good results were obtained for each, especially in terms of image quality and durability.

\ 1 2 A simple fi52 light in the 4.1 direction Figure 1 shows the layer structure of the Kusen'1 ratio member of the present invention as
Schematic layer structure for clarity Figure 1 Figures 2 to 10 each illustrate the distribution state of group (I) atoms between layer regions containing m V byc atoms constituting amorphous 1-. FIG. 11 is a schematic explanatory diagram of the apparatus used in the present invention.

100... Light guide peak member 1010・Support 102...first amorphous/1) 103...layer area (V) 104 fist... layer area (131 105...Second amorphous layer (il1 106...Free surface Applicant: Canon Co., Ltd. Agent Maru Shima Gi -□ 3 Continuation of page 1 ・Yo Ohri, the 7th speaker 3-30 Shimomaruko, Ota-ku, Tokyo No. 2 Canon Co., Ltd. 12. Initiator: Shigeru Shirai 3-30 Shimomaruko, Ota-ku, Tokyo No. 2 Canon Co., Ltd.

Claims (1)

[Claims] (1) A support for a photoconductive member, a first amorphous layer having photoconductivity composed of an amorphous material having silicon atoms as a matrix, and silicon atoms, carbon atoms, and hydrogen atoms. and a second amorphous layer made of an amorphous material containing, wherein the first amorphous layer contains oxygen atoms as constituent atoms and is unevenly distributed toward the support side. a first layer region which is continuous in the layer thickness direction, and which contains atoms belonging to group Ⅰ of the periodic table as constituent atoms, with a greater distribution toward the support side; A photoconductive member comprising: