JPS6410064B2 - - 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 constituting a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, a document reading device, etc., it is highly sensitive,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], has spectral characteristics of the electromagnetic waves to be irradiated, has good photoresponsiveness, and has a desired dark resistance value.
Imaging devices are required to have characteristics such as being non-polluting to the human body during use, and being able to easily remove afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the pollution-free nature 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.
No. 2855718 describes its application as an electrophotographic image forming member, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as weather resistance and moisture resistance. There are points that can be further improved in terms of usage environment characteristics such as performance, and practical solid-state imaging devices, reading devices, electrophotographic image forming members, etc. need to be improved in terms of productivity and mass production. The reality is that it cannot be used effectively by taking into account the situation. For example, when applied to electrophotographic image forming members or solid-state imaging devices, it is often observed that residual potential remains during use, and when such photoconductive members are used repeatedly for a long time, There have been many inconveniences, such as the accumulation of fatigue due to repeated use and the generation of afterimages, the so-called ghost phenomenon. Furthermore, according to many experiments conducted by the present inventors, for example, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member can be used as a material constituting the photoconductive layer of an electrophotographic image forming member. An electrophotographic image having a single-layer photoconductive layer made of a-Si, which has many advantages compared to (organic photoconductive members), but also has properties suitable for use in conventional solar cells. Even if the photoconductive layer of the forming member is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotographic methods;
The above tendency is remarkable in a humid atmosphere.
It has been found that there are some problems that can be solved, such as in some cases, the charge cannot be retained at all until the development time. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to obtain desired electrical, optical, and photoconductive properties when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we found that it contains silicon atoms as a matrix and contains hydrogen atoms. It is designed to have a layer structure in which a specific intermediate layer is interposed between a photoconductive layer made of an amorphous material, so-called hydrogenated amorphous silicon (hereinafter referred to as a-Si; H), and a support that supports the photoconductive layer. The photoconductive member produced by this method is not only usable for practical use, but also superior in most respects to conventional photoconductive members, especially when used in electrophotography. This is based on the discovery that it has extremely excellent properties as a conductive member. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent resistance to light fatigue and does not cause deterioration even after repeated use. The main object of the present invention is to provide a photoconductive member for electrophotography in which no or almost no residual potential is observed. Another object of the present invention is to provide a photoconductive member for electrophotography which has high photosensitivity, has a spectral sensitivity region that covers substantially the entire visible light region, and has fast photoresponsiveness. Another object of the present invention is to have charge retention properties during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. An object of the present invention is to provide a photoconductive member for electrophotography, which has sufficient electrophotographic properties and has excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere. 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. The electrophotographic photoconductive member of the present invention includes a support;
a photoconductive layer made of an amorphous material containing silicon atoms as a matrix and hydrogen atoms; Preventing carriers from flowing into the photoconductive layer from the support side, and causing carriers generated in the photoconductive layer and moving toward the support side from the photoconductive layer side to the support side by electromagnetic wave irradiation. It is characterized by having an intermediate layer that allows passage. The electrophotographic photoconductive member of the present invention designed to have the layer structure described above can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. and usage environment characteristics. That is, 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, and has stable electrical properties even in a humid atmosphere. With high sensitivity,
It has a high signal-to-noise ratio, is extremely resistant to light fatigue, has excellent repeatability, and can obtain high-quality visible images with high density, clear halftones, and high resolution. Furthermore, when applied as an electrophotographic image forming member, a-Si:H with high dark resistance has low photosensitivity, and conversely, a-Si:H with high photosensitivity has a dark resistance of at most 10 ⁸ Ωcm.
In either case, a photoconductive layer with a conventional layer structure could not be applied to an electrophotographic image forming member, whereas the present invention has a relatively low resistance. (5×10 ⁸ Ωcm or more) a-
Since a photoconductive layer for electrophotography can be formed using a Si:H layer, a-Si:H, which has a relatively low resistance but high sensitivity, can also be used, and the characteristics of a-Si:H constraints can be alleviated. Hereinafter, according to the drawings, a photoconductive member for electrophotography of the present invention (hereinafter simply referred to as "photoconductive member") will be described.
This will be explained in detail. FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has an intermediate layer 102,
This layer structure includes a photoconductive layer 103 provided in direct contact with the intermediate layer 102, and is the most basic example of the present invention. The support 101 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au, Ir,
Examples include metals such as Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, its surface may be NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
If it is conductive treated by providing a thin film of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), or if it is a synthetic resin film such as polyether film, NiCr, Al, Ag , Pb, Zn, Ni, Au, Cr,
The surface is treated with a metal such as Mo, Ir, Nb, Ta, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, and the surface thereof is conductive. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. Within this range, it is made as thin as possible. However, in such a case, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The intermediate layer 102 is made of a preferably non-photoconductive amorphous material [a-( _{SixO1 -x} ) _y :H1 _-y] containing silicon atoms and oxygen atoms, and containing hydrogen atoms. However, 0<x<1, 0<y<1], which effectively prevents carriers from flowing into the photoconductive layer 103 from the support 101 side and prevents carriers from flowing into the photoconductive layer 103 by electromagnetic wave irradiation. occurs in the support 1
This has a function of easily allowing the photo carrier moving toward the photoconductive layer 103 to pass from the photoconductive layer 103 side to the support 101 side. a-(Si _x O _1-x ) _y : Intermediate layer 10 composed of H _1-y
2 is formed by glow discharge method, sputtering method,
This is done by ion implantation method, ion plating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method or the spacing method has the advantages that it is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member, and that it is easy to introduce oxygen atoms and hydrogen atoms together with silicon atoms into the intermediate layer to be manufactured. The Tuttering method is preferably employed. Furthermore, in the present invention, the intermediate layer 102 may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the intermediate layer 102 by the glow discharge method, the raw material gas for forming a-(Si _x O _1-x ) _y :H _1-y is mixed with dilution gas at a predetermined mixing ratio as necessary. The mixed gas is introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and a-(Si _x O _1-x ) _y : H _1-y may be deposited. In the present invention, the starting material serving as the raw material gas for forming a-(Si _x O _1-x ) _y :H _1-y is a gas containing at least one of Si, O, and H as a constituent atom. Most of the gasified materials or gasified materials that can be gasified can be used. When using a raw material gas containing Si as one of Si, O, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing O as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si and a raw material gas containing O and H may be mixed at a desired mixing ratio. or with a raw material gas containing Si as a constituent atom,
It can be used in combination with a raw material gas whose constituent atoms are Si, O, and H. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing O as constituent atoms. In the present invention, the starting materials that can be effectively used as the raw material gas for forming the intermediate layer 102 are SiH ₄ , Si ₂ H ₆ , and
Silicon hydride gas such as silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ ; disiloxane H ₃ SiOSiH ₃ and trisiloxane whose constituent atoms are Si, O, and H;
Preferred examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ , oxygen O ₂ containing O as a constituent atom, ozone O ₃ and H ₂ containing H as a constituent atom. To form the intermediate layer 102 by the sputtering method, target a single-crystal or polycrystalline Si wafer or SiO ₂ wafer, or a wafer containing a mixture of Si and SiO ₂ or a SiO ₂ wafer. These may be performed by sputtering in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gases for introducing O and H are diluted with diluting gas as necessary and introduced into the deposition chamber for sputtering, and the gases of these gases are diluted with diluting gas as necessary. The Si wafer may be sputtered by forming plasma. Separately, by using Si and SiO ₂ as separate targets or using a single mixed target of Si and SiO ₂ , sputtering can be performed in a gas atmosphere containing at least H atoms as a constituent. It is done by tuttering. As the raw material gas for introducing Si, O, or H, the raw material gases shown in the glow discharge example described above can be used as effective gases also in the case of sputtering. In the present invention, the diluent gas used when forming the intermediate layer 102 by a glow discharge method or a sputtering method is a so-called rare gas such as He,
Preferable examples include Ne, Ar, and the like. The intermediate layer 102 in the present invention is carefully formed to provide the desired properties. In other words, materials whose constituent atoms are Si, O, and H can have structural forms ranging from crystalline to amorphous, depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. and properties between photoconductive and non-photoconductive properties.
In the present invention, preferably,
It is desirable that the formation conditions be strictly selected so that non-photoconductive a-(Si _x O _1-x ) _y :H _1-y is formed. a-(Si _x
O _1-x ) _y :H _1-y has the function of the intermediate layer 102 to prevent the injection of carriers from the support 101 side into the photoconductive layer 103 and to prevent the photocarriers generated in the photoconductive layer 103 from being injected into the photoconductive layer 103 . Since it is intended to easily allow movement and passage to the support body 101 side, it is formed to exhibit electrically insulating behavior. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, it has a mobility value with respect to the carrier that passes through the intermediate layer 102 smoothly.
−(Si _x O _1-x ) _y : H _1-y is created. a-(Si _x O _1-x ) _y : H _1-y with the above characteristics
An important factor in the production conditions for production is the temperature of the support during production. That is, on the surface of the support 101, a-(Si _x O _1-x ) _y :
When forming the intermediate layer 102 consisting of H _1-y , the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. a-(Si _x O _1-x ) _y having the property of:
The support temperature during layer formation is strictly controlled so that H _1-y can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the intermediate layer 102 is appropriately selected in an optimal range in accordance with the method of forming the intermediate layer 102. is executed, but
Normally 100℃~300℃ Preferably 150℃~250℃
It is desirable that this is the case. Middle layer 102
For forming each layer, each layer can be formed successively in the same system from the intermediate layer 102 to the photoconductive layer 103, and further, if necessary, the third layer formed on the photoconductive layer 103. The glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms and control of layer thickness are relatively easy compared to other methods. When forming the intermediate layer 102 by the layer forming method described above, the discharge power _and gas pressure during layer formation are created in the same way as the support _temperature described above _. This can be cited as an important factor that influences the characteristics of _1-y . The discharge power conditions for effectively forming a-(Si _x O _1-x ) _y :H _1-y with good productivity that have the characteristics to achieve the purpose of the present invention are usually 1
~300W, preferably 2-150W. Furthermore, the gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8 Torr.
It is desirable that it be approximately ×10 ^-3 to 0.5 Torr. The amounts of oxygen atoms and hydrogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are as follows:
Similar to the manufacturing conditions of No. 02, this is an important factor in forming an intermediate layer that provides the desired properties to achieve the object of the present invention. The amount of oxygen atoms contained in the intermediate layer 102 in the present invention is usually 39 to 66 atomic%, preferably 42 atomic%.
It is desirable that the content be ~64 atomic%.
The content of hydrogen atoms is usually 2~
It is desirable that the hydrogen content be 35 atomic %, preferably 5 to 30 atomic %, and photoconductive members formed when the hydrogen content is in this range can be sufficiently applied as excellent materials in practice. It is something. That is, if expressed as a-(Si _x O _1-x ) _y :H _1-y, x is usually 0.33 to 0.40, preferably 0.33 to 0.37, and y
is usually 0.98 to 0.65, preferably 0.95 to 0.70. The numerical range of the layer thickness of the intermediate layer 102 in the present invention is one of the important factors for effectively achieving the object of the present invention. If the layer thickness of the intermediate layer 102 is too thin, it will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the support 101 side, and if it is too thick, , the probability that photocarriers generated in the photoconductive layer 103 will pass to the side of the support 101 becomes extremely small, and therefore, in both cases, the object of the present invention cannot be effectively achieved. Intermediate layer 1 for effectively achieving the object of the present invention
The layer thickness of 02 is usually 30 to 1000 Å, preferably 50 to 600 Å. In the present invention, in order to effectively achieve the purpose, a photoconductive layer 10 laminated on an intermediate layer 102 is used.
3 is a-Si:H having the semiconductor properties shown below.
Consists of. P-type a-Si:H... Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). P-type a-Si: Lightly doped with a so-called p-type impurity having a low acceptor concentration (Na) in the H... type. n-type a-Si:H... Contains only a donor. Or one that contains both donor and acceptor and has a high concentration of donor (Nd). The donor concentration (Nd) is low in the n ^- type a-Si:H... type. Lightly doped with so-called n-type impurities. i-type a-Si:H...NaNdO or
NaNd stuff. In the present invention, by providing the intermediate layer 102, a-Si:H constituting the photoconductive layer 103 as described above may be of relatively high resistance compared to the conventional one. However, in order to obtain even better results, the dark resistance of the photoconductive layer 103 to be formed is preferably 5×10 ⁹ Ωcm or more, optimally 10 ¹⁰ Ωcm.
It is preferable that the photoconductive layer 103 is formed to have a thickness of cm or more. In particular, this numerical condition for the dark resistance value is required when the produced photoconductive member is used as an image forming member for electrophotography, a highly sensitive reader or solid-state imaging device used in a low-light region, or a photoelectric conversion device. This is an important element when doing so. The layer thickness of the photoconductive layer of the photoconductive layer member in the present invention is appropriately determined according to the purpose of the application, such as a reading device, a solid-state imaging device, or an electrophotographic image forming member. . In the present invention, the layer thickness of the photoconductive layer is as follows:
The thickness relationship between the photoconductive layer and the intermediate layer can be appropriately determined as desired so that the functions of the photoconductive layer and the intermediate layer can be effectively utilized and the objects of the present invention can be effectively achieved. In normal cases, the layer thickness is preferably several hundred to several thousand times or more than the thickness of the intermediate layer. A specific value is usually 1 to 100μ, preferably 2 to 50μ. In the present invention, in order to make the photoconductive layer a layer composed of a-Si:H, when forming these layers, H is incorporated into the layer by the following method. . Here, "H is contained in the layer" means "a state in which H is combined with Si", "a state in which H is ionized and incorporated into the layer", or "a state in which H is ionized and incorporated into the _layer ". It means any of the states "incorporated into" or a combination thereof. As a method for incorporating H into the photoconductive layer, for example, when forming the layer, SiH ₄ , Si ₂ H ₆ ,
Introduced in the form of silicon compounds such as silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ , these compounds are decomposed by a glow discharge decomposition method, and the contained substances are removed as the layer grows. Ru. When forming a photoconductive layer by this glow discharge method, the starting materials for forming a-Si are SiH ₄ ,
When silicon hydride gas such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is decomposed to form a layer, H is automatically contained in the layer. When using the reaction sputtering method, He or
When performing sputtering with Si as a target in an inert gas such as Ar or a mixed gas atmosphere based on these gases, H ₂ gas is introduced or SiH ₄ , Si ₂ H ₄ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like, or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping. According to the findings of the present inventors, the H content of the photoconductive layer composed of a-Si:H influences whether the formed photoconductive member can be sufficiently applied in practice. It has been found that this is one of the major factors and is extremely important. In the present invention, in order for the photoconductive member to be formed to be sufficiently applicable to practical applications, the amount of H contained in the photoconductive layer is usually 1 to 40 atomic%, preferably 5 to 30 atomic%. It is preferable to set it as %. The amount of H contained in the layer can be controlled, for example, by controlling the temperature of the deposition support, the amount of starting material used to incorporate H into the deposition system, the discharge force, etc. Just do it. In order to make the photoconductive layer n-type or p-type, an n-type impurity, a p-type impurity, or both impurities are added to the formed layer during layer formation using a glow discharge method, a reactive sputtering method, etc. This is achieved by doping while controlling the amount. As impurities to be doped into the photoconductive layer, in order to make the photoconductive layer p-type, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferable. , in the case of n-type, elements of group A of the periodic table, such as N, P, As,
Preferred examples include Sb and Bi. Since the amount of these impurities contained in the layer is on the order of ppm, it is not necessary to pay as much attention to their pollution properties as the main materials that make up the photoconductive layer, but we use materials that are as non-polluting as possible. It is preferable to do so. From this point of view, B, As, P, Sb, etc. are optimal, taking into consideration the electrical and optical characteristics of the layer to be formed. In addition, it is also possible to control the material to be n-type by, for example, interstitial doping with Li or the like by thermal diffusion or implantation. The amount of impurity doped into the photoconductive layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group A of the periodic table,
Usually 10 ^-6 ~ 10 ^-3 atomic%, preferably 10 ^-5 ~
10 ^-4 atomic%, usually 10 ^-8 to 10 ^-3 atomic% in the case of group A of the periodic table, preferably 10 ^-8 to
It is desirable to set it to 10 ^-4 atomic%. FIG. 2 shows a schematic configuration diagram for explaining the configuration of another embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 is similar to the photoconductive member 100 shown in FIG. 1 except that an upper layer 205 having the same function as the intermediate layer 202 is provided on the photoconductive layer 203 It has a layered structure. That is, the photoconductive member 200 uses a-(Si _x O _1-x ) _y :H _1-y, which is a material similar to the material constituting the intermediate layer 202 on the support 201, and has the same function. An intermediate layer 202 formed to have a-Si:
A photoconductive layer 203 composed of H and the photoconductive layer 2
03 and has a top layer 205 having a free surface 204. When the upper layer 205 is used, for example, when the free surface 204 of the photoconductive member 200 is subjected to charging treatment to form a charge image, the charge that can be held on the free surface 204 is transferred to the photoconductive layer 203. photocarriers generated in the photoconductive layer 203 when irradiated with electromagnetic waves;
It has a function of easily allowing photo carriers or charged charges to pass through so as to cause recombination with the charged charges in the area irradiated with electromagnetic waves. The upper layer 205 is composed of a-(Si _x O _1-x ) _y :H _1-y , which has the same characteristics as the middle layer 202, and also has a
-Si _a N _1-a , a-(Si _a N _1-a ) _b :H _1-b , a-Si _c
C _1-c , a-(Si _c C _1-c ) _d : H _1-d , a-Si _z O _1-z, etc. A silicon atom, which is the host atom constituting the photoconductive layer, and a nitrogen atom or oxygen Al 2 O 3 , amorphous amorphous materials containing hydrogen atoms in place of or in addition to hydrogen atoms in the above-mentioned amorphous materials, Al ₂ O ₃ It can also be made of an inorganic insulating material such as polyester, polyparaxylylene, polyurethane, or the like. However, the material constituting the upper layer 205 is a-(S _a N _1-a ) _b :
H _1-b or a-(Si _c C _1-c ) _d : Consisting of H _1-d , or
It is preferable to use a-Si _a N _1-a or a-Si _x C _1-x , which do not contain hydrogen atoms. In addition to the materials listed above, suitable materials for forming the upper layer 205 include silicon atoms and at least two atoms among C, N, and O, and halogen atoms or halogen atoms. Examples include amorphous materials containing hydrogen atoms and hydrogen atoms. Examples of the halogen atom include F, Cl, Br, etc. Among the above amorphous materials, those containing F are effective from the viewpoint of thermal stability. The upper layer 205 can be formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, etc. similar to the method for forming the intermediate layer described above. After forming the above-mentioned upper layer 205, other necessary atoms such as oxygen atoms and nitrogen atoms are added in addition to halogen atoms, which makes it relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having desired characteristics. The glow discharge method or the reactive sputtering method is preferably employed because of the advantages that carbon atoms, hydrogen atoms, and halogen atoms can be easily introduced into the upper layer to be formed. For example, in order to form the upper layer 205 by a glow discharge method, a raw material gas for forming the upper layer is mixed with a dilution gas at a predetermined mixing ratio as necessary,
The material for forming the upper layer 205 may be deposited on the photoconductive layer 203 by introducing the gas into a deposition chamber for vacuum deposition and generating a glow discharge to turn the introduced gas into gas plasma. In the present invention, the starting material serving as the raw material gas for forming the upper layer is a gaseous substance or a gasifiable substance containing at least one of Si, C, N, O, H, and X as a constituent atom. Most gasified materials can be used. In the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., which have Si and H as constituent atoms, are effectively used as starting materials for forming the upper layer 205. Silicon hydride gas such as silanes, saturated hydrocarbons containing C and H as constituent atoms, for example, having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, and 2 to 4 carbon atoms. Examples include acetylene hydrocarbons. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ), pentane ( _{C5H10 )} , _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of starting materials containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these starting materials for forming the upper layer, there are of course starting materials for H introduction.
_H2 is also used as valid. Examples of the starting material for introducing the halogen atom (X) include simple halogen, hydrogen halide, interhalogen compounds, silicon halide, and halogen-substituted silicon hydride. Specifically, halogen gases such as fluorine, chlorine, bromine, and iodine are used as simple halogens, FH, HI, HCI, and HBr are used as hydrogen halides, and BrF, C1F, C1F ₃ , C1F ₅ , and interhalogen compounds are used.
BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , IC1, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiCl ₂ Br ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₃ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃
etc. can be mentioned. In addition to these, CC1 ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , SiC1 (CH ₃ ) ₃ , SiC1 ₂ (CH ₃ ) ₂ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiC1 ₃ CH ₃ can also be mentioned as effective. Examples of starting materials for introducing nitrogen atoms include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), and ammonium azide (NH ₄ N ₃ ). etc. can be mentioned. As starting materials for introducing oxygen atoms, those mentioned above as starting materials for forming an intermediate layer can be mentioned as effective ones. In addition to these starting materials for the formation of the upper layer, e.g. carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen dioxide (NO ₂ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), and the like. To form the intermediate layer 102 by the sputtering method, a single crystal or polycrystalline Si wafer and C, a SiO ₂ or Si ₃ N ₄ wafer, or Si and C,
This can be carried out by targeting a wafer containing a mixture of SiO ₂ or Si ₃ N ₄ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, raw material gases such as H ₂ and N ₂ or
H ₂ and NH ₃ , H ₂ and C ₂ H ₆ , etc. are diluted with diluent gas such as Ar as necessary and introduced into a sputtering deposition chamber to form a gas plasma of these gases. Then, the Si wafer may be sputtered. Alternatively, Si and C, SiO ₂ or Si ₃ N ₄ may be used as separate targets, or Si and C, SiO ₂ may be used as separate targets.
Alternatively, sputtering may be performed in a sputtering gas atmosphere using a single target formed by mixing Si ₃ N ₄ . In this case, if H or/and halogen atoms are contained in the upper layer formed, H or/and
In order to introduce halogen atoms, the above-mentioned starting material gas may be introduced into the sputtering deposition chamber during sputtering. The selection of the material constituting the upper layer 205 and the determination of its layer thickness are carried out from the upper layer 205 side to the photoconductive layer 20.
When the photoconductive member 200 is used in such a manner as to irradiate the electromagnetic waves that it senses in step 3, the irradiated electromagnetic waves reach the photoconductive layer 203 in the following amount, efficiently,
This is done carefully to induce the generation of photocarriers. The layer thickness of the upper layer 205 in the present invention is as follows:
In order to fully exhibit the above-mentioned functions, it is determined as desired depending on the material constituting the layer, the layer formation conditions, etc. The layer thickness of the upper layer 205 in the present invention is as follows:
Usually, the thickness is preferably 30 to 1000 Å, preferably 50 to 600 Å. If a certain type of electrophotographic process is employed when the photoconductive member of the present invention is used as an electrophotographic imaging member, the free surface of the photoconductive member has a layer configuration as shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer on top. In this case, the surface coating layer is, for example,
If an electrophotographic process such as the NP method described in Publications No. 23910 and No. 43-24748 is applied, it must be electrically insulating and have a low ability to retain static charge when subjected to charging treatment. Although it is required to have sufficient thickness and a certain level of thickness, for example, if an electrophotographic process such as the Carlson process is to be applied, it is desirable that the bright and dark potentials after electrostatic image formation be very small. The surface coating layer is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer should not have any adverse chemical or physical effects on the photoconductive layer or the upper layer, and should have electrical contact with the photoconductive layer or the upper layer. It is formed in consideration of wearability, moisture resistance, abrasion resistance, cleaning properties, etc. Typical materials effectively used for forming the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Organic insulators such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polypuden, polyvinyl butyral, polyurethane, polyparaxylylene, etc., silicone Examples include inorganic insulators such as nitrides and silicon oxides. Among these, synthetic resins or cellulose derivatives may be formed into a film and laminated onto the photoconductive layer or upper layer, or a coating solution may be formed and the photoconductive layer or upper layer may be coated. It may be coated on top to form a layer. The thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, it is usually 10μ or less, and conversely, when it is required to function as an electrical insulating layer, it is usually It is considered to be 10μ or more. However, the layer thickness value that differentiates this protective layer from the electrically insulating layer depends on the materials used, the applied electrophotographic process,
The above value of 10μ is not absolute, as it varies depending on the designed structure of the image forming member. Furthermore, if this surface coating layer also serves as an antireflection layer, its function will be further expanded and it will become more effective. Example 1 Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations. A molybdenum plate (substrate) 309 having a surface cleaned and having a thickness of 0.5 mm and 10 cm square was firmly fixed to a fixing member 303 at a predetermined position in the glow discharge deposition chamber 301 . The substrate 309 is heated with an accuracy of ±0.5° C. by the heater 308 inside the fixing member 303.
Temperature was measured directly on the back side of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 310 is fully opened, and the chamber 301 is closed.
The inside was evacuated to a vacuum level of approximately 5×10 ^-6 Torr.
Thereafter, the input voltage to the heater 308 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 200°C. After that, the auxiliary valve 341, then the outflow valves 326, 327, 328 and the inflow valve 321,
322 and 323 are fully opened, and the flow meter 31
The interior of 6,317,318 was also sufficiently degassed and vacuumed. Auxiliary valve 341, valves 326, 327,
After closing 328, 321, 322, 323,
_SiH4 gas diluted to 10vol% with _H2 (purity 99.999
%, hereinafter abbreviated as SiH ₄ /H ₂ ) valve 331 of the cylinder 311, valve 332 of the O ₂ gas cylinder 312
Open the outlet pressure gauges 336, 337 to 1.
Adjust to Kg/cm ² and gradually open the inflow valves 321 and 322 to enter the flow meters 316 and 317.
SiH ₄ /H ₂ gas and O ₂ gas were introduced. Subsequently, the outflow valves 326 and 327 were gradually opened, and then the auxiliary valve 341 was gradually opened. At this time
The inflow valves 321 and 322 were adjusted so that the ratio of SiH ₄ /H ₂ gas flow rate to O ₂ gas flow rate was 10:1.
Next, the opening of the auxiliary valve 341 was adjusted while observing the reading on the Pirani gauge 342, and the auxiliary valve 341 was opened until the inside of the chamber 301 became 1×10 ⁻² Torr. After the internal pressure of the chamber 301 became stable, the main valve 310 was gradually closed and the opening was throttled until the reading on the Pirani gauge 342 reached 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the switch of the high frequency power supply 343, close the shutter (also serves as an electrode) 305, and close the electrode 3.
03, 13.56MHz high frequency power was applied between the shutters 305 to generate glow discharge in the chamber 301, resulting in an input power of 3W. In order to deposit a-( _{SixO1 -x} ) _y :H1 _-y on the substrate under the above conditions, the conditions were maintained for 1 minute to form an intermediate layer. Thereafter, the high frequency power source 343 is turned off, the glow discharge is stopped, the outflow valve 327 is closed, and then the H ₂
B ₂ H ₆ gas diluted to 50 vol ppm with
(abbreviated as B ₂ H ₆ /H ₂ ) from Ponbe 313 to Valve 33
Gas pressure of 1Kg/cm ² through 3 (outlet pressure gauge 33
8 reading), open the inflow valve 323 to flow B ₂ H ₆ /H ₂ gas into the flow meter 318, and adjust the outflow valve 328 to adjust the reading of the flow meter 318 to the flow rate of SiH ₄ /H ₂ gas. The opening of the outflow valve 328 was determined to be 1/50 and stabilized. Subsequently, the high frequency power supply 343 was turned on again to restart the glow discharge. The input power at that time was set to 10W, which is higher than before. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heating heater 308 is turned off.
The high frequency power supply 343 is also turned off, and the substrate temperature is 100℃.
After waiting for the temperature to reach ℃, the outflow valves 326, 32
8 and inflow valves 321 and 323, and fully open the main valve 310 to drain the inside of the chamber 301.
After reducing the pressure to 10 ^-5 Torr or less, the main valve 310 was closed, and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained is placed in a charging exposure experiment device,
Corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. 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 tone reproducibility was obtained. Next, the image forming member was corona charged for 0.2 seconds at 5.5 KV using a charging exposure experimental device.
Immediately perform image exposure with a light intensity of 0.8lux・sec,
Immediately thereafter, a charged developer was cascaded onto the surface of the member, and then transferred and fixed onto transfer paper, resulting in an extremely clear image. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 2 Samples were prepared under the same conditions and procedures as in Example 1, except that the glow discharge holding time when forming the intermediate layer on the molybdenum substrate was varied as shown in Table 1 below. Image forming members designated by No. 1 were prepared, placed in the same charging exposure experimental apparatus as in Example 1, and subjected to image formation in the same manner as in Example 1. Results as shown in Table 1 below were obtained. As can be seen from the results shown in Table 1, in order to achieve the object of the present invention, the thickness of the intermediate layer must be between 30 Å and 1000 Å.
It is necessary to form within the range of .

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes ×: Impossible
Intermediate layer film deposition rate: 1Å/sec
Example 3 The process was exactly the same as Example 1, except that the flow rate ratio of SiH ₄ /H ₂ and O ₂ in the intermediate layer was varied as shown in Table 2 when forming the intermediate layer on the molybdenum substrate. Image forming members shown in samples Nos. 9 to 15 were prepared according to the conditions and procedures, and were installed in the charging exposure experimental apparatus exactly as in Example 1 to form images in the same manner, as shown in Table 2. The results shown are obtained. Furthermore, the sample
Table 3 shows the results of analyzing only the intermediate layers of Nos. 11 to 15 by electron microprobe method and hydrogen gas mass spectrometry method generated by heating. As can be seen from the results shown in Tables 2 and 3, x regarding the composition ratio of Si and O in the intermediate layer must be
It is necessary to form it in the range of 0.33 to 0.40.

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes ×: Impossible

[Table] Example 4 A molybdenum substrate was installed in the same manner as in Example 1, and then a vacuum of 5×10 ^-6 Torr was created in the glow discharge deposition chamber 301 by the same operation as in Example 1, and the substrate temperature was After the temperature was maintained at 200°C, the auxiliary valve 341 and then the outflow valve 3 were opened in the same manner as in Example 1.
26, 327 and inflow valves 321, 322 were fully opened, and the insides of flow meters 316, 317 were also sufficiently degassed and vacuumed. After closing the auxiliary valve 341, valves 326, 327, 321, 322,
_SiH4 / _H2 gas diluted to 10 vol% with _H2 (purity
99.999%) Open the valve 331 of the cylinder 311 and the valve 332 of the O ₂ gas cylinder 312, adjust the pressure of the outlet pressure gauges 336, 337 to 1 Kg/cm ² , gradually open the inflow valves 321, 322, and adjust the flow meter 316, SiH ₄ /H ₂ gas and O ₂ were each flowed into 317. Subsequently, the outflow valve 32
6,327 gradually open, then auxiliary valve 34
1 was gradually opened. At this time, the inflow valves 321 and 322 were adjusted so that the ratio of SiH ₄ /H ₂ gas flow rate to O ₂ gas flow rate was 10:1. Next, while watching the reading on the Pirani gauge 342, check the auxiliary valve 341.
The auxiliary valve 341 was opened until the pressure inside the chamber 301 became 1×10 ⁻² Torr. After the internal pressure of the chamber 301 became stable, the main valve 310 was gradually closed and the opening was throttled until the reading on the Pirani gauge 341 reached 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter 305 (which also serves as an electrode), turn on the high frequency power source 343, and connect the electrodes 303 and 305.
High frequency power of 13.56MHz was applied to generate glow discharge in the chamber 301, resulting in an input power of 3W. In order to deposit a-( _{SixO1 -x} ) _y :H1 _-y on the substrate under the above conditions, the conditions were maintained for 1 minute to form an intermediate layer. After that, the high frequency power supply 343 is turned off,
With the glow discharge stopped, the outflow valve 32
7 and then turn on the high frequency power supply 343 again.
I turned it on and restarted the glow discharge. The input power at that time was 10W, which was higher than before.
After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heating heater 308 is turned off, the high frequency power source 343 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 3
26 and the inflow valves 321, 322 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is
After reducing the pressure to below 10 ^-5 Torr, the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, the image quality was higher when the image was formed using corona discharge than when it was formed using corona discharge. The image quality was excellent and extremely clear. From these results, it was found that the photoreceptor obtained in this example had charge polarity dependence. Example 5 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1, the high frequency power source 343 was turned off,
With the glow discharge stopped, the outflow valve 32
7 and then diluted to 25Vol ppm with _H2
PH ₃ gas (hereinafter abbreviated as PH ₃ /H ₂ ) cylinder 314
At a gas pressure of 1 Kg/cm ² (reading of outlet pressure gauge 339) through valve 333 from inlet valve 324
Open the flow meter 319 to flow PH ₃ /H ₂ gas, and adjust the outflow valve 329 so that the reading of the flow meter 319 becomes 1/50 of the flow rate of SiH ₄ /H ₂ gas. The aperture was determined and stabilized. Subsequently, the high frequency power supply 343 was turned on again to restart the glow discharge. The input power at that time was 10W, which was higher than before. After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heater 308 is turned off.
The high frequency power supply 343 is also turned off, and the substrate temperature is 100℃.
After waiting for the temperature to reach ℃, the outflow valves 326, 32
9 and inflow valves 321, 324, and fully open the main valve 310 to drain the inside of the chamber 301.
After reducing the pressure to below 10 ^-5 Torr, the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 11μ. 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. The image quality was excellent and extremely clear. From these results, it was found that the photoreceptors obtained in Examples had charge polarity dependence. Example 6 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1, the high frequency power source 343 was turned off and glow discharge was stopped, and the flow was discharged. Close valve 327 and then inject 1 Kg/cm 2 through valve 333 from B ₂ H ₆ gas cylinder 313 diluted with H ₂ to 50 Vol ppm ^.
at gas pressure (reading on outlet pressure gauge 338), open inlet valve 323 to
By flowing B ₂ H ₆ /H ₂ gas and adjusting the outflow valve 328, the reading of the flow meter 318 changes to SiH ₄ /H 2 gas.
Outflow valve 32 so that the flow rate is 1/10 of the _H2 gas flow rate.
8 openings were defined and stabilized. Subsequently, the high frequency power supply 343 was turned on again to restart the glow discharge. The input power at that time was 10W, which was higher than before. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heating heater 308 is turned off, the high frequency power supply 343 is also turned off, and the substrate temperature reaches 100°C.
Wait until the outflow valves 326, 328
The inflow valves 321 and 323 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is reduced to 10 ^-5 Torr.
After the following, close the main valve 310 and close the chamber 30.
1 was brought to atmospheric pressure using a leak valve 306, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 10μ. 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. The image quality was excellent and extremely clear. From these results, it was found that the photoreceptor obtained in this example had charge polarity dependence. However, the charge polarity dependence was opposite to that of the image forming members obtained in Examples 4 and 5. Example 7 Similar to Example 1, a molybdenum substrate 309 was fixed to a fixing member 303 at a predetermined position in a deposition chamber 301.
was firmly fixed. Target 304 is of high purity
_SiO2 was used. After confirming that all valves in the system are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is evacuated to approximately 5×10 ^-6 Torr.
The vacuum level was set to . Thereafter, the input voltage to the heater 308 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 200°C. Thereafter, the auxiliary valve 341 and the outflow valves 326, 328, 330 were opened, and after the flow meters 316, 318, 320 were sufficiently deaerated, the outflow valves 326, 328, 330 and the auxiliary valve 341 were closed. 30vol of _H2
% containing Ar (purity 99.999%, hereinafter abbreviated as Ar/H ₂ )
After the valve 335 of the gas cylinder 315 was opened and the reading of the outlet pressure gauge 340 was adjusted to 1 Kg/cm ² , the inflow valve 324 was opened to allow Ar/H ₂ gas to flow into the chamber 301 . Pirani gauge 34
The outflow valve 330 is gradually opened until the indication in step 2 reaches 5×10 ^-4 Torr, and after the flow rate stabilizes in this state, the main valve 310 is gradually closed, and the indoor pressure becomes 1×10 ^-2 The aperture was narrowed down to Torr. Operate the shutter rod 307 to open the shutter 305, confirm that the flow meter 320 is stable, and then turn on the high frequency power supply 343.
It was turned on, and AC power of 13.56 MHz and 100 W was input between the target 304 and the fixed member 303. Under these conditions, the layers were formed while performing matching so that stable discharge could continue. Discharge was continued in this manner for 1 minute to form an intermediate layer with a thickness of 100 Å.
Thereafter, the high frequency power source 343 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 330 was closed, and the main valve 310 was fully opened to remove gas from the chamber 301, creating a vacuum of 5×10 ⁻⁷ Torr. After that, the valve 335 is closed and the auxiliary valve 34
1, then the outflow valve 330 and the inflow valve 32
5 was fully opened, and the inside of the flow meter 320 was also sufficiently degassed and vacuumed. After closing the auxiliary valve 341 and outflow valve 330, it was diluted to 10 vol% with _H2 .
SiH ₄ /H ₂ gas (99.999% purity) cylinder 311, valve 331, diluted with H ₂ to 50 vol ppm
Open the valve 333 of the B ₂ H ₆ /H ₂ gas cylinder 313 and set the pressure on the outlet pressure gauges 336 and 338 to 1Kg/cm ²
and gradually open the inflow valves 321 and 323 to allow SiH ₄ /
H ₂ gas B ₂ H ₆ /H ₂ gas was introduced. Subsequently, the outflow valves 326 and 328 were gradually opened, and then the auxiliary valve 341 was gradually opened. At this time
SiH ₄ /H ₂ gas flow rate and B ₂ H ₆ /H ₂ gas flow rate ratio are
The inflow valves 321 and 323 were adjusted so that the ratio was 50:1. Next, the opening of the auxiliary valve 341 was adjusted while observing the reading on the Pirani gauge 342, and the auxiliary valve 341 was opened until the inside of the chamber 301 reached 1×10 ⁻² Torr. After the internal pressure of chamber 301 stabilizes,
The main valve 310 was gradually closed and the opening was throttled until the reading on the Pirani gauge 342 reached 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter 305 and then turn on the high frequency power supply 34.
Turn on the switch No. 3 and turn on the electrodes 303, 3.
05, 13.56MHz high frequency power was applied to room 30.
A glow discharge was generated within the battery, and the input power was 10W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 308 is turned off,
The high frequency power supply 343 is also turned off, and the substrate temperature is 100℃.
After waiting for the temperature to reach ℃, the outflow valves 326, 32
8 and inflow valves 321, 323, and 325, and fully open the main valve 310 to open the chamber 301.
After reducing the internal pressure to 10 ^-5 Torr or less, the main valve 31
0 was closed, the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 6.0 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 0.8 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image is created on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component.
Transferred onto transfer paper with 5.0KV corona charging,
A clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the image forming member was corona charged for 0.2 seconds at 5.5KV using a charging exposure experiment device, and immediately
Immediately after image exposure was performed with a light intensity of 0.8 lux·sec, a charged developer was cascaded onto the surface of the member, and then transferred and fixed onto transfer paper, resulting in an extremely clear image. From this result and the previous results, it was found that the electrophotographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of an amphipolar image forming member. Example 8 A SiH ₄ / _{H 2 gas} cylinder 311 diluted to 10 vol% with H 2 is replaced with an undiluted Si ₂ H ₆ gas cylinder, and a B ₂ H ₆ /H ₂ gas cylinder 313 diluted with H ₂ to 50 vol ppm. , diluted to 500 vol ppm with _H2
After forming an intermediate layer and a photoconductive layer on a molybdenum substrate under the same conditions and procedures as in Example 1 except for changing to a B ₂ H ₆ /H ₂ cylinder, Example 1 was taken out of the deposition chamber 301. Similarly, when we tested the image formation by placing it in a charged exposure experimental device, in the case of a combination of 5.5KV corona discharge and charged developer,
A very good quality, high contrast toner image was obtained on the transfer paper. Example 9 After forming an intermediate layer on a molybdenum substrate for 1 minute and forming a photoconductive layer for 5 hours under the same conditions and procedures as in Example 1, the high frequency power source 343 was turned on.
In the off state, the glow discharge is stopped.
The outflow valve 328 was closed and the outflow valve 327 was opened again to obtain the same conditions as during the formation of the intermediate layer. Then turn on the high frequency power supply again.
The glow discharge was restarted. The input power at that time was also 3W, the same as when forming the intermediate layer. After continuing the glow discharge for 2 hours to form an upper layer on the photoconductive layer, the heating heater 308 is turned on.
off state, and the high frequency power supply 343 is also off state,
After waiting for the substrate temperature to reach 100°C, the outflow valves 326, 327 and the inflow valves 321, 322
Close the main valve 310 and fully open the chamber 30.
After reducing the pressure inside 1 to below 10 ^-5 Torr, open main valve 3.
10 was closed, the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. When a toner image was formed using the thus obtained image forming member in the same manner as in Example 1, the resolution and the combination of the 6KV corona-charged developer and the +6KV corona-charged developer were found to be Images with excellent tonality and image density were obtained. Example 10 Under the same conditions and procedures as in Example 1, an intermediate layer was formed on a molybdenum substrate for 1 minute, and a photoconductive layer was formed for 5 hours to produce 10 sheets, and the upper part shown in Table 4 was prepared. A layer was formed on each photoconductive layer. For sample A, the PH ₃ /H ₂ gas cylinder 314 was previously connected to H ₂
The C ₂ H ₄ /H ₂ gas cylinder diluted to 10 vol% was used, and the flow ratio of SiH ₄ /H ₂ gas and C ₂ H ₄ /H ₂ gas was set to ₁ :9. ₂
Gas cylinder 314 with high purity _N2 gas (99.999%)
Instead of using a cylinder, the flow rate ratio of SiH ₄ /H ₂ gas and N ₂ gas was set to 1:10, and for sample C, PH ₃ /H ₂ gas was
Gas cylinder 314 was diluted to 10vol% with _H2.
Instead of using NH ₃ /H ₂ gas cylinder, use SiH ₄ /H ₂ gas.
The upper layers of Samples A, B, and C were formed under the same conditions and procedures as in Example 9, except that the flow rate ratio of NH ₃ /H ₂ gas was 1:2. In addition, in sample D, the SiH ₄ /H ₂ gas cylinder 311 was replaced with a SiF ₄ /H ₂ gas cylinder containing 10 vol% of H ₂ and the PH ₃ /H ₂ gas cylinder 314 was diluted with H ₂ to 10 vol% of C ₂ H ₄ /H _{2 .} Instead of a gas cylinder, use SiF ₄ /H ₂
The flow rate ratio of gas and C ₂ H ₄ /H ₂ gas was set to 1:9, and in sample E, a PH ₃ /H ₂ gas cylinder 314 was prepared in advance.
to a high-purity _N2 gas (99.999%) cylinder.
The flow rate ratio of SiF ₄ /H ₂ gas and N ₂ gas is 1:50,
For sample F, PH ₃ /H ₂ gas cylinder 31
4 was replaced with a NH ₃ gas cylinder diluted to 10 vol% with H ₂ and the flow rate ratio of SiF ₄ /H ₂ and NH ₃ /H ₂ gas was set to 1:
The upper layers of Samples D, E, and F were formed according to the same conditions and procedures as in Example 9, except that the upper layer was changed to 20%. Furthermore, for sample G, PH ₃ /H ₂ gas cylinder 3
14 was changed to Si(CH ₃ ) ₄ /H ₂ diluted to 10 vol% with H ₂ and after forming the photoconductive layer, the outflow valve 326, 3
28 was closed, the main valve 310 was fully opened, and the room was once evacuated to 5×10 ^-6 Torr. Then Si
(CH ₃ ) ₄ /H ₄ gas was introduced into the chamber through an inlet valve 324 and an outlet valve 329, and an upper layer was formed according to the same conditions and procedures as in Example 9. In samples H and I, the target was prepared using polycrystalline Si.
(99.999%) and Si ₃ N ₄ target, and the PH ₃ /H ₂ gas cylinder 314 was changed to an N ₂ gas cylinder diluted to 50 vol% with Ar. In sample J, the target was graphite on polycrystalline Si. Change it to one installed so that the area ratio is 1:9, and
The PH ₃ /H ₂ gas cylinder 314 was replaced with an Ar gas cylinder, and after each photoconductive layer was formed, the inside of the system was heated 5×.
After exhausting to 10 ^-7 Torr and closing all valves, open valve 334 of cylinder 314 and set the outlet pressure to 1Kg/cm ²
And so. (Reading of outlet pressure gauge 328) Then, open the inflow valve 324, outflow valve 329, and auxiliary valve 341 to introduce gas into the chamber.Adjust the auxiliary valve 341 to bring the internal pressure to 5 × 10 ^-4 Torr.
(Reading of Pirani gauge 342) Furthermore, the internal pressure was set to 1 × 10 ^-2 Torr by the main valve 310, and the shutter rod 307 was operated.
05 is opened and the high frequency power supply 343 is turned on, between the target 304 and the fixed member 303,
An alternating current of 13.56MHz 100W was input. After forming the upper layer in this state for 2 minutes, turn off the high frequency power supply.
state, auxiliary valve 340, outflow valve 32
9. Close the inflow valve 324 and close the main valve 31
0 at full throttle. After the chamber was evacuated to within 10 ^-5 Torr, the main valve 310 was closed, the chamber was brought to atmospheric pressure by the leak valve 306, and the substrate was taken out. When toner images similar to those in Example 1 were formed using the image forming members A to J thus obtained, -
6KV corona charged developer, and +6KV
Images with excellent resolution, tonality, and image density were obtained for both combinations of corona-chargeable developers.

[Table] Example 11 An intermediate layer and a photoconductive layer were formed in the same manner as in Example 1 on a substrate in which a tin oxide transparent electrode was provided on an optically polished glass plate using a conventional method. However, when forming the photoconductive layer, the preparation time was shortened so that the layer thickness was approximately 2.1 μm. Next, it was transferred to a regular evaporation apparatus and 90N of antimony trisulfide was used as a beam landing layer under a vacuum of 5×10 ^-3 Torr using Ar gas.
The photoconductive layer was deposited to a thickness of m. When the photoconductive member prepared in this manner was used as the light receiving surface of a visual image pickup tube, when irradiated with 12 lux of white light at a target applied voltage of 50 V, the signal current was 630 mA, the dark current was less than 0.83 mA, and the afterimage characteristics were 10 after 3 fields. %, good characteristics were obtained.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the photoconductive member for electrophotography of the present invention, and FIG. 3 shows the photoconductive member for electrophotography of the present invention. It is a typical explanatory view showing an example of the device in the case of manufacturing. 100,200...Photoconductive member for electrophotography, 1
01,201...Support, 102,202...Intermediate layer, 103,203...Photoconductive layer, 104,2
04...free surface, 205...upper layer.

Claims (1)

[Scope of Claims] 1. A support, a photoconductive layer composed of an amorphous material having silicon atoms as a matrix and containing hydrogen atoms, and having a hydrogen atom content of 1 to 40 atomic%, and a photoconductive layer between them. The material is made of an amorphous material containing silicon atoms as a matrix and oxygen atoms and hydrogen atoms. A photoconductive member for electrophotography, characterized in that the photoconductive member for electrophotography has an intermediate layer that allows a carrier to pass from the photoconductive layer side to the support side when the carrier is generated and moves toward the support side. 2. The photoconductive member for electrophotography according to claim 1, further comprising an upper layer on the photoconductive layer. 3. The photoconductive member for electrophotography according to claim 2, wherein the upper layer is made of an amorphous material having silicon atoms as a matrix and containing at least one of oxygen atoms, nitrogen atoms, and carbon atoms. . 4 The amorphous material constituting the upper layer is
The electrophotographic photoconductive member according to claim 3, which contains at least one of a hydrogen atom and a halogen atom. 5. The photoconductive member for electrophotography according to claim 2, wherein the upper layer is made of an inorganic insulating material. 6. The photoconductive member for electrophotography according to claim 1, wherein the intermediate layer has a layer thickness of 30 to 1000 Å. 7 The amount of oxygen atoms contained in the intermediate layer is
The photoconductive member for electrophotography according to claim 1, which has a content of 39 to 66 atomic%. 8. The photoconductive member for electrophotography according to claim 1, wherein the amount of hydrogen atoms contained in the intermediate layer is 2 to 35 atomic %. 9. The photoconductive member for electrophotography according to claim 2, wherein the upper layer has a layer thickness of 30 to 1000 Å. 10. The photoconductive member for electrophotography according to claim 1, wherein the photoconductive layer contains either an n-type impurity or a p-type impurity. 11. The photoconductive member for electrophotography according to claim 10, wherein the n-type impurity is an element belonging to Group 3 of the periodic table. 12. The photoconductive member for electrophotography according to claim 10, wherein the p-type impurity is an element belonging to Group 1 of the periodic table.