JPS649625B2 - - 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 dispose of 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.
For example, German Publication No. 2746967 and German Publication No. 2855718 describe its application as an image forming member for electrophotography, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. It has been done. 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 image forming members for electrophotography or solid-state imaging devices, it is often observed that residual potential remains during use, and such photoconductive members can be repeatedly used for long periods of time. Accumulation of fatigue occurs due to use. There have been many disadvantages, such as a so-called ghost phenomenon in which an afterimage occurs. 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. a photoconductive layer made of an amorphous material, so-called hydrogenated amorphous silicon (hereinafter referred to as "a-Si:H");
A photoconductive member designed and manufactured with a layer structure in which a specific intermediate layer is interposed between the photoconductive layer and the support supporting the photoconductive layer is not only usable for practical use, but is also incomparable with conventional photoconductive members. This is based on the fact that it has been found to be superior in most respects, especially when compared, and has particularly excellent properties as a photoconductive member for electrophotography. 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 maintain electrolyte 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. It is an object of the present invention to provide a photoconductive member for electrophotography, which has sufficient performance and 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 containing 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. A photoconductive member for electrophotography 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, as well as an environment in which it can be used. Show characteristics. When the photoconductive member for electrophotography of the present invention is 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 remains stable even in a humid atmosphere. It has stable electrical properties, high sensitivity, and a high signal-to-noise ratio, and has excellent resistance to light fatigue and repeated use. Furthermore, in the case of electrophotographic image forming members, it has high density and clear halftones. It is possible to obtain high-quality visible images with 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 low dark resistance of around 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 Since a photoconductive layer for electrophotography can be constructed even with an a-Si:H layer having a resistance of ⁹ Ωcm or more, a high-sensitivity a-Si:
H can also be used sufficiently, and restrictions from the characteristics of a-Si:H 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 conductive, electrical, or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, Ir, 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 polyester 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, so that the surface thereof is conductive. The shape of the support is
It can be of any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined depending on the desire, but for example,
If the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for 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 non-photoconductive amorphous material [hereinafter abbreviated as "a-(Si _x N _1-x ) _y :H _1-y "] that has silicon atoms as its base material and contains nitrogen atoms and hydrogen atoms. However, it is composed of 0<x<1, 0<y<1],
This effectively prevents the inflow of carriers into the photoconductive layer 103 from the side of the support 101 and prevents photocarriers generated in the photoconductive layer 103 by the irradiation of electromagnetic waves and moving toward the side of the support 101. Photoconductive layer 1
03 side to the support body 101 side. a-(Si _x N _1-x ) _y : Intermediate layer 10 composed of H _1-y
2 is formed by glow discharge method, sputtering method,
This is accomplished by an ion implantation method, an ion plating method, an electron beam method, or the like. 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 is preferred because it is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member, and it is also easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the intermediate layer to be manufactured. Alternatively, a sputtering 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 system.To form the intermediate layer 102 by the glow discharge method , a-(Si _x N _1-x ) _y : The raw material gas for forming H _1-y is mixed with dilution gas at a predetermined mixing ratio as needed, and the mixture is heated to the vacuum where the support 101 is installed. The gas is introduced into a deposition chamber for deposition, and the introduced gas is turned into glass plasma by generating a glow discharge, and a-(Si _x N _1-x ) _y :H _1-y is deposited on the support 101. That's fine. In the present invention, the raw material gas for forming a-(Si _x N _1-x ) _y :H _1-y is a gaseous substance or gasified substance containing at least one of Si, N, and H as a constituent atom. Most of the gasified materials available can be used. When using a raw material gas containing Si as one of Si, N, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing N as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing N and H as constituent atoms may be mixed at a desired mixing ratio. Can be used by mixing. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, starting materials that can be effectively used as raw material gas for forming the intermediate layer 102 include SiH ₄ , Si ₂ H 6 , and SiH ₄ whose constituent atoms are Si and H.
Silicon hydride N such as silanes such as Si ₄ H ₁₀
or N and H as constituent atoms, such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (NH ₃ ), ammonium azide (NH ₄ Mention may be made of gaseous or gasifiable nitrogen such as N ₃ ), nitrogen compounds such as nitrides and azides. In addition to these starting materials for forming the intermediate layer, H ₂ is of course also used as an effective raw material gas for introducing H. To form the intermediate layer 102 by the sputtering method, target a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer containing a mixture of Si and Si ₃ N ₄ ,
This may be done by sputtering in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing N and H, e.g.
H ₂ and N ₂ or NH ₃ are diluted with diluted gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer. Just do it. Alternatively, by using Si and Si ₃ N ₄ as separate targets or by using a single target formed by mixing Si and Si ₃ N ₄ , a gas containing at least H atoms can be produced. This is done by sputtering in an atmosphere. As a raw material gas for introducing N or H, the starting material gas for forming the intermediate layer shown in the glow discharge example described above can also be used as an effective gas for sputtering. In the present invention, 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, N, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. and the properties between photoconductive and non-photoconductive properties,
Therefore, in the present invention, the preparation conditions are strictly selected so that preferably non-photoconductive a-(Si _x N _1-x ) _y :H _1-y is formed. It is desirable that a-(Si _x
N _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 N _1-x ) _y : H _1-y is created. a-(Si _x N _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 N _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 N _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 the middle layer 10
2, the intermediate layer 102 to the photoconductive layer 103, and further the photoconductive layer 103 as necessary, are formed in the same system.
It can be formed continuously up to the third layer formed on top. Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. , when forming the intermediate layer 102 using these layer forming methods, the discharge power and gas pressure during layer formation are created in the same manner as the support temperature described above.a-(Si _x N _1-x ) _y : One of the important factors that influences the characteristics of H _1-y . The discharge power conditions for effectively forming a-(Si _x N _1-x ) _y :H _1-y with good productivity, which have the characteristics to achieve the purpose of the present invention, are usually 1
~300W, preferably 2-100W. The gas pressure in the deposition chamber is usually about 0.01 to 5 Torr, preferably about 0.1 to 0.5 Torr when layer formation is performed by glow discharge, and usually about 0.1 to 0.5 Torr when layer formation is performed by sputtering method. It is desirable to set it at about 10 ^-3 to 5 x 10 ^-2 Torr, preferably about 8 x 10 ^-3 to 3 x 10 ^-2 Torr. The amounts of nitrogen 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 nitrogen atoms contained in the intermediate layer 102 in the present invention is usually 25 to 55 atomic %, preferably 35 atomic %.
It is desirable that the content be ~55 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 products in practice. It is something. That is, if expressed as above a-(Si _x N _1-x ) _y :H _1-y , x is usually 0.43 to 0.60, preferably 0.43 to 0.50,
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 the photocarriers generated in the photoconductive layer 103 will pass to the support 101 side becomes extremely small, and therefore the object of the invention cannot be effectively achieved in any case. 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 that constitutes the photoconductive layer 103 as described above can be used with a relatively low resistance compared to the conventional one. However, in order to obtain better results, the dark resistance of the photoconductive layer 103 to be formed is preferably 5 to 10 ⁹ Ωcm or more, most preferably 10 ¹⁰
It is desirable that the photoconductive layer 103 be formed so that the resistance is Ωcm or more. In particular, this numerical condition for the dark resistance value is required when the manufactured photoconductive member is used as an image forming member for electrophotography, a highly sensitive reading device 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 member for electrophotography 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 image forming member for electrophotography. be done. 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, H is incorporated into the layer by the following method when forming these layers. 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 of these states. 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
H ₂ gas is introduced when performing sputtering targeting Si in an inert gas atmosphere such as SiH 4 , Ar, etc., or a mixed gas atmosphere based on these gases, or SiH ₄ , Si ₂ H ₄ , Si A silicon hydride gas such as ₃ H ₈ or S ₄ H ₁₀ or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping may be introduced. According to the knowledge of the present inventors, the H content of the photoconductive layer composed of a-Si:H determines whether the formed photoconductive member can be sufficiently applied in practice. It has been found that this is one of the major influencing 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 4 atomic%, preferably 5 to 30 atomic%. It is preferable to set it as %. The amount of H contained in the layer can be controlled by, for example, the temperature of the deposition support or the amount of starting material used to contain H introduced into the deposition system;
All you have to do is control the discharge force, etc. 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, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferably used to make the photoconductive layer p-type. and when making it 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 constituting the photoconductive layer, but it is important to use materials that are as non-polluting as possible. is preferred. From this point of view, B, Ga, 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 interstitial doping with Li or the like by thermal diffusion or implantation, for example. 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, it is usually 10 ^-6 to 10 ^-3 atomic%, preferably 10 ^-5 to 10 ^-4 atomic%, usually 10 -8 to 10 -3 atomic%, preferably 10 ^-8 to ^{10 -3} atomic% in the case of Group A of the periodic table.
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 has a-(Si _x
N _1-x ) _y : An intermediate layer 202 formed using H _1-y to have a similar function, a photoconductive layer 203 composed of a-Si:H, and the photoconductive layer 203 It comprises a top layer 205 having a free surface 204 thereon. 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 retained 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 N _1-x ) _y :H _1-y , which has the same characteristics as the middle layer 202, and also has a
-Si _a C _1-a , (a-Si _a C _1-a ) _b :H _1-b , (a-Si _c
O _1-c ) _d : A host atom constituting a photoconductive layer such as H _1-d . Amorphous materials composed of silicon atoms and nitrogen atoms or oxygen atoms, or containing hydrogen atoms based on these atoms, or such amorphous materials further containing halogen atoms,
It can also be composed of an inorganic insulating material such as Al ₂ O ₃ or an organic insulating material such as polyester, polyparaxylene, or polyurethane. However, the material constituting the upper layer 205 is a-(Si), which has the same characteristics as the intermediate layer 202 from the viewpoint of productivity, mass production, and electrical and usage environment stability of the formed layer. _x N _1-x ) _y : H _1-y or a-Sia _{C 1-a} , a-( _Sia C _1-a ) _b : H _1-b ,
a-Si _c N _1-c , a-(Si _d C _1-d ) _e :L _1-e , a-(Si _f
C _1-f ) _g : (H+X) _1-g , a-(Si _h N _1-h ) _i : X _1-i , 1
-(Si _j N _1-j ) _k : (H+X) _1-k is desirable. In addition to the above-mentioned materials, 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. Mention may be made of amorphous materials containing 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 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 203.
When using the photoconductive member 200 in such a manner that the electromagnetic waves that are detected by done carefully. The upper layer 205 can be formed using the same method as the intermediate layer 202, such as a glow discharge method or a reactive sputtering method. Upper layer 205
As starting materials used in the formation, in addition to the above-mentioned materials used for forming the intermediate layer, examples of starting materials for introducing carbon atoms include saturated hydrocarbons having 1 to 4 carbon atoms. , ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of starting materials for incorporating oxygen atoms into the upper layer 205 include enzymes (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ),
Examples include nitric oxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen monoxide (N ₂ O). In addition to these, as one of the starting materials for forming the upper layer 205, for example, CCl ₄ , CHF ₃ , CH ₂ F ₂ ,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ F, 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 , Si(CH ₃ ) ₄ , Alkyl silicides such as Si(C ₂ H ₅ ) ₄ , SiCl(CH ₃ ) ₃ , SiCl ₂ C
Derivatives of silanes such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These starting materials for forming the upper layer 205 include predetermined atoms as constituent atoms of the upper layer 2 to be formed.
05, they are appropriately selected and used during layer formation. For example, if a glow discharge method is used, Si
Single gas such as (CH ₃ ) ₄ , SiCl ₂ (CH ₃ ) ₂ or SiH ₄ −
O ₂ (−Aγ) system, SiH ₄ −NO ₂ system, SiH ₄ −O ₂ −N ₂
system, SiCl ₄ −CO ₂ −H ₂ system, SiCl ₄ −NO−H ₂ system,
SiH ₄ −NH ₃ system, SiCl ₄ −NH ₄ system, SiH ₄ −N ₂ system,
SiH ₄ −NH ₃ −NO system, Si(CH ₃ ) ₄ −SiH ₄ system, SiCl ₂
A mixed gas such as a ( _CH3 ) ₂ - _SiH4 system can be used as a starting material for forming the upper layer 105. 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. It is required that the thickness is sufficient and above a certain level, for example,
If an electrophotographic process such as the Carlson process is applied, it is desirable that the bright and dark potentials after electrostatic image formation be very small, so the surface coating layer is required to be very 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 insulating feathers such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polybutene, polyvinyl butyral, polyurethane, polyparaxylylene, etc., silicone Examples include inorganic insulating materials such as nitrides and silicon oxides. These synthetic resins or cellulose derivatives may be made into a film and laminated onto the photoconductive layer or the upper layer, or a coating solution thereof may be formed and applied onto the photoconductive layer or the upper layer. However, a layer may be formed. 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 a glow discharge deposition chamber 301 placed on a support stand 302 . The substrate 309 is heated by the heater 308 inside the fixing member 303.
Heated with an accuracy of 0.5℃. 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 inside of the chamber 301 is evacuated.
The vacuum level was set to ×10 ^-6 Torr. Then heater 3
The input voltage of 08 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 340, then the outflow valves 325, 326, 327 and the inflow valve 320-
2,321,322 fully open, flow meter 3
16, 317, and 318 were also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 325, 32
After closing 6,327,320-2,321,322, _SiH4 gas diluted to 10 vol% with _H2 (hereinafter
Abbreviated as SiH ₄ /H ₂ . Purity 99.999%) Cylinder 311
Open the valve 330 of the N ₂ (99.999% purity) gas cylinder 312, and open the outlet pressure gauge 33.
The pressure of 5,336 was adjusted to 1 Kg/cm ² and the inflow valves 320-2, 321 were gradually opened to allow SiH ₄ /H ₂ gas and N ₂ gas to flow into the flow meters 316 and 317. Subsequently, the outflow valves 325, 32
6 was gradually opened, and then the auxiliary valve 340 was gradually opened. At this time, _the inflow _{valve 320-}
2,321 were adjusted. Next, Pirani Gauge 34
The opening of the auxiliary valve 340 was adjusted while observing the reading of 1, and the auxiliary valve 340 was opened until the inside of the chamber 301 became 1×10 ⁻² Torr. After the internal pressure of the chamber 301 stabilizes, the main valve 310 is gradually closed.
The aperture was closed until the reading on the Pirani gauge 341 was 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 342 and apply 13.56M to the induction coil 343.
A high frequency power of Hz was applied to generate glow discharge in the chamber 301 of the coil section (upper part of the chamber), resulting in an input power of 3W. a-(Si _x N _1-x ) _y on the substrate under the above conditions:
To deposit H _1-y , conditions were maintained for 1 minute to form an intermediate layer. After that, turn on the high frequency power supply 342.
In the off state and with the glow discharge stopped,
Close the outflow valve 326 and then 50vol ppm with _H2
B ₂ H ₆ (hereinafter abbreviated as B ₂ H ₆ /H ₂ ) diluted to
Gas pressure in Kg/cm ² (outlet pressure gauge 337 reading)
Then, by adjusting the inflow valve 322 and outflow valve 327, the reading of the flow meter 318 becomes
The opening of the outflow valve 327 was set to be 1/50 of the SiH ₄ /H ₂ gas flow rate to stabilize it. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was set to 10W. In this way, the glow discharge continues for three more times.
After forming the photoconductive layer for a certain period of time, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
After the substrate temperature reaches 100℃, the outflow valves 325, 327 and the inflow valve 3 are turned off.
After closing 20-2 and 322 and fully opening the main valve 310 to reduce the inside of the chamber 31 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 344, 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 1.01 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) onto 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 tone reproducibility was obtained. Next, the image forming member was corona charged for 0.2 seconds at 5.5 KV using a charging exposure experiment device, and then imagewise exposed at a light intensity of 0.8 lux・sec, and then a charging developer was immediately applied. When cascaded onto the surface of the component and then transferred and fixed onto transfer paper,
An extremely clear image was obtained. 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 The glow discharge holding time when forming an intermediate layer on a molybdenum substrate was as shown in Table 1 below.
Except for various changes, image forming members indicated by Sample No. ~ were prepared under the same conditions and procedures as in Example 1, and were placed in the same charging exposure experimental apparatus as in Example 1. When images were formed, the results 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 ×: Not possible Film deposition rate of intermediate layer: 1 Å/sec
Example 3 The process was exactly the same as Example 1, except that the flow rate ratio of SiH ₄ /H ₂ and N ₂ in the intermediate layer was varied as shown in Table 2 when forming the intermediate layer on the molybdenum substrate. Image forming members indicated by sample numbers ~ were prepared according to the conditions and procedures, and were installed in the same charging exposure experimental apparatus as in Example 1 to form images in the same manner as shown in Table 2. I got similar results. Furthermore, the sample
Table 3 shows the results of analyzing only the intermediate layers of Nos. 1 to 3 by Auger electron spectroscopy. As can be seen from the results shown in Tables 2 and 3, in order to achieve the object of the present invention, it is necessary to form the intermediate layer with x, which is related to the composition ratio of Si and N, in the range of 0.60 to 0.43.

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes ×:
Not possible

[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 340 and then the outflow valve 3 were opened by the same operation as in Example 1.
25, 326, and inflow valve 320-2, 32
1 was fully opened, and the insides of the flow meters 316 and 317 were also sufficiently degassed and vacuumed. auxiliary valve 340,
After closing the valves 325, 326, 320-2, 321, the valve 330 of the SiH ₄ gas (purity 99.999%, SiH ₄ /H ₂ ) gas cylinder 311 diluted to 10 vol% with H ₂ and the valve 331 of the gas cylinder 312 are opened. Open the outlet pressure gauges 335 and 336 and set the pressure to 1 m/cm ²
and gradually open the inflow valves 320-2 and 321 to enter the flow meters 316 and 317.
SiH ₄ /H ₂ gas and N ₂ gas were introduced. Subsequently, the outflow valves 325 and 326 were gradually opened, and then the auxiliary valve 340 was gradually opened. At this time
The inflow valves 320-2 and 321 were adjusted so that the ratio of SiH ₄ /H ₂ gas flow rate to N ₂ gas flow rate was 1:10. Next, while watching the reading on the Pirani gauge 341, adjust the opening of the auxiliary valve 340, and
Auxiliary valve 340 until the inside becomes 1×10 ^-2 Torr.
I opened it. After the internal pressure of the chamber 301 becomes stable, the main valve 310 is gradually closed and the Pirani gauge 34 is closed.
The aperture was narrowed down until the instruction in step 1 was 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 342, and
A high frequency power of 13.56 MHz was applied to the induction coil 343 to generate glow discharge in the chamber 301 in the coil section (upper part of the chamber), resulting in an input power of 3 W. In order to deposit a-(Si _x N _1-x ) _y :H _1-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 342 was turned off to stop glow discharge, the outflow valve 326 was closed, and then the high frequency power source 342 was turned on again to restart the glow discharge. The input power at that time was set to 10W. After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
OFF state, wait for the substrate temperature to reach 100°C, and then open the outflow valve 325 and inflow valve 320-
2, 321 was closed and the main valve 310 was fully opened to bring the inside of the chamber 301 to 10 ^-5 Torr or less, and then the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 344, and the substrate was taken out. The total thickness of the layer formed in this case 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,
Images formed by corona discharge had better image quality and were extremely clear than images formed by corona discharge. 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 342 was turned off,
With the glow discharge stopped, the outflow valve 32
Close 6 and then _PH3 diluted to 25volppm with _H2
At a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 338Z) from the gas cylinder (hereinafter abbreviated as PH ₃ /H ₂ ) 314 through the inflow valve 323, the inflow valve 32
3. By adjusting the outflow valve 328, the reading of the flow meter 319 becomes 1/5 of the flow rate of SiH ₄ /H ₂ gas.
The opening of the outflow valve 328 was set so as to be 0, and the outflow valve 328 was stabilized. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was set to 10W. In this way, the glow discharge is further increased by 4
After forming the photoconductive layer for a certain period of time, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
After the substrate temperature reaches 100℃, the outflow valves 325, 328 and the inflow valve 3 are turned off.
After closing 20-2 and 323 and fully opening the main valve 310 to reduce the inside of the chamber 301 to 10 ^-5 Torr or less, close the main valve 310 and bring the inside of the chamber 301 to atmospheric pressure using the leak valve 344 and take out the substrate. Ta. In this case, the total thickness of the formed layer is approximately 11μ
It was hot. 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. 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 342 was turned off and glow discharge was stopped, and the flow was discharged. The valve 326 is closed, and then B ₂ H ₆ diluted with H ₂ to 50 volppm is injected from the bomb 313 through the inflow valve 322.
Gas pressure in Kg/cm ² (outlet pressure gauge 337 reading)
By adjusting the inflow valve 322 and outflow valve 327, the reading of the flow meter 318 changes to SiH ₄ /
Outflow valve 32 so that the flow rate is 1/10 of the _H2 gas flow rate.
7 openings were defined and stabilized. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was set to 10W. In this way, the glow discharge continues for three more times.
After forming the photoconductive layer for a period of time, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
After the substrate temperature reaches 100°C, the outflow valves 325, 327 and the inflow valve 32 are closed.
After closing the main valve 310 and reducing the inside of the chamber 301 to 10 ^-5 torr or less, the main valve 310 is closed and the inside of the chamber 301 is opened by the leak valve 3.
44 to bring the pressure to atmospheric pressure and take out the substrate. 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 superior and extremely clear compared to images formed by corona discharge. 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 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 342 was turned on.
In the off state, the glow discharge is stopped.
The outflow valve 327 was closed and the outflow valve 326 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 minutes to form an upper layer on the photoconductive layer, the heating heater 308 is turned on.
off state, and the high frequency power supply 342 is also off state,
After the substrate temperature reaches 100°C, the outflow valves 325, 326 and the inflow valves 320-2, 3
21 and fully open the main valve 310.
After reducing the inside of the chamber 301 to 10 ^-5 torr or less, the main valve 310 is closed and the inside of the chamber 301 is closed using the leak valve 344.
The substrate was taken out at atmospheric pressure. The image forming member thus obtained was placed in a charging exposure experimental apparatus similar to that in Example 1, corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The light image is
Using a tungsten lamp light source, a light intensity of 1.01 ux·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. Example 8 When forming a photoconductive layer, an undiluted _{Si 2 H 6} cylinder 315 is used in place of the SiH ₄ gas cylinder 311 diluted to 10 vol% with H 2 to form a Si ₂ H ₆ gas.
After forming an intermediate layer and a photoconductive layer on a molybdenum substrate under the same conditions and procedures as in Example 1, except that the flow rate ratio of B ₂ H ₆ /H ₂ was set to 5:1,
When the image formation test was carried out by taking it out of the deposition chamber 301 and placing it in the charged exposure experimental apparatus in the same manner as in Example 1, it was found that the combination of the 5.5KV corona discharge chargeable developer showed extremely good quality and contrast. A high toner image was obtained on the transfer paper. Example 9 After forming an intermediate layer and a photoconductive layer on a molybdenum substrate under the same conditions and procedures as in Example 1, a fourth layer was formed.
Predetermined fixing member 403 in the deposition chamber 401 shown in the figure
The substrate 402 was fixed with the photoconductive layer facing down. The leak valve 411 was closed, the main valve 412 was opened, and the chamber was evacuated to 5×10 ⁻⁷ torr. After that, the auxiliary valve 409 outflow valves 413 to 419,
After fully opening the inflow valves 427 to 433 and exhausting the gas in the system, the auxiliary valve 409, the outflow valves 413 to 419, and the inflow valves 427 to 433 were closed. Heater 404 inside fixing member 403
After turning ON and setting the temperature to a predetermined temperature, select the outlet valve (441 to 4
48), and the outlet pressure was set to 1 Kg/cm ² (reading of outlet pressure gauges 434 to 440), and the flow rate of the gas flowing through the flow meters 420 to 426 was controlled to a predetermined value by the inflow valve and the outflow valve. After that, open the auxiliary valve 409 to let gas flow into the room,
Indoor pressure was controlled by main valve 412 (reading of Pirani gauge 410). After the flow rate and room pressure have stabilized, in the case of glow discharge decomposition, turn on shutter 4.
07 was closed, and in the case of sputtering, the shutter 407 was opened and the high frequency power source 408 was turned on to generate glow discharge in the room and form a layer. After forming the layer for a predetermined time, a high frequency power source 40
8 and the heater 404 were turned off, the auxiliary valve 409 was closed, and the main valve 412 was fully opened. After waiting for the substrate temperature to reach 100° C., the main valve 412 was closed, and the chamber was brought to atmospheric pressure using the leaf valve 411, and the substrate was taken out. In addition, when sputtering, target 40
In No. 5, polycrystalline Si, partially laminated graphite on polycrystalline Si, and Si ₃ N ₄ were used as necessary. Further, the types of gas in each cylinder in FIG. 4 are as follows. Cylinder 449: SiH ₄ gas (diluted to 10 vol% with H ₂ ), Cylinder 450: SiF ₄ gas (contains 10 vol% of H ₂ ), Cylinder 451: Si(CH ₃ ) ₄ (diluted to 10 vol% with H ₂ ), Cylinder 452: C ₂ H ₄ gas (diluted to 10 vol% with H ₂ ), Cylinder 453: NH ₃ gas (10 vol % with H ₂ )
diluted), cylinder 454: Ar gas, cylinder 45
5: N ₂ gas Each of the image forming members A to H produced in this way was charged, exposed and transferred with respect to bipolarity in the same manner as in Example 1. An extremely clear toner image was obtained.

[Table] Example 10 After changing the N ₂ gas cylinder to an NH ₃ gas cylinder diluted to 10 vol% with H ₂ and following the same procedure as in Example 1, NH ₃ /N ₂ gas and SiH ₄ /H ₂ gas were mixed. An intermediate layer was formed using a flow rate ratio of 2:1, and a photoconductive layer was further formed under similar conditions and procedures. The substrate was fixed to a predetermined fixing member in the apparatus shown in FIG. 5, and samples I to Q shown in Table 5 below were produced by the same procedure as in Example 9. In the same manner as in Example 1, charging with respect to bipolarity,
When exposure and transfer were performed, extremely clear toner images were obtained that were free of dependence on charging polarity.

[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 μm. Next, it was transferred to a regular evaporation apparatus and 80N 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 way was used as the light receiving surface of a visual image pickup tube, when white light 121ux was irradiated with a target applied voltage of 55V, the signal current was 650mA, the dark current was less than 0.8mA, and the afterimage characteristic was 8 after 3 fields. %, good characteristics were obtained.

[Brief explanation of the drawing]

1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the electrophotographic image forming member of the present invention, and FIGS. 3 and 4 are respectively schematic diagrams of the electrophotographic image forming member of the present invention. It is a typical explanatory view showing an example of the apparatus in the case of manufacturing a photoconductive member for use. 100,200...Photoconductive member for electrophotography, 1
01,102...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 made of an amorphous material containing silicon atoms as a matrix and containing hydrogen atoms, and having a hydrogen atom content of 1 to 40 atomic%;
It is provided between these and is made of an amorphous material containing silicon atoms as a matrix and nitrogen atoms and hydrogen atoms, and prevents carriers from flowing into the photoconductive layer from the support side and prevents carriers from flowing into the photoconductive layer by electromagnetic wave irradiation. an intermediate layer that allows carriers generated in the photoconductive layer and moving toward the support to pass from the photoconductive layer side to the support side, the intermediate layer having an amount of nitrogen atoms of 25 A photoconductive member for electrophotography, characterized in that the amount of hydrogen atoms is 0.25 to 35 atomic%. 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 photoconductive member for electrophotography according to claim 2, wherein the upper layer has a layer thickness of 30 to 1000 Å. 8. The photoconductive member for electrophotography according to claim 1, wherein the photoconductive layer contains either an n-type impurity or a p-type impurity. 9. The photoconductive member for electrophotography according to claim 8, wherein the n-type impurity is an element belonging to Group 3 of the periodic table. 10. The photoconductive member for electrophotography according to claim 8, wherein the p-type impurity is an element belonging to Group 1 of the periodic table.