JPS6310421B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a desired time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, which requires a comprehensive improvement in characteristics. For example, when applied to electrophotographic image forming members, when trying to achieve high light sensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use; When a conductive member is repeatedly used for a long period of time, fatigue due to repeated use accumulates, resulting in a number of disadvantages such as the so-called ghost phenomenon in which an afterimage occurs. For example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is a conventional inorganic photoconductive material such as Se, CdS, ZnO, etc. Although it has many advantages compared to organic photoconductive materials such as PVCz and TNF, it has a single-layer photoconductive layer made of a-Si that has properties suitable for use in conventional solar cells. Even if the photoconductive layer of a photographic image forming member is subjected to charging treatment for electrostatic image formation, dark decay (dark decay) occurs.
(decay) is extremely fast, making it difficult to apply normal electrophotographic methods, and in a humid atmosphere.
It has been found that the above-mentioned tendency is remarkable, and in some cases, there are cases in which the electrostatic charge can hardly be retained until the development time, and that there are problems that can be solved. Furthermore, a-Si materials can be impregnated with hydrogen atoms or halogen atoms such as fluorine atoms or chlorine atoms to improve their electrical and photoconductive properties, and boron atoms or phosphorus atoms to control their electrical conductivity. However, depending on how these constituent atoms are contained, problems may arise in the mechanical properties when the layer is formed. There are cases. In other words, in the case of electrophotographic image forming members, an a-Si layer is usually formed on a cylindrical support made of a metal material such as aluminum, but the extent of the formation depends on the conditions for forming the layer. However, due to the magnitude of its strain characteristics, inconveniences such as the layer cracking, floating off the support, or the entire layer peeling off occur in many cases. In addition, the normal a-Si layer itself does not generally exhibit very good adhesion properties to supports made of metal materials such as aluminum, and therefore there are problems with long-term repeated use characteristics. There is also the problem that it is difficult to form good electrical contact between the support and the a-Si layer due to changes over time. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is. The present invention has been made in view of the above points, and includes a
-As a result of intensive and intensive research into Si from the viewpoint of its applicability and applicability as a photoconductive member used as an image forming member for electrophotography, we found that Si has a silicon atom as its base material and a hydrogen atom ( Amorphous materials containing at least one of H) or halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as a generic term for these a -Si(H,X)
Photoconductive members for electrophotography designed and produced with a specific layer structure having a photoconductive layer composed of a photoconductive layer that uses a photoconductive layer that uses a photoconductive layer that uses a photoconductive layer that uses photoconductive materials for electrophotography exhibit extremely excellent properties in practical use. Rather, it is based on the discovery that it is superior in all respects to conventional photoconductive materials, and in particular has significantly superior properties as a photoconductive material for electrophotography. . The electrical, optical, and photoconductive properties of the present invention are always stable, and it is an all-environment type that is hardly controlled by the usage environment.It is extremely resistant to light fatigue and does not cause deterioration even when used repeatedly. Excellent durability,
The main object of the present invention is to provide a photoconductive member for electrophotography in which no or almost no residual potential is observed. Another object of the present invention is that when applied as an image forming member for electrophotography, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties that can be used. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member for electrophotography that has high adhesion and good electrical contact with a support. The photoconductive member for electrophotography of the present invention exhibits photoconductivity and is composed of a support for electrophotography and an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms. In the photoconductive member, the amorphous layer includes a lower region and an upper layer from the support side. These layer regions each have a substantially uniform chemical composition, and the oxygen atoms are contained only in the lower layer region over the entire region, and each of these layer regions has a substantially uniform chemical composition. It is characterized in that atoms belonging to group 1 of the Table of Contents are contained at least in the lower layer region. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, and photoconductive properties and a usage environment. Show characteristics. In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio and is extremely good in light fatigue resistance, repeated use characteristics, especially in a humid atmosphere, and has high density, clear halftones, and high resolution. A quality visible image can be obtained. DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photoconductive member of the present invention will be described in detail below with reference to the drawings. FIGS. 1a to 1c are schematic structural diagrams schematically shown to explain the layer structure of a photoconductive member according to each embodiment of the present invention. The photoconductive member 100 shown in FIGS. 1a to 1c is an a-Si
Amorphous layer 1 with photoconductivity consisting of (H,X)
02, the amorphous layer 102 has a lower layer region 103 containing oxygen atoms as constituent atoms over its entire region, and a layer containing atoms of Group Group of the Periodic Table throughout its entire region as constituent atoms. It has a layered structure configured to have a region 104. The upper layer region 105 of the amorphous layer 102 does not contain oxygen atoms, which are considered to be a factor affecting humidity resistance and corona ion resistance, and oxygen atoms are contained only in the lower layer region 103. Lower area 103
In the upper layer region 105, high dark resistance and adhesion are focused on by containing oxygen atoms, and high sensitivity is focused on increasing sensitivity without containing oxygen atoms in the upper layer region 105. The amount of oxygen atoms contained in the lower layer region 103 is determined as desired depending on the characteristics required of the photoconductive member to be formed, but is usually 0.01 to 20 atomic%, preferably 0.02 atomic%. ~
It is desirable that the content be 10 atomic%, optimally 0.03 to 5 atomic%. Similarly to the amount of oxygen atoms, the amount of atoms of Group Group of the periodic table contained in the layer region 104 is determined as desired, and is usually 0.01 to 5×10 ^{4 .} atomic ppm, preferably 1
~100 atomic ppm, more preferably 3~
It is desirable that the content be 20 atomic ppm. The layer thicknesses of the lower layer region 103 and the upper layer region 105 are:
As this is one of the important factors for effectively achieving the object of the present invention, sufficient care must be taken when designing the photoconductive member so that the formed photoconductive member has sufficient desired properties. needs to be paid. In the present invention, the layer thickness of the lower layer region 103 is closely related to the layer thickness of the amorphous layer 102 itself. The layer thickness of the lower layer region 103 is usually 3 to 100μ,
The thickness is preferably 5 to 50μ, most preferably 7 to 30μ. In addition, the layer thickness of the upper layer region 105 is usually as follows:
0.02-10μ, preferably 0.03-5μ, optimally 0.05-
It is desirable to set it to 2μ. In the photoconductive member for electrophotography of the present invention,
As shown in FIG. 1a, the upper layer region 105 also contains atoms of Group Group of the periodic table as constituent atoms, and the entire amorphous layer 102 is made into a layer region 104. Similarly, the lower layer region 103 and the layer region 104 can be made into the same layer region without containing atoms of Group Group of the periodic table in the upper layer region 105. The photoconductive member according to the embodiment in which the upper layer region 105 does not contain atoms of Group Group of the Periodic Table exhibits remarkable characteristics particularly when used repeatedly in a humid atmosphere, and has excellent characteristics when used repeatedly in a humid atmosphere. Demonstrates sufficient durability for use. Further, as shown in FIG. 1c, a case where a layer region 104 is formed within the lower layer region 103 can also be cited as one of the preferred embodiments. Furthermore, in the present invention, an intermediate layer made of a metal oxide such as A ₂ O ₃ and acting as a so-called electrical barrier may be provided between the support 101 and the lower layer region 103. In the present invention, atoms belonging to group of the periodic table contained in the layer region 104 include B, Al, Ga, In, and Tl, particularly B,
Ga may be used as preferred. The support may be electrically conductive or electrically insulating. As the conductive support, for example,
NiCr, stainless steel, Al, Cr, Mo, Au, Nb,
Examples include metals such as Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb', Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. , imparts conductivity to its surface. The shape of the support body is cylindrical,
The photoconductive member 100 of FIG. 1 may be used as an electrophotographic image forming member for continuous high-speed copying, for example, although it may have any shape such as a belt shape or a plate shape, and the shape is determined as desired. If so, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that the desired photoconductive member is formed, but when flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as a thing. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A-Si is introduced into the chamber to generate a glow discharge in the deposition chamber, and the a-Si
It is sufficient to form a layer consisting of (H,X). or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
A photoconductive layer made of a-Si:X can be formed on a given support. When manufacturing an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber in which an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, an amorphous layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases to form a layer. It may be formed. 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. In order to form an amorphous layer made of a-Si(H, In the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam method (EB method). This can be done by heating and evaporating the flying evaporated material using a method such as the method (method), etc., 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 plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, and hydrogen halides such as HF, HCl, HBr, and HI are also used. , SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ ,
Halogen-substituted silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also effective starting points for forming an amorphous layer. It can be mentioned as a substance. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer. It is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be achieved by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, an amorphous layer made of a-Si(H,X) is formed on the substrate. Furthermore, impurity doping can also be repeated and a gas such as B ₂ H ₆ can be introduced. In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms contained in the amorphous layer of the photoconductive member to be formed is usually 1 It is desirable that the content is ~40 atomic%, preferably 5-30 gtomic%. Hydrogen atoms (H) or / contained in the photoconductive layer
and the amount of halogen atoms (X), for example by controlling the deposition support temperature or/and hydrogen atoms (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In order to introduce group atoms and oxygen atoms into the amorphous layer to form the lower layer region 103 and the layer region 104, when forming the layer by a glow discharge method, a reactive sputtering method, etc., By using the starting material, the starting material for introducing oxygen atoms, or both starting materials together with the starting material for forming the amorphous layer described above, the amount of the starting material is controlled in the layer to be formed. It will be done. When the glow discharge method is used to form the lower layer region 103 constituting the amorphous layer, the starting material that becomes the raw material gas for forming the lower layer region is one of the starting materials for forming the amorphous layer described above. A starting material for introducing oxygen atoms is added to one selected from among them as desired. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are oxygen atoms (O) and hydrogen atoms (H) are used. are also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) are mixed. It can be used in combination with a raw material gas having two constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms as constituent atoms, for example,
Disiloxane H ₃ SiOSiH ₃ , Trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like. To form the lower layer region containing oxygen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or _SiO2 wafer or Si and
The sputtering may be carried out by targeting wafers containing a mixture of SiO ₂ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, Si and SiO ₂ may be used as separate targets, or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least hydrogen. This is accomplished by sputtering in a gas atmosphere containing atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, so-called rare gases such as He, Ne,
Ar and the like can be cited as suitable examples. In order to form the layer region 104 constituting the amorphous layer, in addition to the raw material gas for forming the amorphous layer described above when forming the amorphous layer, a gas state for introducing group atoms is used. It is sufficient to introduce the starting material which can be gasified into the vacuum deposition chamber for forming the amorphous layer in a gaseous state. The content of group atoms introduced into the layer region 104 can be arbitrarily determined by controlling the gas flow rate, gas flow rate ratio, discharge power, etc. of the starting material for introducing group atoms introduced into the deposition chamber. Can be controlled. In the present invention, the starting materials for introducing group atoms that are effectively used for introducing boron atoms are B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ ，
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , etc., BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ .
Other examples include AlCl ₃ , GaCl ₃ , InCl ₃ and TlCl ₃ . Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 2 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. 202, 203, 204, 205, 20 in the diagram
Gas cylinder 6 is sealed with raw material gas for forming each layer of the present invention, and as an example, 202 is SiH ₄ diluted with He.
gas (purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 203 is B ₂ H ₆ gas diluted with He (purity
99.999%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 2
04 is Si ₂ H ₆ gas diluted with He (purity 99.99%,
Hereinafter, it will be abbreviated as Si ₂ H ₆ /He. ) cylinder, 205 is SiF ₄ gas diluted with He (purity 99.999%, hereinafter SiF ₄ /
Abbreviated as He. ) cylinder, 206 is an NO gas cylinder. In order to flow these gases into the reaction chamber 201, the valves 222 to 22 of the gas cylinders 202 to 206 are used.
6. Check that the leak valve 235 is closed, and check that the inflow valves 212 to 216, the outflow valves 217 to 221, and the auxiliary valves 232 to 233 are open. First, open the main valve 2.
34 is opened to exhaust the inside of the reaction chamber 201 and gas piping. Next, when the reading on the vacuum gauge 236 reaches approximately 5×10 ⁻⁶ torr, the auxiliary valves 232 to 233 and the outflow valves 217 to 221 are closed. To give an example of forming the lower layer region on the base cylinder 237, from the gas cylinder 202
SiH ₄ /He gas, B ₂ H ₆ / from gas cylinder 203
Inject He gas and NO gas from the gas cylinder 211, open the valves 222, 223, and 226, adjust the pressure of the outlet pressure gauges 227, 228, and 231 to 1 kg/cm ² , and gradually open the inflow valves 212, 213, and 216. , mass flow controller 207, 20
8,211. Subsequently, the outflow valves 217, 218, 221, the auxiliary valve 232,
233 is gradually opened to supply each gas to the reaction chamber 201.
to flow into. SiH ₄ /He gas flow rate at this time,
The outflow valves 217 and 21 are adjusted so that the ratio between the B ₂ H ₆ /He gas flow rate and the NO gas flow rate becomes the desired value.
8, 221, and the opening of the main valve 234 while checking the reading on the vacuum gauge 236 so that the pressure inside the reaction chamber reaches the desired value. Then, the temperature of the base cylinder 237 is increased by the heating heater 238.
After confirming that the temperature is set at 50 to 400° C., the power source 240 is set to a desired power to generate a glow discharge in the reaction chamber 201 and form a lower layer region on the base cylinder. When halogen atoms are contained in the lower layer region, SiF ₄ /He, for example, is further added to the above gas and fed into the reaction chamber. To form the upper layer region 105, layer formation is performed without the oxygen atom-containing gas used in forming the lower layer region. It goes without saying that all outflow valves for gases other than those required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 201 and the outflow valves 217 to 217 are closed. 221
In order to avoid remaining in the piping leading from to the reaction chamber 201, the outflow valves 217 to 221 are closed, the auxiliary valves 232 and 233 are opened, and the main valve 234 is fully opened to temporarily evacuate the system to a high vacuum. Perform the operations as necessary. During layer formation, the base cylinder 237 is rotated at a constant speed by a motor 239 in order to ensure uniform layer formation. Examples will be described below. Example 1 A layer was formed on an Al cylinder using the manufacturing apparatus shown in FIG. 2 under the following conditions. The image forming member thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 kV for 0.2 seconds.
Immediately, a light image was irradiated using a tungsten lamp light source, and a light intensity of 1.5 ux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. When the toner image on the member was transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

[Table] Example 2 A layer was formed on the A cylinder under the following conditions using the manufacturing apparatus shown in FIG. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 3 Image formation was performed by forming a lower layer region and an upper layer region under the same conditions as in Example ¹ , except that the flow rate ratio of NO/SiH ₄ when forming the lower layer region was 6 × 10 -2. A member was prepared, and when an image was formed on a transfer paper using the image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 4 A layer was formed on the A cylinder under the following conditions using the manufacturing apparatus shown in FIG. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 5 Using a Si ₂ H ₆ /He gas cylinder instead of the SiH ₄ /He gas cylinder used in Example 1, a layer was formed on the A cylinder using the manufacturing equipment shown in Fig. 2 under the following conditions. Formation was carried out. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 6 Example 1 was placed on the A cylinder which had been oxidized by anodization to form A ₂ O ₃ to a thickness of 800 Å.
An image forming member was prepared by forming a lower layer region and an upper layer region under the same conditions and procedures as described above. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Brief explanation of the drawing]

1A to 1C are schematic layer structure diagrams for explaining the layer structure of the electrophotographic photoconductive member of the present invention, and FIG. 2 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic photoconductive member of the present invention. FIG. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer, 103...Lower region, 104
. . . Layer region containing atoms of Group Group of the Periodic Table over its entire region, 105 . . . Upper layer region.

Claims (1)

[Claims] 1. A support for electrophotography and an amorphous layer exhibiting photoconductivity, which is composed of an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms and halogen atoms. and in which the amorphous layer contains oxygen atoms and atoms belonging to Group Group of the Periodic Table, the amorphous layer has a lower layer region and an upper layer region from the support side. These layer regions each have a substantially uniform chemical composition, and the oxygen atoms are contained only in the lower layer region throughout the region, and the oxygen atoms are contained in the entire region of the lower layer region. A photoconductive member for electrophotography, characterized in that atoms belonging to the group are contained at least in the lower layer region. 2. The photoconductive material for electrophotography according to claim 1, wherein the layer region containing atoms belonging to group 3 of the periodic table extends over the entire amorphous layer. Element. 3. The electrophotographic photoconductive device according to claim 1, wherein the layer region containing atoms belonging to Group 3 of the periodic table over its entire region is substantially the same as the lower layer region. Element. 4. The photoconductive member for electrophotography according to claim 1, wherein the lower layer region includes a layer region containing atoms belonging to group 3 of the periodic table over its entire region.