JPH0150905B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed 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. [Prior Art] Photoconductive materials constituting image forming members for electrophotography in the image forming field are highly sensitive, have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], and are suitable for irradiation. It is required to have characteristics such as having electromagnetic wave spectral characteristics, good photoresponsiveness, a desired dark resistance value, and being non-polluting to the human body during use. 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 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. . [Problems to be Solved by the Invention] However, conventional photoconductive members for electrophotography having a photoconductive layer composed of a-Si have poor electrical properties such as dark resistance, photosensitivity, and photoresponsiveness. There are points that can be further improved in terms of usage environment characteristics such as optical and photoconductive properties and moisture resistance, and practical electrophotographic imaging members have improved productivity and mass production. The reality is that it cannot be used effectively, taking into account the following. For example, when applied to electrophotographic image forming members, it is often observed that residual potential remains during use, and such photoconductive members for electrophotography may repeatedly be 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, for example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional Se, CdS, ZnO, PVCz, TNF, etc. It has many advantages compared to OPC (organic electrophotographic photoconductive material), but it has a single-layer photoconductive layer made of a-Si that has properties suitable for use in conventional solar cells. Even if the photoconductive layer of an electrophotographic image forming member is subjected to charging treatment for electrostatic image formation, dark decay (dark decay) remains.
(decay) is extremely fast, making it difficult to apply normal electrophotographic methods, and the above tendency is significant in humid atmospheres, and in some cases, it may not be possible to retain the charged charge at all until the development time. It has been found that there are possible points that can be solved. 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 for electrophotography. be. 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 as a photoconductive member for electrophotography used in image forming members for electrophotography and its applicability, we found that silicon atoms are used as a matrix and hydrogen atoms are used as a matrix. A layer in which a specific intermediate layer is interposed between a photoconductive layer made of an amorphous material containing hydrogenated amorphous silicon (hereinafter referred to as a-Si; H) and a support that supports the photoconductive layer. The photoconductive member for electrophotography designed and manufactured according to the structure is not only usable for practical use, but also superior in most respects when compared with conventional photoconductive members for electrophotography. This is based on the discovery that it has particularly excellent properties as a photoconductive member for electrophotography. [Objective of the present invention] The present invention has stable electrical, optical, and photoconductive properties at all times, is applicable to all environments with almost no restrictions on usage environments, is extremely resistant to light fatigue, and is suitable for repeated use. The main object of the present invention is to provide a photoconductive member for electrophotography that does not cause any deterioration phenomenon and has no or almost no residual potential 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 charge retention 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 obtain high-quality images with high density, clear halftones, and high resolution. be. [Structure of the present invention] The photoconductive member for electrophotography of the present invention is provided between a support, a photoconductive layer made of an amorphous material having silicon atoms as a matrix and containing hydrogen atoms, and A function of preventing carriers from flowing into the photoconductive layer from the support side and allowing carriers generated in the photoconductive layer and moving toward the support side by electromagnetic wave irradiation to pass from the photoconductive layer side to the support side. In a photoconductive member for electrophotography, the intermediate layer comprises silicon atoms and 40 to 40
Carbon atoms in an amount of 90 atomic% as a base, and halogen atoms in an amount of 1 to 20 atomic%, or halogen atoms and hydrogen atoms in an amount of 1 to 20 atomic% as the sum of both.
It is characterized by being composed of a non-photoconductive amorphous material containing 20 atomic%. DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photoconductive member of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown for explaining a basic configuration example of a photoconductive member for electrophotography according to the present invention. The electrophotographic photoconductive member 100 shown in FIG.
The present invention has a layer structure consisting of an intermediate layer 102 and a photoconductive layer 103 provided in direct contact with the intermediate layer 102 on a support 101 for use as a photoconductive member for electrophotography. This is the most basic example of the 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, 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 the surface is glass, NiCr, Al, etc.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd,
If it is conductive treated by providing a thin film of In _{2 O 3 , SnO 2 , ITO (In 2 O 3 + SnO 2} ), or a synthetic resin film such as polyester film,
NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo,
Vacuum deposition of metals such as Ir, Nb, Ta, V, Ti, Pt, etc.
The surface is made conductive by processing by electron beam evaporation, sputtering, etc., or by laminating with the metal. The shape of the support body is cylindrical,
It can be obtained in any shape such as a belt shape or a plate shape, and the shape is determined depending on the desire.
If the photoconductive member 100 for electrophotography shown in the figure is used as an image forming member for electrophotography, it is preferable that the photoconductive member 100 be in the shape of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is appropriately determined so as to form a desired photoconductive member for electrophotography, but if flexibility is required as a photoconductive member for electrophotography, the thickness of the support may be determined as desired. It is made as thin as possible within the range where its functions can be fully demonstrated. However, in such cases, in manufacturing and handling of the support,
In terms of mechanical strength, etc., the thickness is usually 10 μm or more. The intermediate layer 102 is made of a non-photoconductive amorphous material [a-(Si _x C _1-x ) containing silicon atoms and carbon atoms and halogen atoms (denoted as X).
_y : Abbreviated as X1 _-y . However, 0<x<1, 0<y<
1], which effectively prevents carriers from flowing into the photoconductive layer 103 from the support 101 side, and which is generated in the photoconductive layer 103 by electromagnetic wave irradiation and directed toward the support 101 side. It has a function of easily allowing the photo carrier moving along the substrate to pass from the side of the photoconductive layer 103 to the side of the support 101. a-(Si _x C _1-x ) _y : Intermediate layer 1 composed of X _1-y
02 is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member for electrophotography to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member for electrophotography having desired characteristics. Carbon atoms and halogen atoms can be easily introduced into the intermediate layer to be manufactured along with silicon atoms. Due to these advantages, the glow discharge method or the 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 apparatus system. In order to form the intermediate layer 102 by the glow discharge method, the raw material gas for forming a-(Si _x C _{1 -x} ) _y : 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 to form a-(Si) on the support 101. _x C _1-x ) _y : Just deposit X _1-y . In the present invention, the raw material gas for forming a-(Si _x C _1-x ) _y :X _1-y is a gaseous substance containing at least one of Si, C, and X as a constituent atom. Alternatively, most gasified substances can be used. When using a raw material gas containing Si as one of Si, C, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing Alternatively, a raw material gas containing Si and a raw material gas containing C and X may be mixed at a desired mixing ratio. or with a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, preferred halogen atoms X are F, Cl, Br, and I, with F and Cl being particularly preferred. In the present invention, the intermediate layer 102 is a-(Si _x
C _1-x ) _y :Although it is composed of X _1-y , the intermediate layer 102 can further contain hydrogen atoms. The inclusion of hydrogen atoms in the intermediate layer 102 is advantageous in terms of production costs since it is possible to share some of the raw material gas types when forming a continuous layer with the photoconductive layer 103. In the present invention, raw material gases that can be effectively used to form the intermediate layer 102 include gaseous materials or substances that can be easily gasified at room temperature and normal pressure. . Such substances for forming the intermediate layer include, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, simple halogens, and halogenated hydrocarbons. Examples include hydrogen, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
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 ,
Acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF ₃ , ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr,
Examples of silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
SiCl ₃ Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ ,
Examples of halogen-substituted silicon hydride include SiH ₂ F ₂ ,
SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ ,
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₆ ,
Examples include silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ . In addition to these, CCl 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, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ may also be mentioned as useful. These intermediate layer forming substances are used during the formation of the intermediate layer so that the intermediate layer to be formed contains silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. be selected and used as desired. For example, SiHCl _{3 and} SiCl contain Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form an intermediate layer with desired characteristics. ₄ , SiH ₂ Cl ₂ or SiH ₃ Cl, etc. in a gaseous state at a predetermined mixing ratio is introduced into the intermediate layer forming apparatus system to generate a glow discharge, thereby producing a-Si _x C _1-x : An intermediate layer consisting of Cl:H can be formed. To form the intermediate layer 102 by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are combined with halogen. Depending on the requirements, sputtering may be performed in various gas atmospheres containing hydrogen as a constituent. For example, if a Si wafer is used as a target, the raw material gas for introducing C and The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least halogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. C and X, H as necessary
As the material serving as the raw material gas for introduction, the material for forming the intermediate layer shown in the glow discharge example described above can also be used as an effective material in the sputtering method. In the present invention, a so-called rare gas, such as He,
Preferable examples include Ne and Ar. The intermediate layer 102 in the present invention is carefully formed to provide the desired properties. In other words, substances whose constituent atoms are Si, C, X, and optionally H have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrical properties ranging from conductivity to amorphous. In the present invention, non-photoconductive a-(Si _x The creation conditions are strictly selected so that C _1-x ) _y :X _1-y is formed. a-(Si _x
C _1-x ) _y :X _1-y indicates that the function of the intermediate layer 102 is that of the support 1
This serves to prevent carriers from flowing into the photoconductive layer 103 from the 01 side, and to easily allow photocarriers generated in the photoconductive layer 103 to move and pass to the support 101 side. Therefore,
It is formed to exhibit electrically insulating behavior. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, a has a mobility value for the passing carrier to such an extent that the photocarrier passes through the intermediate layer 102 smoothly. -(Si _x C _1-x ) _y :X _1-y is an important factor in the production conditions, including the temperature of the support during production. That is, a-(Si _x C _1-x ) is formed on the surface of the support 101.
When forming the intermediate layer 102 consisting of y:X1 _-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 C _1-x ) having the desired properties
The temperature of the support during layer formation is strictly controlled so that _y : X _1-y can be formed as desired. In order to effectively achieve the desired purpose of the present invention, the temperature of the support when forming the intermediate layer 102 is appropriately selected in an optimum range in accordance with the method of forming the intermediate layer 102. 102 formation is carried out, typically between 100°C and 300°C, preferably at 150°C.
It is desirable that the temperature is between ℃ and 250℃. For forming the intermediate layer 102, the intermediate layer 102 is formed in the same system.
Fine control of the composition ratio of atoms constituting each layer and layer thickness allows continuous formation from the photoconductive layer 103 to the third layer formed on the photoconductive layer 103 if necessary. It is advantageous to adopt a glow discharge method or a sputtering method because the control is relatively easy compared to other methods. However, when forming the intermediate layer 102 using these layer forming methods, for,
Similar to the support temperature described above, the discharge power during layer formation is one of the important factors that influences the characteristics of a-(Si _x C _1-x ) _y :X _1-y created. The discharge power conditions for effectively producing a-(Si _x C _{1-x ) y} :
10-200W, preferably 20-100W. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. The amount of carbon atoms and halogen atoms contained in the intermediate layer 102 in the photoconductive member for electrophotography of the present invention is such that, similar to the manufacturing conditions of the intermediate layer 102, desired characteristics to achieve the object of the present invention can be obtained. This is an important factor in the formation of the intermediate layer. The amount of carbon atoms contained in the intermediate layer 102 in the present invention is usually 40 to 90 atomic%, preferably
It is desirable that the content be 50 to 90 atomic%, most preferably 60 to 80 atomic%. The content of halogen atoms is usually 1 to 20 atomic%, preferably 2 to 15 atomic%,
Electrophotographic photoconductive members prepared when the halogen content is within these ranges can be sufficiently applied to practical applications. The content of hydrogen atoms that are included as necessary is usually 19 atomic.
% or less, preferably 13 atomic % or less. That is, the previous a-(Si _x C _1-x )
_y : If expressed _as
0.99~0.80, preferably 0.99~0.82, optimally 0.98~
It is 0.85. When both halogen atoms _and hydrogen atoms _are included, the numerical range of x and _y in this case _is also a ―
(Si _x C _1-x ) _y : Almost the same as in the case of X _1-y . 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,
If the thickness is too thick, the photoconductive layer 1 will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the side of the support 101.
Photocarrier support 1 produced in 03
The probability of passing to the 01 side becomes extremely small,
Therefore, in either case, 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 103 is laminated on the intermediate layer 102.
is composed of a-Si having the semiconductor properties shown below. 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: H... type lightly doped with a so-called p-type impurity that has a low acceptor concentration (Na). n-type a-Si:H...Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd). n ^- type a-Si:H...type with low donor concentration (Nd), 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 5×10 ⁹ Ωcm or more, most preferably 10 ¹⁰ Ωcm.
It is desirable that the photoconductive layer 103 be formed as described above. In particular, this numerical condition of the dark resistance value is an important factor when the produced photoconductive member for electrophotography is used as an image forming member for electrophotography. The layer thickness of the photoconductive layer of the photoconductive member for electrophotography in the present invention is suitably determined as desired in accordance with the purpose. 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 100 μm, preferably 2 to 50 μm. In the present invention, in order to make the photoconductive layer a layer composed of a-Si:H, when forming these layers, H is contained in the layer by the following method. . Here, "H is contained in the layer"
This means that there is 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 incorporated into the layer as _H2 , or a combination of these. means the state of being As a method for incorporating H into the photoconductive layer, for example, when forming the layer, SiH ₄ , Si ₂ H ₆ ,
It is introduced in the form of silicon compounds such as silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ , and these compounds are decomposed by the glow discharge decomposition method to remove the contained substances as the layer grows. Ru. When forming a photoconductive layer by this glow discharge method, the starting material for forming a-Si is 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 ₆ , Si ₃ H is used. Silicon hydride gas such as ₈ , Si 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 findings of the present inventors, the H content of the photoconductive layer composed of a-Si:H is sufficient to determine whether the formed photoconductive member for electrophotography can be sufficiently applied in practice. It turned out that this is one of the major factors that influences the situation and is extremely important. In order for the photoconductive member for electrophotography to be formed in the present invention to be sufficiently applicable to practical applications, the amount of H contained in the photoconductive layer is usually 1 to 1.
It is desirable that the content be 40 atomic %, preferably 5 to 30 atomic %. 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 controlling the amount of doping. 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,
Preferable 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 use 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 n-type by interstitial doping with Li or the like by thermal diffusion or ioplantation, for example. The amount of impurity doped into the photoconductive layer is
It is determined as appropriate 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 -3 atomic%.
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 electrophotographic photoconductive member of the present invention. Electrophotographic photoconductive member 200 shown in FIG.
has the same layer structure as the electrophotographic 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. . That is, the electrophotographic photoconductive member 200 includes an intermediate layer 202 formed on a support 201 using the same material as the intermediate layer 102 and having the same function, and a
- A photoconductive layer 203 composed of Si:H and an upper layer 205 provided on the photoconductive layer 203 and having a free surface 204. When the upper layer 205 is used, for example, when the electrophotographic photoconductive member 200 is subjected to a charging treatment on the free surface 204 to form a charge image, the charge that can be held on the free surface 204 is used to conduct photoconductivity. layer 203
When the photoconductive layer 203 is prevented from flowing into the photoconductive layer 203 and is irradiated with electromagnetic waves, the photocarriers generated in the photoconductive layer 203 and the charged charges on the portions irradiated with the electromagnetic waves are recombined. In addition, it has a function of easily allowing photo carriers or charged charges to pass through. The upper layer 205 is made of a-(Si _x
C _1-x ) _y : Composed of X _{1-y and} a-Si _a N _1-a , a-
(Si _a N _1-a ) _b : H _1-b , a-(Si _a N _1-a ) _b : (H+X) _1
-b , a-Si _c O _1-c , a- (Si _c O _1-c ) _d : H _1-d , a-
(Si _c O _{1-c ) d} : (H + It must be composed of an amorphous material containing hydrogen atoms (H) and/or halogen atoms (X), inorganic insulating materials such as SiNO and Al ₃ O ₃ , and organic insulating materials such as polyester, polyparaxylylene, and polyurethane. You can also do it. However, the material constituting the upper layer 205 is a-( Si _x C _1-x ) _y : a _- Si x consisting of X _1-y or containing no halogen atom
It is preferable to configure it with C _1-x . 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. 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 the photoconductive member 200 for electrophotography is used in such a manner as to irradiate electromagnetic waves that are detected by It is done carefully so that it can be done. 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:
In general, the thickness is preferably 30 to 1000 Å, preferably 50 to 600 Å. If a certain type of electrophotographic process is employed when the electrophotographic photoconductive member of the present invention is used as an electrophotographic image forming member, FIG.
It is necessary to provide a further surface coating layer on the free surface of the photoconductive material in the layer configuration shown in the figure. In this case, the surface coating layer is, for example, disclosed in Japanese Patent Publication No. 42-23910,
If an electrophotographic process such as the NP method described in Publication No. 43-24748 is to be applied, it must be electrically insulating and have sufficient electrostatic charge retention ability when subjected to charging treatment. Although a certain thickness is required, for example, if an electrophotographic process such as the Carlson process is applied, it is desirable that the potential of the bright area after electrostatic image formation is very small, so the surface coating layer is The thickness is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer must not have any adverse chemical or physical effects on the photoconductive layer or the upper layer, and must not have electrical contact with the photoconductive layer or the upper layer. It is formed in consideration of adhesion, moisture resistance, abrasion resistance, cleanability, etc. Typical materials effectively used as forming members for the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polypinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Organic insulators such as polyvinyl fluoride, polypynylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polybutene, polyvinyl butyral, polyurethane, polyparaxylylene, silicon nitride and inorganic insulators such as silicon oxide. 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 may be formed,
It may be coated on the photoconductive layer or the upper layer 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 40 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, the thickness is usually 10 μm or less,
Conversely, when a function as an electrically insulating layer is required, the thickness is usually 10 μm or more. However,
The layer thickness that distinguishes between the protective layer and the electrically insulating layer varies depending on the materials used, the electrophotographic process applied, and the structure of the image forming member designed, and the above value of 10 μm is an absolute value. It's not something. 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
It is heated with an accuracy of ±0.5° C. by a heater 308 inside the fixed member 303. Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system were closed, the main bubble 310 was fully opened to exhaust the inside of the deposition chamber 301 to a degree of vacuum of approximately 5×10 ⁻⁶ Torr. After that, the input voltage of the heater 308 is increased, and the input voltage is changed while detecting the molybdenum substrate temperature.
It was stabilized until it reached a constant value of 200℃. After that, the auxiliary valve 340, then the outflow valves 325, 326, 327, 329, and the inflow valves 320, 321, 322, 324 were fully opened, and the inside of the flow meters 316, 317, 318, 320 was sufficiently degassed and vacuumed. . Auxiliary valve 34
0, valve 325, 326, 327, 329, 3
After closing 20, 321, 322, 324, H _2
SiF4 gas diluted to 70vol% (purity 99.999%)
Valve 330 of cylinder 311, valve 331 of _{C 2 H 4} gas cylinder 312 diluted to 10 vol% with H 2
, and set the pressure on the outlet pressure gauges 335 and 336 to 1.
Adjust to Kg/cm ² and gradually open the inflow valves 320 and 321 to enter the flow meters 316 and 317.
SiF ₆ gas and C ₂ H ₄ gas were introduced. Subsequently,
The outflow valves 325, 326 were gradually opened, and then the auxiliary valve 340 was gradually opened. At this time, SiF ₄
The inflow valves 320 and 321 were adjusted so that the ratio of gas flow rate to C ₂ H ₄ gas flow rate was 1:60. Next, while watching the reading on the Pirani gauge 341, adjust the opening of the auxiliary valve 340 so that the inside of the chamber 301 is 1×.
Auxiliary valve 340 was opened until 10 ^-2 Torr.
After the internal pressure of the deposition 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. It was confirmed that the gas inflow was stable and the internal pressure was stable. Next, the switch of the high frequency power supply 342 was turned on, and 13.56 MHz high frequency power was applied to the induction coil 343 to generate a glow discharge in the deposition chamber 301 in the coil section (upper part of the chamber), resulting in an input power of 60 W. . In order to deposit the intermediate layer 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 342
When the is turned off and the glow discharge is stopped,
Close the outflow valves 325, 326 and then with _H2
Open the valve 332 of the _B2H6 gas cylinder 313 diluted to _50volppm and the valve 334 of the _SiH4 cylinder 315 diluted to 10vol% with _H2 , and adjust the pressure of the outlet pressure gauges 337, 339 to 1Kg/ ^cm2. Then, the inflow valves 322 and 324 were gradually opened to allow B ₂ H ₆ gas and SiH ₄ gas to flow into the flow meters 318 and 320. Subsequently, the outflow valves 327, 329
I gradually opened it. At this time, B ₂ H ₆ gas flow rate and SiH ₄
Inlet valve 32 so that the gas flow ratio is 1:50.
2,324 were adjusted. Next, as in the case of forming the intermediate layer, the openings of the auxiliary valve 340 and the main valve 310 were adjusted so that the reading on the Pirani gauge 341 was 0.5 Torr, and the temperature was stabilized. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at this time was reduced to 10W compared to 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 342 is also turned off, and the substrate temperature reaches 100°C.
Wait until the outflow valves 327, 329
and inflow valves 320, 321, 322, 324
was closed and the main valve 310 was fully opened to reduce the pressure inside the deposition chamber 301 to 10 ^-3 Torr or less, then the main valve 310 was closed and the inside of the deposition chamber 301 was brought to atmospheric pressure by the leak valve 343, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9 μm. The electrophotographic image forming member obtained in this way was installed in a charging exposure experimental device and exposed to 6.0KV.
Corona charging was performed for 0.2 seconds, and a light image was immediately irradiated. The optical image is created using a tungsten lamp light source.
A light intensity of 0.8 lux·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 gradation reproducibility was obtained. Next, the image forming member is corona charged at 5.5 KV for 0.2 seconds using a charging exposure experiment device, and immediately subjected to image exposure at a light intensity of 0.8 lux・sec. Immediately thereafter, a charged developer is applied to the surface of the member. When the image was 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 the charging electrode and had the characteristics of a bipolar image forming member. Example 2 Sample No. An electrophotographic image forming member shown in .~ was prepared, and when it was installed in the charging exposure experimental apparatus exactly as in Example 1 and the same image formation was performed, 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 purpose of the present invention, the thickness of the intermediate layer is 30 Å to 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 When forming an intermediate layer on a molybdenum substrate,
Electrophotographs of sample No. ~ were taken under the same conditions and procedures as in Example 1, except that the SiF ₄ gas flow rate and C ₂ H ₄ gas flow rate ratio were varied as shown in Table 2 below. An image forming member was prepared, and when it was installed in the same charging exposure experimental apparatus as in Example 1 and the same image formation was carried out, the results shown in Table 2 below were obtained. Regarding sample No.~, electron
When analyzed by microprobe method, the results shown in Table 3 were obtained. 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 a composition ratio x of Si to C within the range of 0.1 to 0.35.

【table】

[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 was maintained at 200°C, the SiF ₄ , C ₂ H ₄ , and SiH ₄ gas inflow system was brought to a vacuum of 5×10 ^-6 Torr by the same operation as in Example 1, and then the auxiliary valve 340 and each outflow valve 325, 326, 32
9. After closing each inlet valve 320, 321, 324, valve 330 of SiF ₄ gas cylinder 311 diluted with H ₂ to 70 vol%, valve 331 of _{C 2 H 4} gas cylinder 312 diluted to 10 vol% with H 2 Open the
Adjust the pressure of the outlet pressure gauges 335, 336 to 1 Kg/cm ² and gradually open the inflow valves 320, 321 to introduce SiF ₄ gas into the flow meters 316, 317.
C ₂ H ₄ gas was introduced. Subsequently, the outflow valves 325 and 326 were gradually opened, and then the auxiliary valve 340 was gradually opened. At this time, the SiF ₄ gas flow rate and
The inflow valves 320 and 321 were adjusted so that the C ₂ H ₄ gas flow rate ratio was 1:60. Next, while paying close attention to the reading on the Pirani gauge 341, open the auxiliary valve 340.
The auxiliary valve 340 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 the gas inflow stabilizes, the indoor pressure becomes constant, and the substrate temperature stabilizes at 200℃,
As in Example 1, the high frequency power supply 342 was turned on, and glow discharge was started with an input power of 60W.
After forming the intermediate layer on the substrate by maintaining the same conditions for 1 minute, the high frequency power source 342 is turned off, and the outflow valves 325, 32 are turned off with the glow discharge stopped.
6,322, then open the valve 334 of the SiH ₄ cylinder 315 diluted to 10 vol% with H ₂ , adjust the pressure of the outlet pressure gauge 339 to 1 Kg/cm ² , and gradually open the inflow valve 324. flow meter 32
SiH ₄ gas was flowed into the 0. Subsequently, the outflow valve 329 was gradually opened. Next, the instructions on the Pirani gauge 341 are as same as when forming the intermediate layer.
The openings of the auxiliary valve 340 and main valve 310 were adjusted to stabilize the pressure to 0.5 Torr. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was reduced to 10W compared to before. After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heater 308 is turned off, the high frequency power supply 342 is also turned off, and the substrate temperature reaches 100°C.
After waiting until
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 344, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15 μm. When an image was formed on a transfer paper using this electrophotographic image forming member under the same conditions and procedures as in Example 1, the image formation with corona charging was better than the image formation with corona charging. The image quality was excellent and extremely clear. From this result, it was confirmed that the electrophotographic image forming member obtained in this example had a dependence on charging function. Example 5 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1,
With the high frequency power supply 342 turned off and the glow discharge stopped, the outflow valves 325 and 326 are closed, and then the valve 333 of the PH 3 gas cylinder 314 diluted with H ₂ to 25 volppm, and the valve 333 of the PH ₃ gas cylinder 314 diluted with H ₂ to 10 vol%. Open the valve 334 of the SiH ₄ cylinder 315,
Adjust the pressure of the outlet pressure gauges 338, 339 to 1 Kg/cm ² and gradually open the inflow valves 323, 324 to inject PH ₃ gas into the flow meters 319, 320.
SiH ₄ gas was introduced. Subsequently, the outflow valves 328, 329 were gradually opened. At this time, the inflow valves 323 and 324 were adjusted so that the ratio of PH ₃ gas flow rate to SiH ₄ gas flow rate was 1:50. Next, in the same way as when forming the intermediate layer, Pirani gauge 3
Auxiliary valve 34 so that the instruction of 41 becomes 0.5 Torr.
0. The opening of the main valve 310 was adjusted 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 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 setting the off state and waiting for the substrate temperature to reach 100°C, open the outflow valves 328, 329 and the inflow valve 3.
20, 321, 323, and 324, and fully open the main valve 310, the inside of the chamber 301 is
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 344, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 11 μm. An image was formed on a transfer paper using the thus obtained electrophotographic image forming member under the same conditions and procedures as in Example 1.
The image quality was superior to images formed by corona discharge, and they were extremely clear. From this result, it was found that the electrophotographic image forming member obtained in this example had a dependence on charging polarity. Example 6 After forming an intermediate layer on a molybdenum substrate, the B ₂ H ₆ gas flow rate was changed to SiH ₄ when subsequently forming a photoconductive layer.
Example 1 except that the gas flow rate was set to 1/10 of the gas flow rate.
An intermediate layer and a photoconductive layer were formed on a molybdenum substrate under the same conditions and procedures as described above. An image was formed on a transfer paper using the thus obtained electrophotographic image forming member under the same conditions and procedures as in Example 1. The image quality was better than that of the original, and it was extremely clear. From this result, it was found that the photoreceptor obtained in this example had charge polarity dependence. However, the dependence on charging polarity was opposite to that of the electrophotographic image forming members obtained in Examples 3 and 4. 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.
The outflow valves 327 and 329 were closed while the glow discharge was stopped as the off state, and the outflow valves 325 and 326 were opened again to obtain the same conditions as when forming the intermediate layer. Subsequently, the high frequency power supply was turned on again to restart the glow discharge. The input power at that time is the same as when forming the intermediate layer.
It was set to 60W. After sustaining the glow discharge for 2 minutes to form an upper layer on the photoconductive layer, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
After setting the off state and waiting for the substrate temperature to reach 100°C, open the outflow valves 325, 326 and the inflow valve 3.
20, 321, 322, and 324, and fully open the main valve 310, the inside of the chamber 301 is
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 343, and the substrate was taken out. The electrophotographic image forming member thus obtained was placed in the same charging exposure experimental apparatus as 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 1.0 lux·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 gradation reproducibility was obtained. Example 8 Diluted to 10 vol% with H ₂ in the apparatus shown in FIG. 3 prior to formation of an electrophotographic imaging member.
C ₂ H ₄ cylinder 312 was diluted to 10 vol% with H ₂
Changed to SiCl (CH ₃ ) gas (purity 99.999%) cylinder. Next, one side of the cleaned Corning 7059 glass (1 mm thick, 4 x 4 cm, polished on both sides) was coated with 1000% ITO by electron beam evaporation.
The Å vapor-deposited material was placed in the same apparatus as in Example 1 (the third
It was placed on the fixing member 303 (see figure) with the ITO deposition surface facing upward. Subsequently, the same operating board as in Example 1 was installed, and the inside of the glow discharge deposition chamber 301 was made into a vacuum of 5×10 ^-6 Torr. After the substrate temperature was maintained at 150°C, the auxiliary valve 340 , then outflow valves 326, 327, 329, and inflow valve 3
21, 322, and 324 were fully opened, and the insides of flow meters 317, 318, and 320 were also sufficiently degassed to a vacuum state. Auxiliary valve 340, valves 326, 32
After closing 7,329,317,318,320, open SiCl (CH ₃ ) ₃ gas (99.999% purity) cylinder 312 diluted to 10 vol% with H ₂ and valve 331, and set the pressure on the outlet pressure gauge to 1 Kg/ cm ² and gradually open the inflow valve 321 to connect the flow meter 31.
SiCl(CH ₃ ) ₃ gas was flowed into 7. Subsequently,
The outflow valve 326 was gradually opened. While paying close attention to the reading on the Pirani gauge 341, check the auxiliary valve 340.
The auxiliary valve 340 was opened until the pressure inside the chamber 301 became 1×10 ⁻² Torr. After the internal pressure in the chamber 301 stabilizes, the main valve 310 is gradually closed and the Pirani gauge 341 reads 0.5 Torr.
I narrowed my aperture until it was. Confirm that the gas inflow is stable and the internal pressure is stable, then turn on the high frequency power supply 34.
Turn on the switch to the induction coil 343.
13.56MHz high frequency power is applied to generate a glow discharge in the chamber 301 of the coil part (upper part of the chamber).
The input power was 20W. After maintaining the same conditions for 1 minute to form an intermediate layer, the high frequency power source 342 is turned off to stop glow discharge, and after a while, the outflow valve 329 and inflow valve 326 are closed, and the substrate temperature is raised to 200°C. Raised. Then 10vol with _H2
Open the valve 334 of the SiH ₄ gas cylinder 315 diluted to 50 volppm with H ₂ and the valve 332 of the B ₂ H ₄ gas cylinder 313 diluted to 50 volppm with H 2 , adjust the pressure of the outlet pressure gauges 339 and 337 to 1 Kg/cm ² , The inflow valves 324 and 322 were gradually opened to allow SiH ₄ gas and B ₂ H ₆ gas to flow into the flowmeters 320 and 318, respectively. Subsequently, the outflow valve 329,3
27 was gradually opened. At this time, the openings of the inflow valves 324 and 322 were set so that the ratio of the SiH ₄ gas flow rate to the B ₂ H ₆ gas flow rate was 50:1 and stabilized. Incidentally, the valve adjustment operation was performed in the same manner as when forming the intermediate layer so that the internal pressure in the chamber 301 was 0.5 Torr. After that, turn on the high frequency power supply 342 again.
state, and the glow discharge was restarted. The input power at that time was reduced to 10W compared to 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 342 is also turned off, and the substrate temperature is increased.
After waiting for the temperature to reach 100℃, the outflow valve 327,
329 and the inflow valves 321, 322, 324 are closed, the main valve 310 is fully opened, and the chamber 30 is closed.
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 344, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9 μm. The electrophotographic image forming member thus obtained was placed in a charging exposure experiment apparatus, corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was generated 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 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 gradation reproducibility was obtained. Further, even when the corona charge polarity was changed to 1 and the developer polarity was changed to 1, a clear and good image was obtained in the same manner as in Example 1. Example 9 SiH ₄ Bond 315 diluted to 10 vol% with H ₂ was added to an undiluted Si ₂ H ₆ cylinder with H ₂
B ₂ H ₆ cylinder 313 diluted to 50 volppm,
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 using a B ₂ H ₆ cylinder diluted with H ₂ to 500 volppm, the layer was placed outside the deposition chamber 301. When the toner was taken out and placed in a charged exposure experimental device in the same manner as in Example 1 for an image formation test, it was found that in the case of a combination of 5.5 KV corona charging and a charged developer, the toner was of extremely good quality and had high contrast. An image was obtained on the transfer paper. Example 10 Using the apparatus shown in FIG. 4, an intermediate layer was formed on a molybdenum substrate by the following operations. A 0.5 mm thick, 10 cm square molybdenum plate (substrate) 402 whose surface was cleaned was firmly fixed to a fixing member 406 at a predetermined position in the deposition chamber 401 . Board 4
02 is a heater 407 inside the fixed member 406
heated with an accuracy of ±0.5℃. Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system were closed, the main valve 427 was fully opened to evacuate the chamber 401 to a degree of vacuum of approximately 5×10 ⁻⁶ Torr. After that, the input voltage of the heater 407 is increased, and the input voltage is changed while detecting the molybdenum substrate temperature.
It was stabilized until it reached a constant value of 200℃. Thereafter, the auxiliary valve 425 and then the outflow valves 421, 424, and 417, 420 were fully opened, and the insides of the flow meters 432, 345 were also sufficiently degassed and vacuumed. Auxiliary valve 425, valve 417,
420, 421, and 424, open the valve 416 of the SiF ₄ gas (purity 99.999%) cylinder 412 and the valve 413 of the Ar gas cylinder 409,
The pressures of the outlet pressure gauges 428 and 431 were adjusted to 1 Kg/cm ² , and the inflow valves 417 and 420 were gradually opened to allow SiF ₄ gas and Ar gas to flow into the flow meters 432 and 435, respectively. Subsequently, the outflow valves 421 and 424 were gradually opened, and then the auxiliary valve 425 was gradually opened. At this time, the SiF ₄ gas flow rate and
The inflow valves 417 and 420 were adjusted so that the Ar gas flow rate ratio was 1:20. Next, the opening of the auxiliary valve 425 was adjusted while observing the reading on the Pirani gauge 436, and the auxiliary valve 425 was opened until the inside of the chamber 401 reached 1×10 ⁻² Torr. After the internal pressure of the chamber 401 became stable, the main valve 427 was gradually closed, and the opening was throttled until the reading on the Pirani gauge 436 reached 0.5 Torr. After opening the shutter 408 and confirming that the flow meters 432 and 435 are stable, the high frequency power supply 437 is turned on and the area ratio is 1:9.
AC power of 13.56 MHz and 100 W was input between targets 403 and 404 made of monocrystalline or polycrystalline pure silicon and high-purity graphite, and a fixing member 406. Under these conditions, the layers were formed while performing matching so that stable discharge could continue.
Continue discharging in this way for 2 minutes to form a 100 Å thick a-
Si _x C _1-x :F was formed. Then high frequency power supply 43
7 was turned off to temporarily stop the discharge. Subsequently, the outflow valves 421 and 424 are closed and the main valve 427 is fully opened to remove the gas from the chamber 401.
Vacuum was applied to ×10 ^-7 Torr. Next, SiH ₄ gas (purity 99.999%) diluted to 10 vol% with H ₂ cylinder 410
valve 414, diluted to 50 volppm with _H2
Open the valve 415 of the B ₂ H ₆ gas cylinder 411,
Adjust the pressure of the outlet pressure gauges 428, 430 to 1 Kg/cm ² and gradually open the inflow valves 417, 419 to inject SiH ₄ gas into the flow meters 432, 434.
B ₂ H ₆ gas was introduced. Subsequently, the outflow valve 4
21,423 gradually open, then auxiliary valve 4
25 was gradually opened. At this time, the SiH ₄ gas flow rate and
The inlet valves 417 and 419 were adjusted so that the B ₂ H ₆ gas flow rate ratio was 50:1. Next, while paying close attention to the reading on the Pirani gauge 436, the auxiliary valve 425 is
The auxiliary valve 425 was opened until the pressure inside the chamber 401 became 1×10 ⁻² Torr. After the internal pressure of the chamber 401 became stable, the main valve 427 was gradually closed and the opening was throttled until the reading on the Pirani gauge 436 reached 0.5 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 408 is closed, and then the high frequency power source 437 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 407 and 408, and the chamber 401 is turned on. 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 407 is turned off, and the high frequency power source 437 is turned off.
After waiting for the substrate temperature to reach 100°C, the outflow valves 422, 423 and inflow valves 418, 419 were closed, and the main valve 427 was fully opened to reduce the temperature inside the chamber 401 to 10 ^-5 Torr or less. rear,
The main valve 427 was closed, and the inside of the chamber 401 was brought to atmospheric pressure by the leak valve 426, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9 μm. The electrophotographic image forming member obtained in this way was installed in a charging exposure experiment equipment, and was heated at 6.0 KV for 0.2 seconds.
Corona charging was performed for a while, and a light image was immediately irradiated. The light image uses a tungsten lamp light source, 0.8lux・
A light intensity of 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 gradation reproducibility was obtained. Next, the image forming member is corona charged for 0.2 seconds at 5.5 KV using a charging exposure experiment device, and image exposure is immediately performed at a light intensity of 0.8 lux・sec. Immediately thereafter, a charged developer is applied to the surface of the member. When the image was transferred and fixed onto transfer paper, an extremely clear image was obtained. Based on the previous results, the electrophotographic photoreceptor obtained in this example has no dependence on the charging electrode.
It has been found to possess the characteristics of an ambipolar imaging member. [Effects of the Invention] The electrophotographic photoconductive member of the present invention designed to have the above-described layer structure exhibits extremely excellent electrical, optical, and photoconductive properties as well as usage environment properties. In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has stable electrical properties even in a humid atmosphere. With high sensitivity,
It has a high signal-to-noise ratio and is extremely resistant to light fatigue and repeated use. Furthermore, it is possible to obtain high-quality visible images with high density, clear halftones, and high resolution. In addition, 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 both cases, the conventional layer structure Whereas the photoconductive layer could not be applied as it is to an electrophotographic image forming member, in the case of the present invention,
a-Si:H with relatively low resistance (5×10 ⁹ Ωcm or more)
Since a photoconductive layer for electrophotography can be constructed even with a layer, a-
Si:H can also be used satisfactorily, and restrictions from the characteristics of a-Si:H can be alleviated.

[Brief explanation of drawings]

1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the electrophotographic photoconductive member of the present invention, and FIGS. 3 and 4 are respectively schematic diagrams of the electrophotographic photoconductive 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, 10
1,201... Support, 102,202... Intermediate layer,
103,203...Photoconductive layer, 104,204...Free surface, 205...Upper layer.

Claims (1)

[Scope of Claims] 1. A support, a photoconductive layer made of an amorphous material having silicon atoms as a matrix and containing hydrogen atoms, and a photoconductive layer that is provided between the support and the photoconductive layer from the support side to the photoconductive layer. an intermediate layer having a function of blocking the inflow of carriers and allowing carriers generated in the photoconductive layer and moving toward the support by electromagnetic wave irradiation to pass from the photoconductive layer side to the support side; In the photographic photoconductive member, the intermediate layer comprises silicon atoms and 40 to 40
Carbon atoms in an amount of 90 atomic% as a matrix, halogen atoms in an amount of 1 to 20 atomic%, or halogen atoms and hydrogen atoms in an amount of 1 to 20 atomic% as the sum of both.
A photoconductive member for electrophotography, comprising a non-photoconductive amorphous material containing 20 atomic%. 2. Claim 1 further comprising, on the upper surface of the photoconductive layer, an upper layer made of a non-photoconductive amorphous material having silicon atoms as a host and containing at least either hydrogen atoms or halogen atoms. photoconductive member for electrophotography. 3. The photoconductive member for electrophotography according to claim 1, further comprising an upper layer made of an inorganic insulating material or an organic insulating material on the upper surface of the photoconductive layer. 4. The photoconductive member for electrophotography according to claim 1, wherein the intermediate layer has a thickness of 30 to 1000 Å. 5. The photoconductive member for electrophotography according to claim 2, wherein the upper layer contains carbon atoms. 6. The photoconductive member for electrophotography according to claim 2, wherein the upper layer contains nitrogen atoms. 7. The photoconductive member for electrophotography according to claim 2, wherein the upper layer contains at least two of carbon atoms, nitrogen atoms, and oxygen atoms. 8. The photoconductive member for electrophotography according to claims 2 to 3, wherein the upper layer has a thickness of 30 to 1000 Å. 9. A photoconductive member for electrophotography according to claims 1 to 3, further comprising a surface coating layer having a free surface serving as a charge image forming surface and having a layer thickness of 0.5 to 70 μm. 10 The amount of hydrogen atoms contained in the intermediate layer is
The photoconductive member for electrophotography according to claim 1, which has a content of 19 atomic % or less.