JPS58159545A - 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 halogen. 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 halogen. The layer 102 comprises the first layer region 103 contg. O as a component, a layer region 104 consisting of the region 103 and the second layer region 105 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 range of tB-ti 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 t1-tT, where tT is an interface between the layer regions 105 and 106, and this region 106 contg. neither O nor said element.

Description

[Detailed description of the invention] The present invention is based on light (here, light in a broad sense, ultraviolet light).

The present invention relates to photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, gamma rays, etc.

For solid-state imaging devices or electrophotography in the image forming field■
As a photoconductive material for forming a photoconductive layer in an original forming member or a document reading device, it is highly sensitive and has a low S/N ratio [light'1 current (l
p)/dark current (ld)) is high, has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has a high light weight A- property (, has a desired dark resistance value, and has a desired dark resistance value during use. be non-polluting to the human body;
Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time.

Particularly, in the case of an electrophotographic chair forming member that is incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-pollution during use is an important point.

Based on this point, amorphous silicon (hereinafter abbreviated as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and German Published Publication No. 2951411 describes its application to a photoelectric conversion/reading device.

Heigo et al., a conventional optical terminal with an optical The reality is that there are points that can be further improved in terms of use environment characteristics such as moisture and dry resistance, and furthermore, in terms of stability over time, which requires comprehensive improvement of characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When used repeatedly for a long period of time, fatigue caused by repeated use occurs, resulting in a new ghost phenomenon, which causes an afterimage.

Or, for example, according to many experiments by the present inventors, 'a as a material constituting the photoconductive layer of an electrophotographic image forming member.
Although -8T has many advantages compared to conventional inorganic photoconductive materials such as Se, Cdg, and ZnO or organic photoconductive materials such as PVCz and TNF, it has some characteristics for use in conventional solar cells. Even if the above photoconductive I- of an electrophotographic image forming member having a single-layer photoconductive layer consisting of a-8f imparted with an electrostatic image is subjected to a charging treatment for forming an electrostatic image, dark decay does not occur. is significantly faster,
This can be solved because it is difficult to apply ordinary electrophotographic methods, and in a humid atmosphere, the above tendency is remarkable, and in some cases, it may be impossible to hold the tungsten particles until the development time. It has been found that possible points exist.

Furthermore, when a photoconductive layer is composed of a-8i material, boron atoms, phosphorus atoms, etc. are used to control electrical conductivity, or other atoms are used as constituent atoms to improve other properties. However, depending on how these constituent atoms are contained, problems may arise in the electrical bending (and photoconductive properties) of the formed layer.

That is, for example, the lifetime of photocarriers generated in the layer formed by light irradiation in the formed light guide 'tJjL layer is insufficient, or 'e' from the support side in a dark area.
4t, there are many cases where the prevention of load injection is not sufficient.

Therefore, while the characteristics of the a-8i material itself are being improved, the above-mentioned methods were used when designing the original $1 tffi member.
1! It is necessary to devise ways to obtain the desired spiracle, optical and light-permissive properties.

The present invention has been made based on the above points, and the applicability of a-8i as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, K7R removal devices, etc., and its application. Comprehensive and intensive research from the viewpoint of performance (amorphous materials (non-crystalline materials) containing hydrogen, amorphous silicon with accumulated water, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as these, etc.)] Photoconductive materials designed and manufactured to be generically specific not only show extremely superior properties in practical use (compared to conventional photoconducting IM and HIS materials, but also
This is based on the discovery that it is superior in all respects, and in particular has extremely excellent properties as a photoconductive member for electrophotography.

The present invention is an all-environment type in which the electrical and optical one-dimensional conductive 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. Excellent durability with no or almost no residual α position.
The main object of the present invention is to provide a photoconductive member that will not be washed away.

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 band processing for electrostatic image formation, making ordinary electrophotographic methods extremely effective. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties that can be applied.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality yellow 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 comprises a support for the photoconductive member, an amorphous material having silicon atoms as a matrix and preferably containing at least either a hydrogen atom side or a halogen atom (3) as a constituent atom. a-8i(H, an amorphous layer, the first amorphous layer contains oxygen atoms as a constituent atom, and has a first layer region unevenly distributed toward the support side as described in iif above, and a first layer region in the layer thickness direction. It is defined as having a second layer region that is continuous and is distributed more toward the support side, and contains atoms belonging to Group Ⅰ of the periodic table as constituent atoms.

It exhibits characteristics designed to have the layer structure described above.

In particular, when applied as an electrophotographic image forming member, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical characteristics, and has excellent Hatake sensitivity. It has a high signal-to-noise ratio, has good resistance to fatigue, repeated use characteristics, especially in a humid atmosphere, and has high density, clear halftones, and high resolution. You can get the quality of the picture you want.

Hereinafter, according to the drawings, a light guide 111 of the present invention. The parts will be explained in detail.

FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure on the photoconductive part side of the present invention.

The light 2!4 cage member 100 shown in FIG. 1 is a-8t (H,
First amorphous layer (1) consisting of carbon and exhibiting photoconductivity 10
2 and the first amorphous layer (1) 102, a second amorphous layer (nNO7 and have

The amorphous 1171 layer F11102 is a first layer region (0) 1o6 containing oxygen atoms as constituent atoms, number 1 of the periodic table.
A second layer region (V) 104 containing atoms belonging to the group (Group Ⅰ atoms), and a layer region 10 that does not contain oxygen atoms and Group Ⅰ atoms on the second layer region (V1104)
It has a layered structure consisting of 6.

The layer region 105 provided between the first layer region (01105 and the layer region 106) contains group (I) atoms but does not contain oxygen atoms.

Group Ⅰ atoms contained in the second layer region (V) 104 are:
It is continuously and non-uniformly distributed in the layer thickness direction, and the support lQ
10 is continuously and substantially uniformly distributed in a plane substantially parallel to the surface.

In the present invention, oxygen atoms contained in the first layer region (ONO3) are distributed in a substantially uniform manner in the layer thickness direction and in a plane parallel to the surface of the support 1010.
It is contained in the entire layer area of the first layer area (0) 103.

In the present invention, an emphasis is placed on improving the adhesion between the first layer region (Q) and the support on which the first amorphous layer (1) is directly provided by containing oxygen atoms. It is measured.

In the photoconductive member of the present invention such as the example shown in FIG.
One layer has a layer region (corresponding to the layer region 106 shown in FIG. 1) that does not contain oxygen atoms and group (I) atoms, but
A layer region (layer region 105 shown in FIG. 1) that contains group (I) atoms but does not contain oxygen atoms does not necessarily need to be provided.

That is, for example, in FIG. 1, the first layer region (0) 10
6 and the second layer region (V) 104 may be the same layer region, or even if the second layer region (V) 104 is provided in the first layer region + 0) 103. It's good.

In the light guide 'tJL member of the present invention, the first 19 region (1) which constitutes a part of the amorphous layer (1) and contains oxygen atoms (
0) is amorphous layer (11) for the purpose of improving adhesion with the support, and also constitutes a part of the amorphous layer (1) and contains group Ⅰ atoms. The second layer region (■) contained in the amorphous layer (11) is caused, in part, by charging the inside of the amorphous layer (11) from the support side when the free surface side of the amorphous 74 layer (It) is subjected to charging treatment. For the purpose of preventing implantation, an amorphous layer (I
) as part of the support and amorphous Ii! The layer (1) is provided in a structure in which at least a portion of the layer region to which the layer (1) is bonded is shared.

In addition, in order to more effectively improve the adhesion between the second layer region (■) or the layer region provided directly on the second layer region (V), From the contact interface with the support, the first j-region (0) to the second layer region (■)
It is preferable to provide a support layer region (0) in the amorphous layer (1) so as to enclose the support layer region (0).

The group (III) atoms contained between the layer regions are continuous in the layer thickness direction and are located on the side opposite to the side on which the support is provided (the amorphous side in FIG. 1). (V) in the j-region so that it is distributed more toward the support side than the mass layer (n) (107 mu).
Contains K.

In the present invention, the atoms belonging to Group Ⅰ of the periodic table contained in the second layer region (②) constituting the amorphous layer fl) are P (phosphorus) and As (arsenic). These include sb (antimony), Bi (bismuth), etc., and P and As are particularly preferably used.

In the present invention, the distribution state of Group (1) atoms contained in the 1-region (1) 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.

FIGS. 2 to 10 show typical distribution states of group (I) atoms in the layer thickness direction contained between layer regions constituting the first amorphous layer pile of the photoconductive member of the present invention. An example is 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;
In the examples shown in FIGS. 2 to 10, in the following description, the layer region (0) containing oxygen atoms will not be discussed unless a specific explanation is required.

In FIGS. 2 to 10, the horizontal axis represents the content C of group (I) atoms, and the vertical axis represents the first amorphous layer (I) exhibiting photoconductivity.
Indicates the layer thickness of the layer region containing Group V atoms (■) provided in Between layer regions containing group (2) atoms, layers are formed toward the tT side rather than the ta side.

In the present invention, the atoms of group (I) are unevenly distributed on the support side containing the atoms.

In Fig. 2, the layer region constituting the first amorphous layer (I) is shown.
) A first typical example of the distribution state of group (I) atoms contained in the layer thickness direction is shown.

In the example shown in FIG.
0 surface) and the surface of the layer region (2) from the interface position ta to the position tl, the distribution concentration C of the group ■ atoms takes a constant value CI, and the group ■T continuously has been reduced. At the interface position ['h, the distribution concentration C of Group Ⅰ atoms is assumed to be Cs.

In the example shown in FIG. 6, the distribution concentration C of the Group III atoms contained gradually and continuously decreases from the distribution concentration C4 from position t6 to position d, and at position tT, the concentration Cs The distribution state is formed as follows.

In the case of FIG. 4, the distribution density C is reduced from position t6 to position ITS, and the distribution density C is substantially zero at position tT.

In the case of FIG. 5, the group (III) atoms are continuously and gradually reduced from the distribution concentration C8 until they are concentrated from the position t8 to the position fltT, and are substantially zero at the position tT. In the example shown in the figure, the distribution concentration C of the VIk atom
Between position ta and position 18, the distribution main density C is linearly decreased from position t8 to position ttT on axis j.

In the example shown in FIG. 7, from position @tB to position t4
From position t4 to position tT, the distribution concentration C1l takes a constant value, and from the distribution concentration C1z to the distribution concentration Cts -
It is assumed that the distribution state decreases in number.

In the example shown in FIG. 8, from the position ta to the position tT, the distribution concentration C of group (I) atoms decreases linearly from the concentration C14 to zero.

In FIG. 9, from position Ii\tB to position tll, the distribution concentration C of group V atoms decreases linearly with the distribution structure degree C3zst', and from position Ii\tB to position tll.
6 and position tT, an example is shown in which the distribution density ax is kept at a constant value.

In the example shown in FIG. 10, the distribution concentration C of group (III) atoms is the distribution concentration Gl'l at the position Wi t B, and the distribution concentration C'17 is slowly increasing until the position t is reached. It is decreased rapidly near the position t, and the distribution concentration becomes C1@ at the position t.

Between position t and position t, the distribution density is first rapidly decreased, and then gradually decreased until it reaches position C11 at position t, and between position t and position 〇. Then, the concentration is gradually decreased very slowly and reaches the distributed concentration CaO at position t8. Between position t8 and position t1, the distribution density C'20 seems to become substantially zero ((
It is reduced according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 2 to 10, some examples of bait types of distribution state charts in the layer thickness direction of Group Ⅰ atoms contained in the layer region (V), in the present invention, ,
On the support side, there is a part with a high distribution concentration C of Group (1) atoms, and on the interface tT side, there is a part where the distribution concentration of Group (1) atoms is lower than that on the support side where the distribution concentration is 0.
A layer region (V) containing group atoms is provided in the amorphous layer.

In the present invention, the layer region (V) containing Group Ⅰ atoms constituting the amorphous layer preferably contains Group Ⅰ atoms at a high concentration toward the support side as described above. It has a localized region (A).

The localized region (A) will be described using the symbols shown in FIGS. 2 to 10, and is provided within 5 μm from the interface position tB.

In the present invention, the localized region (A) is the interface position @t
It may be the entire layer region LT up to 5μ thick from B, or it may be a part of the layer region LT.

Whether the localized region (A) 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 (A) is a distribution state of Group ■ atoms in the thickness direction of 1,000 layers, and the maximum value Cmax of the content distribution value (distribution concentration value) of Group ■ atoms is relative to silicon atoms. Usually 100 atomta ppm or more, preferably 150
atomio ppm or more, optimally 200 ato
It is desirable that the layers be formed in such a way that a distribution state of mic ppm or more can be achieved.

That is, in the present invention, in the layer region (V) containing Group Ⅰ, the maximum value Cmaz of the K distribution concentration exists within 5 μm in layer thickness from the support side (layer region 5 μm thick from tB). It is formed as follows.

As mentioned above, by providing the localized region (A) containing a high concentration of Group Ⅰ atoms on the side of the support in the layer region (V), the charge from the support side to the amorphous material can be reduced. injection can be more effectively prevented.

In the present invention, the content of group (III) atoms contained in the layer region (V) containing group (III) atoms may be adjusted as desired so as to effectively achieve the object of the present invention. It can be determined, but usually 50 to 5 X 10' atoms
tc ppm, preferably 50-1×10 ato
mic l111m is desirable. The location of the oxygen atoms contained in the first layer region (0) can be determined as desired depending on the characteristics required of the photoconductive member formed, but usually 0.00
1-50 atomic%, preferably 0.002-
40 atmoio% optimally 0.003-30ato
mi.

% is preferable.

In the photoconductive member of the present invention, the layer thickness tB of the layer region (V) containing group (I) atoms (in FIG. 1, the layer region 10
5 layer thickness), and the layer region (B layer 1 layer region) provided on the layer region (V) where no Group Ⅰ atoms are present, that is, the layer region excluding the layer region (V). In the figure, the layer thickness T of the layer region *106) is determined appropriately according to the purpose at the time of layer formation so that the first amorphous layer (I) with desired characteristics is formed on the support. be done.

In the present invention, a layer region (V) containing group V atoms
The layer thickness tB is usually 30A to 5μ, and 4U for lighting.
A~4μ,! For &, bOA ~ 6μ, layer area (B
) layer thickness T is usually 0.2 to 95μ, preferably 0.
．． 5 to 76P1, most preferably 1 to 47P.

Further, the sum (T-)-tB) of the layer thickness T and the layer thickness tE is usually 1 to 100μ, preferably 1 to 80μ, and optimally 2 to 50μ. be.

As for the layer thickness of the layer region (0) containing oxygen atoms, the layer region (V) that shares at least a part of the layer region (V)
It is desirable that the thickness be appropriately determined in accordance with the desired purpose in relation to the layer thickness tE. That is, if the purpose is to strengthen the adhesion between the layer region (V) and the support that is in direct contact with the layer region (V), the layer region (0) is the layer region (V). 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 (0) is at most the layer region (
It is sufficient to have a layer thickness tB of V).

To I Mi → Nido D Norita 1 [Sex-Dl To 41 Cheering Woman f4 size H
Hexagonal, C4 region (Vl and a layer region provided directly on the layer region (V) (corresponding to the layer region 106 in FIG. 1)
If you want to strengthen the adhesion between the layer area (0)
It suffices to provide at least the end layer region of the layer region VC (V) opposite to the side where the support is provided, so the layer thickness t0 of the layer region (0) is at most the layer region ( It is sufficient to have a layer thickness tB of V).

Furthermore, considering the case where the above two points are satisfied, the layer thickness t0 of the layer region (0) is at least equal to the layer region (V).
It is necessary that the layer thickness is at least tB, and in this case, it is necessary to have a layer structure in which a layer region (V) is provided in a layer region (0).

layer region (V) and j provided directly on the layer region (V)
In order to more effectively measure the adhesion between layer regions,
It is preferred that C(0) extends above the layer region (V) (in the direction opposite to the side on which the support is located).

In the present invention, the amorphous layer (1) of the amorphous layer (1)
III! Since it is necessary to provide a 1 part that does not contain oxygen atoms in the I end layer region and to make the layer region (0) locally unevenly distributed on the support side of the amorphous layer (1), the layer region (0
) layer thickness t0 is usually 10A to 10μ,
Preferably, it is 2oX to 8μ, most preferably 30A to 5μ.

In the present invention, the amorphous layer (1) composed of a-8i (H, done by law. for example,
In order to form the amorphous layer (I) composed of a-81 (H, , for introducing a hydrogen atom (H) or/and a halogen atom (X
) A raw material gas for introduction is introduced into a deposition chamber whose inside can be reduced in pressure to cause a pressure glow discharge in the deposition chamber, and a-8i is deposited on the surface of a predetermined support that has been installed at a predetermined position in advance.
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 81 in an atmosphere of an inert gas such as 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.

In the present invention, specific examples of the chlorine atom (X) contained in the amorphous layer (I) if necessary include fluorine, chlorine, bromine, and iodine, particularly fluorine and chlorine. This can be mentioned as a suitable example.

The raw material gases for S1 supply used at the pressure of the present invention include 5iHa, Si*Hg, Si*H8, 5i4H
Engineering. Hydrogenated silicon (silanes) in a crab state or capable of being gasified are mentioned as those which can be effectively used, and in particular,
5 in terms of ease of handling layer creation work, good S1 supply efficiency, etc.
Preferred examples include tH4, St, and H.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives. Alternatively, halogen compounds that are easily gasified are preferably mentioned.

Furthermore, silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective compounds in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases of fluorine, chlorine, Okusue, and iodine, BrF, CjIF, GeFs, BrF5
．． Interhalogen compounds such as BrF5゜FI, IFY, IC4: [Br can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, 5
Preferred examples include silicon halides such as IF4.5taF, E31014.5tBr4, and the like.

When employing such a silicon compound containing a halogen atom and forming the characteristic photoconductive member of the present invention by a glow discharge method, silium is supplied and silicon hydride gas is used as a raw material gas for the insulating material. At least, an amorphous gi layer (I) made of a-Si containing halogen atoms can be formed on a predetermined support.

When forming an amorphous layer (1) containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying S1, and Ar are used.

Gases such as H, H, etc. are introduced into the deposition chamber where the amorphous layer (1) is to be formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to generate plasma of these gases. By forming an atmosphere, an amorphous layer (I) is formed on a predetermined support.
However, 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.

An amorphous layer (1) made of a-Si (H,X) is formed by reactive sputtering or ion blating.
For example, in the case of sputtering method, S
This is sputtered in a predetermined gas plasma atmosphere using a target consisting of 1, and in the case of the ion blasting method, polycrystalline silicon or single crystal silicon is housed in a fi deposition boat as an evaporation source, and this silicon The evaporation source may be resistance heating method or electron beam method (EB method).
This can be carried out by heating and evaporating the flying evaporated matter using a method such as the above method, 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, 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 water droplets, for example, Hl or the above-mentioned silane gases, is introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do shite.

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, halogen compounds such as HF, HCI, HBr, HI, etc. Hydrogen oxide, SIHgFz, SIH*Is, 81Hm
C11m.

Halogen 7 such as 5iHC14SiHgBr45iHBr3
Gaseous or gasifiable halogen compounds having a hydrogen atom as one of their constituents, such as m-substituted silicon hydride, can also be mentioned as effective starting materials for forming the amorphous layer (I).

These halides containing hydrogen atoms form an amorphous layer (I
) 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.

K, which structurally introduces hydrogen atoms into the amorphous layer (I), is
In addition to the above, H2 or SiH4,5lsHa, 51
This can also be achieved by causing a discharge by causing a silicon hydride gas such as gH45x4H1° to coexist with a silicon compound for supplying 81 in the deposition chamber.

For example, in the case of the reactive sputtering method, an S1 target is used, and a gas for introducing halogen atoms and H8 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to create a plasma atmosphere. By forming and sputtering the S1 target, an amorphous layer (1) consisting of a-8i(H,X) is formed on the substrate.

Furthermore, it is also possible to introduce gases such as B, )(, etc.) also for doping with impurities.

In the present invention, the amorphous layer CI of the photoconductive member to be formed
) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H
-1-X) is usually 1 to 40 atomic%, preferably 5 to 3 Q atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer (1), for example, the support humidity or/and hydrogen atoms (H) or... The amount of the starting material used to contain the atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled.

The amorphous layer (1) has a layer region M (V
) and to provide a layer region (0) containing oxygen atoms,
When forming the amorphous layer (I) by a glow discharge method, a reactive sputtering method, etc., the above-mentioned amorphous layer (1
) by using it together with the starting material for formation and incorporating it into the formed layer while controlling its density.

When the glue discharge method is used to form the layer region (0) containing oxygen atoms and the layer region (V) containing group V atoms, which constitute the amorphous layer CI), each layer region The starting materials to be used as the raw material gas for forming the amorphous layer (I) are those selected as desired from the starting materials for forming the amorphous layer (I) described above, and the starting materials for introducing oxygen atoms or/and Group V Starting material for atom introduction is added. Such a starting material for introducing oxygen atoms or a starting material for introducing group Ⅰ atoms may be a gaseous substance or a gasified substance containing at least an oxygen atom or a group Ⅰ atom as a constituent atom. Most of them can be used.

For example, to form a 1.4 region (0), a source gas containing silicon atoms (Sl), a source gas containing oxygen atoms (○), and hydrogen atoms ( H) or/and... A raw material gas containing rogen atoms (X) is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Sl) and oxygen are used. A raw material gas whose constituent atoms are atoms (0) and hydrogen atoms (H) are mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Sl) and silicon atoms (Si) can be used in combination with a raw material gas containing six constituent atoms: oxygen atoms (0) and hydrogen atoms (H).

You can also use it.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (Os), ozone (Os), -nitrogen oxide (NO), nitrogen dioxide (NOx), -nitrogen dioxide (
N, O), nitrogen sesquioxide (NxOs), nitrogen tetroxide (NsOa), nitrogen sesquioxide (N30 black), nitrogen trioxide (NOg), silicon atom (Sl), oxygen atom (0), and hydrogen atom (H) as constituent atoms, for example,
Examples include lower grade siloxanes such as disiloxane Hg5iO8iHx, ) resiloxane H, 510StH, and 08tHs.

When the layer region (V) is formed using a glow discharge method, the starting materials for introducing group (III) atoms that are effectively used in the present invention are PH, P, and P for introducing phosphorus atoms.
, H, etc. hydrogen north neighbor, PHaI, PFg, PFM
.

PCjls, PCla, PBrm, PBra,
Examples of effective starting materials for introducing group III atoms include PIs and the like having a high hydrogen ratio.

The content of group (III) atoms introduced into the layer region (V) containing group V atoms is determined by the gas flow rate of the starting material for introducing group (III) atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge It can be arbitrarily controlled by controlling power, support humidity, pressure in the deposition chamber, etc.

To form a layer region (0) containing oxygen atoms by the sputtering method, target a single crystal or polycrystalline S1 wafer, a Sto wafer, or a wafer containing a mixture of Sl and $101. This can be done 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 wafer No. 81 may be sputtered by introducing these gases into the wafer and forming a gas plasma of these gases.

Alternatively, by using St and Stag as separate targets or using a single mixed target of Sl and 8101, at least hydrogen atoms (H ) or/and by sputtering in a gas atmosphere containing rogen 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 example of glow discharge described above can be used as an effective gas also in the case of sputtering.

In the present invention, the diluting gas used when forming the amorphous layer (1) by the glow discharge method or the sputtering gas used when forming the amorphous layer (1) by the sputtering/gluing method is a so-called diluting gas. Suitable gases include Hs, Nθ, Ar, and the like.

In the photoconductive member of the present invention, a layer region (B) not containing group V atoms (corresponding to layer region 106 in FIG. 1) is provided on the layer region (V) containing group By incorporating a substance that controls the conduction characteristics into the layer region (B), the conduction characteristics of the layer region (B) can be arbitrarily controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-8i (H, , a P-type impurity that provides P-type conductivity, specifically, an atom belonging to Group Ⅰ of the periodic table (Group Ⅰ atom), such as B
(boron), Al (aluminum), G& (gallium), In (indium).

Examples include Tl (thallium), among which B and Ga are particularly preferably used.

In the present invention, the content of the substance that controls the conductive properties contained in the layer region (B) is determined by the conductive properties required for the layer region (B) or the substance that controls the conductive properties in direct contact with the layer region (B). In the present invention, the material contained in the layer region (B) can be appropriately selected depending on the organic relationship, such as the characteristics of other layer regions provided and the relationship with the characteristics at the contact interface with the prestige layer region. The content of the substance that controls the conduction properties is usually 0.0
It is desirable that the range is 0.01 to 1000 atomic ppm, preferably 0.05 to 500 atomic ppm, and optimally 0.1 to 200 atomic ppm.

In the layer region (B) there is a substance controlling the conduction properties, e.g.
In order to introduce structural pressure of group atoms, the first II
The starting material for introducing group atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the amorphous layer. As the starting material for such introduction of Group 1 atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing such a group Ⅰ atom, BIH# gB is used for introducing a boron atom.
4HIO, BaHe, BaHxx, BIIHIO,
Boron hydride such as BaHxx, B@HX4, BFs,
Examples include boron halides such as BGls and BBrs. In addition, AlC15, GaCA! 3. GIL (
CHg)s, InG15°Tl06. 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), but the present invention is not limited thereto; for example, The amorphous layer (I) may be formed so that the layer thickness of the layer region (0) is sufficiently thicker than that of the layer region that does not contain oxygen atoms.

In this case, since the amorphous layer (I) needs to be formed to exhibit photoconductivity, the upper limit of the oxygen atoms contained in the layer region (0) is usually 5 Q at
omic%, preferably 10 atomj, c%, optimally 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. 1, the second amorphous layer f formed on the first amorphous layer (1) 1021
it) 107 has a free surface 108 and is mainly moisture resistant,
It is provided in order to achieve the objectives of the present invention in terms of continuous repeated use characteristics, pressure resistance, usage environment characteristics, and durability.

Further, in the present invention, each of the amorphous materials constituting the first amorphous layer (I) 102 and the second amorphous layer (It) 107 has a common constituent element of silicon atoms. Therefore, the laminated interface is sufficiently acidified to ensure chemical stability.

The second amorphous layer (1107 is an amorphous material Ca composed of silicon atoms, carbon atoms, and halogen atoms (X)
(S!xc+-x)yXl-y+where O<x, y<1
] is formed.

The second amorphous layer (11) composed of a-(5i)(CI-x)yXl-Y can be formed by glow discharge method, sputtering method, ion plantation method, ion blating method, electron beam method, etc. done by.

These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level 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 the conductive member, and carbon atoms and halogen atoms are added to the second amorphous layer to be manufactured (for example, carbon atoms and halogen atoms can be easily introduced into Ifj). Due to their advantages, the glow discharge method or the sputtering method is preferably employed.

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 layer (u
)Y may be formed.

In order to form the second amorphous layer (II) by the glow discharge method, the raw material gas for forming a-(S 1xc1-x )yXl-y is mixed with a dilution gas at a predetermined mixing ratio as necessary. The gas is mixed with the support and introduced into a deposition chamber for vacuum deposition where the support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge to remove the gas already formed on the support. a-(Si)(C) on the first amorphous layer (1)
+-x) yXl-y'l deposition is good.

In the present invention, a (8jxC1-x)yXl-y
As the raw material gas for formation, most of gaseous substances containing at least one of Si, C, and X as a constituent atom or gasified substances that can be gasified can be used.

When using a raw material gas that has Si ke constituent atoms as one of Si, C, and X, for example, a raw material gas that has 8i as constituent atoms, a raw material gas that has C as constituent atoms, and Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing C and X as constituent atoms may be mixed at a desired mixing ratio. Alternatively, a raw material gas containing 8i as a constituent atom and a raw material gas containing Si, C, and X as constituent atoms can be used in combination.

Separately, C is added to the raw material gas containing Si and X as constituent atoms.
A mixture of raw material gases having constituent atoms may be used.

In the present invention, F, C6, and B are suitable as the second amorphous layer (halogen atoms contained in Ill).
r.

(2) F' and Cl are particularly desirable.

In the present invention, the second amorphous layer (■) is a-(5t
Although it is composed of xCt-x)yXl-y, it can further contain a hydrogen atom.

The inclusion of hydrogen atoms in the second amorphous layer (Ill) makes it possible to share some of the source gas species when forming a continuous layer with the first amorphous layer (I). This is advantageous in terms of cost.

In the present invention, raw material gases that can be effectively used to form the second amorphous layer (If) include:
Examples include substances that are in a gaseous state at room temperature and pressure, or substances that can be easily gasified.

Examples of the substance for forming the second amorphous layer (II) include saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 3 carbon atoms. It can oxidize hydrocarbons, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, silicon hydrides, etc.

Specifically, the saturated hydrocarbon is methane ((EH4)
.

Ethane (C2H6), Propane (C3H8), n-
Buta y (n-C4H, 1o), pentane (C5) 1
12); As an ethylene hydrocarbon, ethylene (
(':'2H4)ipropylene (C3HIS).

Butene-1 (C4H8), Butene-2 (C4H8), Isobutylene (C4H8), Pentene (C5H10),
Examples of acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C5H4), butyne (C4H6
), halogen gases include fluorine, chlorine, bromine, and iodine.

Hydrogen halides include PI (, HI, HCI,
HBr, )-O intergen compounds include BrF, Cl
F, (JF5.ClF5.BrF5゜BrF5.IF
7. IF5. I(j!, IBr, Cl silicon genide toshiteha 5IP4. Si2F6.8iC14,5iCJ
3Br, 8iC12Br2.5iCA! Brs.

5iC45I, 8iBr4. As the halogen-substituted silicon hydride, S 1H2F2.8iHz (J 2.81H
C1s, 81H3(J, S 1HsBr, S 1
H2Br2゜5iHBrs, silicon hydride is Si
H4,512H6,8i5Ha.

5i4) Silanes such as 11o,
etc. can be mentioned.

In addition to these, CC1a, CHF3. CH2F2.
CHsF, CH3(Jl.

Halogen-substituted paraffinic hydrocarbons such as CHxBr, CH3I, C2HsCJ, 8F4. Fluorinated sulfur compounds such as SF6.

8i (CHs) 4.5i (C2Hs) 4. etc.f)'
y i 7 k ki k ya S :C1(CH3C,5i
C12(CH3)2.5i(JsQ-13% cr>
Silane derivatives such as silane-containing alkyl silicides can also be cited as effective.

These second amorphous layers ([lj-forming substances include silicon atoms, carbon atoms, and halogen atoms in a predetermined composition ratio in the second amorphous layer (1) to be formed, if necessary. It is selected and used as desired when forming the second amorphous layer (■) so as to contain hydrogen atoms.

For example, S can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form j- with desired characteristics.
i(CH3)4 and 5iHCA containing a halogen atom! 3.8iC14, 5iH2CJ2
．． Alternatively, a (8+xC1
A second amorphous layer (IIIY) consisting of -x)y((4+1()1-y) can be formed.

To form the second amorphous layer (113) by sputtering, a single crystal or polycrystalline SI wafer, a C wafer, or a wafer containing a mixture of Si and C is used as a target. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and, if necessary, hydrogen atoms as constituent elements.

For example, if an Sr wafer is used as a target, the raw material gases for introducing C and The Si wafer may be sputtered by forming plasma.

Separately, 8i and C can be formed by sputtering in a gas atmosphere containing at least halogen atoms, using separate targets or a single mixed target of Si and C. be done.

When the material for forming the second amorphous layer (l[) shown in the glow discharge example mentioned earlier is sputtered, the material that becomes the raw material gas for introducing C, X, and H if necessary is used. It can also be used as an effective substance.

In the present invention, a diluent gas used when forming the second amorphous layer (Ill) by a glow discharge method or a sputtering method is used.
, Ar, etc. can be mentioned as suitable examples.

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

In other words, the constituent atoms of Si, C, X, and optionally H have a structure that ranges from crystalline to amorphous depending on the conditions for their creation, and electrically conductive to semiconductive to semiconductive to In the present invention, a-(si xcl - The preparation conditions are strictly selected as desired so that x)yXl-Y is formed. For example, to provide the second amorphous layer (If) with the main purpose of improving pressure resistance, a-(stxcl-x)y
xl-y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the second amorphous 'II layer (11) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and the irradiated light is In contrast, a-(SixC1-x)yXl-)' is created as an amorphous material having a certain degree of sensitivity.

a (SfxC+-x
) When forming the second amorphous layer fII) consisting of has the desired property a (S'xC1-x)
It is desirable that the temperature of the support during layer formation be tightly controlled so that yXl-y can be formed as desired.

In the present invention, the second amorphous layer (It) is appropriately selected in accordance with the method of forming the second amorphous layer (n) in order to effectively achieve the desired purpose. The formation of
It is desirable that the temperature be 250°C. In forming the second amorphous layer (■), delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. Although it is advantageous to employ a glow discharge method or a sputtering method, when forming the second amorphous layer (l[) using these layer forming methods, the layer forming method should be adjusted at the same temperature as the support temperature described above. When the discharge power is created a(SixC
1-x)yXl-y is one of the important factors that influence the characteristics of y.

a having the characteristics for achieving the object of the present invention;
(SlxCl-x)yXl-y is productive and effective I
The discharge power condition for creating C is usually 10 to 3.
00J is 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 Q, 5 Torr.

In the present invention, the above-mentioned values are listed as the preferable numerical ranges of the support temperature and discharge power for creating the second amorphous layer (If), but these layer creation factors are independent of each other. They are not determined separately, but are mutually organically related so that a second amorphous layer (It) consisting of a-(Sj)(CI□)yX, -y with desired characteristics is formed. It is desirable that the optimum value of each layer creation factor be determined based on this.

Second amorphous layer (II) K in the photoconductive member of the present invention
The carbon atoms and halogen atoms contained in the second amorphous layer (II ) is an important factor in the formation of

The amount of carbon atoms contained in the second amorphous layer (u) in the present invention is usually 1 x 10 to 90 atomJ (ch, preferably 1 to 90 atomic %, optimally 10 to 80 atomJ).
tomic % is desirable. As a lid containing a halogen atom, in the usual case, 1 to 2 Q
atomic%.

Preferably 1-18 atomic%, optimally 2-1
It is desirable that the halogen atom content be within this range, and the photoconductive member to be produced can be sufficiently applied to practical applications. The hydrogen atom content, if necessary, is usually 19 atomic atoms or less, preferably 13 atomic atoms or less. That is, the previous a (
8! xc1-x)y Suitable K k'! , 0.
1~0.99, optimal K 0.15~G, 9. y is usually 0.8 to 0.99. It is preferably 0.82 to 0.99, most preferably 0.85 to 0.98. If both halogen atoms and hydrogen atoms are included, the same a as above
(SixC1-x)y(H+X)1-y, the numerical range a of X and y in this case (SixC
1-x)yXl-y.

The numerical range of the layer thickness of the second amorphous layer (II) in the present invention is one of the important factors for effectively achieving the object of the present invention.

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

Moreover, the layer thickness of the second amorphous layer (It) is the same as that of the first layer region (
The relationship with the layer thickness of 01103 also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region.・In addition, it is desirable to consider economic efficiency by taking into account productivity and mass production. Second amorphous layer f in the present invention
The layer thickness of n) is usually 0.003 to 30 tt,
Suitable 11C is 0.004 to 20 p, optimally 0.0
It is desirable that the thickness be 05 to 10μ.

The support used in the present invention may be electrically conductive or electrically insulating. As a conductive support, for example, NiCr, , X-y-y V-s, Ae,
Cr.

Mo, Au, Nb, Ta, V, Ti, Pt
, Pd, or 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 is applied to its surface.

kl, Cr, Mo, Au, Ir, Nb,
Ta, V, Ti, Pi, pa, In2O3,
Conductivity is imparted by providing a thin film made of SnO2゜ITO (In203-1-8nO2), etc.
Or if it is a synthetic resin film such as polyester film, use NiCr.

kl, Ag, Pb, Zn, Ni, Au, Cr, Mo, I
A thin film of metal such as r, Nb, Ta, V, 'I'i, Pi, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. conductivity is imparted to the The shape of the support may be any shape such as a cylinder, a belt, a plate, etc.
The shape is determined as desired, but for example, the first
If the photoconductive member 100 shown in the figure is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that the 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. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness should normally be 10μ or more.

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 the respective layers of the present invention are sealed. (Purity 99-999%, hereinafter abbreviated as SI H4/)le) Cylinder, 1106 is H
B2H6 gas diluted with e (purity 99.999%, hereinafter B2H6/I (e is omitted)) To the Hon, 1104 is I
- PH3 gas diluted with T, e (purity 99.99%).

Hereinafter, it will be abbreviated as PH5. ) cylinder, 1105 is 5IF4 gas diluted with He (purity 99.999%, hereinafter S + F4./), abbreviated as Ie. ) cylinder, 1106
is a cylinder for NO gas or C2H4 gas (99.99% purity).

In order to flow these gases into the reaction chamber 1101, valves 1122 to 112<S of gas cylinders 1102 to 1106 are used.
, Confirm that the leak valve 1165 is closed, and confirm that the inflow valve 1112-P-1116, the outflow valves 1117 to 1121, and the auxiliary valve 1132 are open, and first open the main valve 1134y5.
It is opened to exhaust the inside of the reaction chamber 1101 and gas piping. Next, when the reading on the vacuum gauge 1166 reaches approximately 5X10 torr, the auxiliary pulp 1132° outflow valve 1117~
1121 Close.

To give an example of forming the first amorphous layer (I) on the base 1137, S+H4A is supplied from the gas cylinder 1102.
Ie gas, PH5/He gas from gas cylinder 1104,
NO gas is supplied from the gas cylinder 1106 to the valve 1122.1.
124.1126 Open the outlet pressure gauge 1127.
Adjust the pressure of 1129.1130 to 1 kV6rA, gradually open the inlet valves 1112, 1114.1116, and connect the mass flow controllers 1107, 1109.1111.
Let them flow into each other. Subsequently, the outflow valve 1117,
1119° 1121, the auxiliary pulps 1132 and 1133 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, 5i14a, 4(e gas flow rate and PH3/H
Adjust the outflow pulps 1117, 1119, and 1121 so that the ratio of e gas flow rate and NO gas flow rate becomes the desired value, and adjust the vacuum gauge 1166 so that the pressure inside the reaction chamber 1101 becomes the desired value. Main valve 116 while checking the reading.
Adjust the opening of 4. After confirming that the temperature of the base 1167 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power supply 114 (In
Set the desired power and emit glow into the reaction chamber 1101.
Phosphorus atoms contained in the layer formed by gradually changing the flow rate of PH3/He gas manually or by a method such as an externally driven motor or the like by gradually changing the flow rate of the PH3/He gas according to a pre-designed change rate curve. (P)
control the distribution concentration of Layer regions (p, o) containing phosphorus atoms and oxygen atoms are formed on the base 1167 as described above.
form.

At this time, by blocking the introduction of PH5/)Ie gas or NO gas into the reaction chamber 1101 by closing the valve of each corresponding gas introduction pipe, the layer region containing phosphorus atoms or The layer thickness of the layer region containing oxygen atoms can be arbitrarily controlled as desired.

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, 0) to a desired layer thickness, and the formation of the first amorphous layer (1) is completed.

When halogen atoms are contained in the first amorphous layer m, for example, 5iP4/He is further added to the above gas and fed into the reaction chamber 1101.

To form the second amorphous layer (I[n) on the first amorphous layer (■), for example, the following procedure is performed.
Open 2. All gas supply valves are once closed, and the reaction chamber 1101 is evacuated by fully opening the main valve 1134.

A target in which a high-purity silicon wafer 1142-1 and a high-purity graphite wafer 1142-2 are placed in advance at a desired area ratio is provided on the electrode 1141 to which high-voltage power is applied.

SiF4/Ar gas was introduced into the reaction chamber 1101 from 1105 into a gas bomb filled with SiF4/Ar gas in advance, and the internal pressure of the reaction chamber 1101 was 0.05.
Adjust the main valve 1134 so that ~itc)rr. By turning on the high voltage power supply and sputtering the target, a second amorphous layer (II)' and a shadow can be formed on the first amorphous layer (1).

Another method of forming the second amorphous layer (Ill) is
For example, SiH4 gas, 5iFa gas, C2H4
Each of the gases is diluted with a diluent gas such as He as necessary and flowed into the reaction chamber 1101 at a desired flow rate ratio, and the glow group i! This is accomplished by causing the

It goes without saying that all outflow valves other than the gas outflow valve (1101) required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is Outflow) Kurub 1117-1121
In order to avoid gas from remaining in the gas piping leading to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valve 1132 is opened, and the main nozzle (lube 1164 is fully opened) to temporarily evacuate the system to a high vacuum. Perform as necessary.

Example 1 A layer was formed on an aluminum substrate under the conditions shown in Table 1 below using the manufacturing apparatus shown in FIG. , 05 KV for 0.28 eC and immediately irradiated the light image.The zero source used a tungsten lamp.
1. To remove O1ux-sθC, 0 was irradiated using a transmission type test chart.Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to form a good toner on the surface of the member. Got the image.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test more than 150,000 times.

Laughter Example 2 Manufacturing apparatus f'fr shown in FIG. 11: Implemented except that the amorphous layer fI) was formed on A/substrate using the content of phosphorus IPI in the layer as a parameter. The same procedure as Example 1 was carried out. At this time, the common manufacturing line V for each sample is the second
As shown in Table -1. Table 2-2 shows the distribution concentration of phosphorus atoms contained in the first amorphous layer (1) at each position in the layer thickness direction from the substrate surface, and the evaluation of the electrophotographic properties of the obtained sample. Score the result by 7.

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 [gradation reproduction] of the image visualized on the transfer paper. Comprehensive evaluation was made based on the merits and demerits such as gender.

57 The values in Table 2-2 each indicate the distribution concentration of phosphorus (atm, ppm).

◎: Excellent 01 Good △: Sufficient for practical use 0 Example 3 Using the manufacturing apparatus shown in FIG. 11, a layer was formed on an AI substrate under the conditions shown in Table 3 below.

Other conditions were the same as in Example 1.

The image forming member thus obtained was placed in a Teiden exposure developing device, corona charged at 05 KV for 0.28 eC, and immediately irradiated with a light image. The light source uses a tungsten lamp,
A light intensity of 1.01hxx·θθC was irradiated using a transmission type test chart.

Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image on the surface of the member.

The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test over 100,000 times.

Example 4 Using the apparatus shown in FIG. 11, A7! A layer was formed on the substrate under the conditions shown in Table 4 below.

Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging source developing device, and
Corona discharge was performed for 0.28 eC at 5 KV, and a tungsten lamp was used as the zero source source that immediately irradiated the optical image.1. O
A light intensity of 1ux-sea was irradiated using a transmission type test chart.

Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image with extremely high density on the surface of the member.

The toner image thus obtained was cleaned with a -H rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test more than 150,000 times.

Example 5 During the formation of the second amorphous #(1), the area of the silicon wafer and graphite was changed to change the content ratio of silicon atoms to carbon atoms in the amorphous layer ([1]). Except for this, an image forming member was prepared in the same manner as in Example 4. After repeating the image forming, developing and cleaning steps as described in Example 1 about 50,000 times for the image forming member thus obtained. When all image evaluations were carried out, the results shown in Table 5 were obtained.

Example 6 Except for changing the layer thickness of the second amorphous layer (II), An imaging member was made in a manner similar to Example 1.

The steps of image formation, development, and cleaning as described in Actual Example 1 were repeated to obtain the results shown in Table 6 below.

Table 6 Example 7 The image forming member 2 was prepared in the same manner as in Example 1 except that the method for forming the second amorphous layer (1) was changed as shown in Table 7 below. Good results were obtained when the evaluation was carried out using a method.

Example 8 An image forming member was prepared in the same manner as in Example 1, except that the method for forming the first amorphous layer (I) was changed as shown in Table 8 below. Example 9 Good results were obtained when evaluated in Example 9 Except for changing the layer creation conditions in the second and third layer creation stages of Example 6 to the conditions shown in Table 9 below. Electrophotographic image forming members were produced according to the conditions and procedures shown in Example 6, and evaluated in the same manner as in Example 1. As a result, each of them had good results, especially in terms of image quality and durability. Obtained.

[Brief explanation of the drawing]

Fig. 1 is a schematic layer structure diagram for explaining the layer structure of the base 24'TM of the present invention and the member, and Figs. Katsuaki diagram, No. 11, for explaining the distribution state of group (■) atoms in the layer region (■)
The figure is a schematic explanatory diagram of the apparatus used in the present invention. 100o・Light guide turtle member 101...Support 102...First amorphous layer (I) 106...No area (V) 104...Layer area (B) 105-・+1 second Amorphous layer (II) 106...free surface Applicant: Canon Co., Ltd. 111-ko □C □C Continued from page 1 (Plastic combination person: Yo Osato - 3-30 Shimomaruko, Ota-ku, Tokyo) No. 2 Canon Co., Ltd. (?■ Inventor Shigeru Shirai No. 2 Canon Co., Ltd., 3-30-2 Shimomaruko, Ota-ku, Tokyo)

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 halogen 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 second layer containing atoms belonging to Group V of the periodic table as constituent atoms, which are continuous in the layer thickness direction and are distributed more toward the support side; A photoconductive member characterized by having a region.