JPS6335980B2 - - 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.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive member 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 has high sensitivity,
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.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily process 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 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 electrophotographic image forming member, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. . However, conventional photoconductive members having photoconductive layers composed of a-Si have excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. There are points that can be further improved in terms of usage environment characteristics, and practical solid-state imaging devices such as reading devices and image forming members for electrophotography will be developed with productivity and mass production taken into consideration. The reality is that it cannot be used effectively. For example, when applied to electrophotographic image forming members or solid-state imaging devices, it is often observed that residual potential remains during use, and when such photoconductive members are used repeatedly for a long time, Accumulation of fatigue occurs due to repeated use. There have been many disadvantages such as so-called ghost development, which causes afterimages. 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. Although it has many advantages compared to OPC (organic photoconductive material), a-Si has been given characteristics for use in conventional solar cells.
Even when the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, compared to ordinary electrophotography. The above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, it may not be possible to retain the electrostatic charge at all until the development time.There are some points that can be solved. is known to exist. 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 as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms Amorphous silicon material containing halogen atoms, so-called halogen-containing amorphous silicon (hereinafter a-
A photoconductive member designed and produced with a layer structure in which a specific intermediate layer is interposed between a photoconductive layer consisting of Si; Not only can it be used, but it is superior in most respects to conventional photoconductive members, and has particularly excellent properties as a photoconductive member for electrophotography. It is based on the discovery of 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 in which no or almost no residual potential is observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity, has a spectral sensitivity range that substantially covers the visible light range, and has fast photoresponsiveness. Another object of the present invention is to have charge retention properties during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has excellent electrophotographic properties with sufficient electrophotographic properties and whose properties hardly deteriorate 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 photoconductive member 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 halogen atoms, and the photoconductive layer is disposed between the support and the photoconductive layer from the support side. an intermediate having a function of preventing carriers from flowing into the photoconductive layer 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 photoconductive member comprising a layer, the intermediate layer is (Si _x C _1-x ) _y
X _1-Y or (Si _x C _1-x ) _y (H+X) _1-y (However, 0.1≦
It is composed of an amorphous material represented by X≦0.35, 0.80≦Y≦0.99), and is characterized by having a layer thickness of 30 to 1000 Å. A photoconductive member designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, photoconductive, photoconductive properties, and use environment properties. . In particular, when applied as an image forming member for electrophotography or a solid-state imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has excellent electrical properties even in a humid atmosphere. is stable, has high sensitivity, and has a high signal-to-noise ratio.
In addition, it has excellent resistance to light fatigue and repeated use, and in the case of electrophotographic image forming members, it is possible to obtain high-quality visible images with high density, clear halftones, and high resolution. . Moreover, when applied to an electrophotographic image forming member,
a-Si:X with high dark resistance has low photosensitivity, and conversely, a-Si:X with high photosensitivity has a low dark resistance of around 10 ⁸ Ωcm. In contrast, in the case of the present invention, even the ^a -Si: A-Si:X, which has relatively low resistance but high sensitivity, can form a photoconductive layer for photography.
can also be used satisfactorily, and restrictions from the characteristics of a-Si:X can be alleviated. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has an intermediate layer 102,
This layer structure includes a photoconductive layer 103 provided in direct contact with the intermediate layer 102, and is the most basic example of the present invention. The support 101 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au,
Examples include metals such as Nb, Ta, V, Ti, Pt, and Pb, 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, and the surface thereof is conductive. The shape of the support may be any shape such as a cylinder, a belt, a plate, etc.
The shape is determined depending on the need, but for example, if the photoconductive member 100 of FIG. It is desirable to do so. 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. It is made as thin as possible within this range. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The intermediate layer 102 is made of a non-photoconductive amorphous material [a-( _{SixC1 -x} ) _y :
Abbreviated as X _1-y . However, 0<x<1, 0<y<1]
The photoconductive layer 10 is formed from the support 101 side.
from the side of the photoconductive layer 103 to the support 101 of the photocarrier that is generated in the photoconductive layer 103 by the irradiation of electromagnetic waves and moves towards the side of the support 101. It has the function of easily allowing passage to the side of the vehicle. a-(Si _x C _1-x ) _y : Intermediate layer 10 composed of X _1-y
2 is formed by glow discharge method, sputtering method,
This is done by ion implantation method, ion plating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method has advantages such as it is relatively easy to control the manufacturing conditions for manufacturing photoconductive members, and it is easy to introduce carbon atoms and halogen 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 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 one of Si, C, and 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 mix with
Alternatively, a raw material gas containing Si as a constituent atom and Si, C
and a raw material gas having three constituent atoms of X can be used in combination. 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 normal 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 1 to 4 carbon atoms, acetylene hydrocarbons having 2 to 4 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 _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and 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,
_ClF3 , _ClF5 , _BrF5 , _BrF3 , _IF7 , _IF5 , ICl, IBr,
Examples of silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
_SiCl3Br , _{SiCl2Br2 , SiClBr3} , _SiCl3I , _SiBr4 ,
Examples of halogen-substituted silicon hydride include SiH ₂ F ₃ ,
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 ₃ and Si ₄ H ₁₀ . In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffin 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 , _{SiH2Cl2 ,}
Alternatively, an intermediate layer consisting of a _- Si _x C _1-x : layers can be formed. To form the intermediate layer 102 by the sputtering method, a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are treated with halogen. This may be carried out by sputtering in various gas atmospheres containing hydrogen as a component, if necessary. 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 a material serving as a 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, the diluent gas used when forming the intermediate layer 102 by a glow discharge method or a sputtering method is a so-called rare gas, such as He,
Be, Ar, etc. can be cited as suitable examples. 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 C _1-x ) _y : The creation conditions are strictly selected so that 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 to prevent carriers from flowing into the photoconductive layer 103 from the support 101 side, and to prevent photocarriers generated in the photoconductive layer 103 from flowing into the photoconductive layer 103 . It is formed to exhibit electrically insulating behavior because it allows the material to easily move and pass through to the support body 101 side. 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 : An important factor in the conditions for producing X _1-y is the temperature of the support during production. That is, a(Si _x C _1-x ) _y on the surface of the support 101:
When forming the _intermediate layer 102 consisting of a-(Si _x C _1-x ) _y having the property of:
The temperature of the support during layer formation is strictly controlled so that X _1-y can be formed as desired. In the present invention, in order to effectively achieve the desired purpose, 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. Formation of layer 102 is carried out, typically at 100-300°C, preferably
The temperature is preferably 150 to 250°C. 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, Similar to the support temperature mentioned 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. be. The discharge power conditions for effectively producing a-(Si _x C 1 _{- x} ) _y : Ten
~200W, preferably 20-100W. It is desirable that the gas pressure in the deposition chamber is usually about 0.001 to 5 Torr, preferably about 0.01 to 0.5 Torr. The amounts of carbon atoms and halogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are the same as the manufacturing conditions of the intermediate layer 102, so that an intermediate layer can be obtained that achieves the desired characteristics to achieve the object of the present invention. This is an important factor. The amount of carbon atoms contained in the intermediate layer 102 in the present invention is usually 40 to 90 atomic %, preferably 50 atomic %.
It is desirable that it be ~90 atomic%, optimally 50-80 atomic%. The content of halogen atoms is usually 1 to 20 atomic%, preferably 215 atomic%, and the photoconductive member formed when the halogen content is in this range is practically It can be fully applied as an excellent product in various fields. The content of hydrogen atoms that are included as necessary is usually
It is desirable that the content be 19 atomic % or less, preferably 13 atomic % or less. That is, the previous a-
(Si _x C _1-x ) _y : If expressed as X _1-y , x is usually 0.1
~0.35, preferably 0.15~0.30, y usually ~0.99
0.80, preferably 0.99-0.82, optimally 0.98-0.85. When both halogen atoms and water atoms are included,
If we display a-(Si _x C _1-x ) _y (H+X) _1-y as before, the numerical range of x and y in this case is also a-(Si _x
C _1-x ) _y : Almost the same as 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.
03, the probability of the pheotocarriers passing to the side of the support 101 becomes extremely small, and therefore, in any 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,
The thickness is 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 composed of a-Si:X having the semiconductor properties shown below. p-type a-Si:X... Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). p ^- type a-Si:X...type, which is lightly doped with a so-called p-type impurity that has a low acceptor concentration (Na). n-type a-Si:X... Contains only a donor.
Or one that contains both donor and acceptor and has a high concentration of donor (Nd). n ^- type a-Si: Lightly doped with so-called n-type impurities, which has a low donor concentration (Nd) in the type of X.... i-type a-Si:X...NaNdO or NaNd. In the present invention, by providing the intermediate layer 102, the a-Si:X constituting 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 even better results, the photoconductive layer 103 is formed so that the dark resistance of the photoconductive layer 103 is preferably 5×10 ⁹ Ωcm or more, optimally 10 ¹⁰ Ωcm or more. It is desirable that the 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 in the present invention is appropriately determined according to the purpose of the application, such as a reading device, a solid-state imaging device, or an electrophotographic image forming member. In the present invention, the layer thickness of the photoconductive layer is as follows:
The thickness relationship between the photoconductive layer and the intermediate layer can be appropriately determined as desired so that the functions of the photoconductive layer and the intermediate layer can be effectively utilized and the objects of the present invention can be effectively achieved. In normal cases, the layer thickness is preferably several hundred to several thousand times or more than that of the intermediate layer. A specific value is usually 1 to 100μ, preferably 2 to 50μ. In the present invention, specific examples of the halogen atom (X) contained in the photoconductive layer include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. Here, "X is contained in the layer"
This means that "X is bonded to Si", "X
It means either a state in which _X2 is ionized and incorporated into the layer, or a state in which X2 is incorporated into the layer, or a combination thereof. In the present invention, the layer composed of a-Si:X is formed by, for example, a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. For example, to form an a-Si:X layer by a glow discharge method, a halogen-introducing raw material gas is introduced into a deposition chamber whose interior can be reduced in pressure, along with a Si-generating raw material gas that can generate Si. A glow discharge may be generated in the deposition chamber to form a layer of a-Si:X on the surface of a predetermined support that has been placed at a predetermined position. In addition, when forming by sputtering method, for example, in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases.
When sputtering a target made of Si, a halogen introduction gas may be introduced into the sputtering deposition chamber. As the Si-generating raw material gas used in the present invention, silicon hydride (silanes) in a gaseous state or which can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₆ , Si ₄ H ₁₀ is effectively used. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of handling during layer formation work, good Si generation efficiency, etc. Many halogen compounds are effective as the raw material gas for halogen introduction used in the present invention, such as halogen gas, halides,
Preferred examples include gaseous or gasifiable halogen compounds such as interhalogen compounds. Further, in the present invention, silicon compounds containing halogen, which are in a gaseous state or can be gasified, and which can generate Si and halogen at the same time, can also be mentioned as effective compounds. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, and IBr. Preferred examples of the silicon compound containing halogen include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ . When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen, silicon hydride gas is used as a raw material gas that can generate Si. At least a layer of a-Si:X can be formed on a given support. When manufacturing the photoconductive member of the present invention according to the glow discharge method, basically a silicon halide gas, which is a raw material gas for Si generation, and a gas such as Ar, H ₂ , He, etc. are mixed in a predetermined manner. Adjust the ratio so that the gas flow rate is a
- an intermediate formed on a given support by introducing a photoconductive layer of Si:X into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases In contact with the layer a-
Although a photoconductive layer consisting of Si:X can be formed, a layer may also be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen with these gases. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to form a photoconductive layer composed of a-Si:X by a reactive sputtering method or an ion plating method, in the case of a sputtering method,
A target made of Si is sputtered in a predetermined gas plasma atmosphere, and in the case of ion plating, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source. This can be done by heating and evaporating a silicon evaporation source using a resistance heating method, an electron beam method (EB method), or the like, and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or the above-mentioned halogen-containing silicon compound is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for halogen introduction, but in addition, HF, HCl, HBr, HI
Hydrogen halides such as SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
Halogenated silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and the like, which are in a gaseous state or can be gasified, and have hydrogen as one of their constituents can also be cited as effective. These hydrogen-containing halides are suitable for halogen introduction in the present invention because H, which is extremely effective for controlling electrical or photoelectric properties, is introduced at the same time as halogen into the layer during layer formation. used as raw material gas for In order to structurally introduce hydrogen into the photoconductive layer composed of a-Si:X, in addition to the above, H ₂ or SiH ₄ ,
This can also be done by causing a discharge by causing silicon hydride gas such as Si ₂ H ₆ , Si ₃ H ₃ , Si ₄ H ₁₀ to coexist with silicon or a silicon compound for producing a-Si in the deposition chamber. I can do it. For example, in the case of the reactive sputtering method, Si
Using a target, introduce gas and
By introducing H ₂ gas, including inert gases such as He and Ar as necessary, into the deposition chamber to form a plasma atmosphere, and sputtering the Si target, a support surface having predetermined characteristics can be formed. A layer consisting of a-Si:X with H introduced thereon is formed. Furthermore, B ₂ H ₃ also serves as impurity doping.
Gases such as PH ₃ and PF ₃ can also be introduced. In the present invention, the amount of X or (H+X) contained in the photoconductive layer of the photoconductive member to be formed is usually 1 to 40 atomic%, preferably 5 to 40 atomic%.
It is desirable to set it 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 doping while controlling the amount. As impurities to be doped into the photoconductive layer, in order to make the photoconductive layer p-type, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferred. 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 use materials that are as non-polluting as possible. Preferably. 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, for example, interstitial doping with Li or the like by thermal diffusion or implantation. 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 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 includes an intermediate layer 202 formed on a support 201 using the same material as the intermediate layer 102 and having a similar function, and an a-Si layer into which H is introduced as necessary. :A photoconductive layer 203 composed of X, provided on the photoconductive layer 203,
A top layer 205 having a free surface 204 is provided. When the upper layer 205 is used, for example, when the free surface 204 of the photoconductive member 200 is subjected to charging treatment to form a charge image, the charge that can be held on the free surface 204 is transferred to the photoconductive layer 203. When the photoconductive layer 203 is irradiated with electromagnetic waves, the photocarriers generated in the photoconductive layer 203 and the electrical charges in the portions irradiated with the electromagnetic waves undergo recombination. Similarly, it has the function of easily allowing the passage of photo carriers or charged charges. The upper layer 205 is made of a-(Si _x
C _1-x ) _y : composed of X _1-y, a-Si _a N _1-a , a-
(Si _a C _1-a ) _b :X _1-b , a-(Si _a H _1-a ) _b :(H+X) _1-
b , a-Si _c O _1-c , a-(Si _c O _1-c ) _d :X _1-d , a-
(Si _c O _{1-c ) d} : (H + Consists of amorphous materials containing hydrogen atoms (H) and/or halogen atoms (X), inorganic insulating materials such as SiNO, Al ₃ O ₃ , and organic insulating materials such as polyester, polyparaxylylene, and polyurethane. You can also do that. However, the material constituting the upper layer 205 is selected from the middle layer 202 in terms of productivity, mass production, and electrical and usage environmental stability of the formed layer.
a-(Si _x C _1-x ) _y which has the same characteristics as: a-Si _x which is composed of X _1-y or does not contain a 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 a silicon atom and at least two atoms among C, N, and O, and a halogen atom or a halogen atom. 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
When using the photoconductive member 200 in such a manner that the electromagnetic waves that the photoconductive layer 203 is sensitive to are irradiated from the 05 side, a sufficient amount of the irradiated electromagnetic waves reach the photoconductive layer 203 and the photocarrier is efficiently This is done carefully so as to induce an outbreak. 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. As the starting material used in forming the upper layer 205, in addition to the above-mentioned materials used to form the intermediate layer, as a starting material for introducing carbon atoms, for example, a material having 1 to 4 carbon atoms is used. Saturated hydrocarbon, ethylene hydrocarbon having 1 to 4 carbon atoms, 2 to 3 carbon atoms
Examples include acetylene hydrocarbons and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₃ ), 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 containing oxygen atoms in the upper layer 205 include oxygen (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 (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 starting materials for forming the upper layer 205 include predetermined atoms as constituent atoms of the upper layer 205 to be formed.
05, they are appropriately selected and used during layer formation. For example, if you use the glow discharge method,
Single gas such as Si (CH ₃ ) ₄ , SiCl ₂ (CH ₃ ) ₂ or SiH ₄
−N ² O system, SiH ₄ −O ₂ (−Ar) 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 −
A mixed gas such as SiH ₄ -based SiCl ₂ (CH ₃ ) ₂ -SiH ₄ -based gas 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, the thickness is appropriately determined depending on the material forming the layer, the layer forming conditions, etc. The layer thickness of the upper layer 205 in the present invention is as follows:
Typically 30-1000Å, preferably 50-600Å
It is desirable that this is the case. 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, disclosed in Japanese Patent Publication No. 42-23910, No. 43-24748.
If an electrophotographic process such as the NP method described in the publication is to be applied, it must be electrically insulating, have sufficient ability to retain static charge when subjected to charging treatment, and be thicker than a certain level. However, if an electrophotographic process such as the Carlson process is applied, it is desirable that the potential in the bright area after electrostatic image formation is very small, so the thickness of the surface coating layer should be is required to be very 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 for forming the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Organic insulators such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride monofluoride vinylidene 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 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 that differentiates the protective layer and the electrically insulating layer varies depending on the materials used, the electrophotographic process applied, and the structure of the imaging member designed.
The above value of 10μ is not an absolute value. 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 0.5 mm thick, 10 cm square molybdenum plate (substrate) 309 whose surface was cleaned 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 are closed, the main valve 310 is fully opened to exhaust the inside of the chamber 301.
The degree of vacuum was set at approximately 5×10 ^-6 torr. Thereafter, the input voltage to the heater 308 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 200°C. After that, the auxiliary valve 340, then the outflow valves 325, 326, 327 and the inflow valve 320,
321 and 322 are fully opened, and the flow meter 31
The interior of 6,317,318 was also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 325, 326,
After closing 327, 320, 321, 322,
Open the valve 330 of the SiF ₄ gas (purity 99.999%) cylinder 311 containing 10 vol% H ₂ and the valve 331 of the C ₂ H ₂ gas cylinder 312 diluted to 10 vol% with H ₂ to check the pressure on the outlet pressure gauges 335 and 336. 1Kg/ ^cm2
and open the inflow valves 320 and 321 too much to allow SiF ₄ gas into the flow meters 316 and 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 1:80. 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 reached 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. It was confirmed that the gas inflow was stable and the internal pressure was stable. Next, turn on the switch of the high frequency power supply 342 and turn on the induction coil 343.
Then, 13.56MHz high frequency power was applied to generate a glow discharge in the chamber 301 of the coil part (upper part of the chamber).
The input power was 60W. In order to deposit a 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 is turned off,
With the glow discharge stopped, the outflow valve 32
6 was closed and then diluted to 500volppm with _H2
Open the valve 332 of the B ₂ H ₆ gas cylinder 313,
Adjust the pressure of the outlet pressure gauge 337 to 1 kg/cm ² and gradually open the inflow valve 322 to increase the flow meter 3.
B ₂ H ₆ gas was flowed into 18. Subsequently, the outflow valve 327 was gradually opened. At this time, the inflow valves 320 and 322 were adjusted so that the ratio of the B ₂ H ₆ gas flow rate to the SIF ₄ gas flow rate was 1:70. 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 that time was set to 60W as 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 source 342 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 325, 327 The inflow valves 320-2, 321, and 322 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is
After reducing the pressure to 10 ^-3 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. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus cut is placed in a charging exposure experiment device,
Corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 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 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 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. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charge polarity and had the characteristics of a bipolar image forming member. Example 2 Sample No. An image forming member shown in . . . . 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 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
Intermediate layer film deposition rate: 1Å/sec
Example 3 SiF ₄ was used when forming an intermediate layer on a molybdenum substrate.
Image forming members represented by sample numbers ~ were prepared under the same conditions and procedures as in Example 1, except that the gas flow rate and C ₂ H ₄ gas flow rate ratio were varied as shown in Table 2 below. When the same image formation was carried out using the same electrostatic exposure experimental apparatus as in Example 11, the results shown in Table 2 below were obtained. Sample No.
When ~ was analyzed by the electron 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 0.47.

【table】

[Table] Example 4 A molybdenum substrate was installed in the same manner as in Example 1, and then a vacuum of 5×10 ^-8 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, and then the SiF ₄ , C ₂ H ₄ gas inflow system was heated 5× by the same operation as in Example 1.
10 ^-6 torr vacuum and then auxiliary valve 340
and each outflow valve 325, 326 each inflow valve 3
After closing 20-2,321, it contains 10 vol% _H2
Valve 330 of SiF ₄ gas cylinder 311, with H ₂
Open the valve 331 of the C ₂ H ₄ gas cylinder 312 diluted to 10 vol%, and check the outlet pressure gauges 335 and 336.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 320-
Gradually open 2,321 and check the flow meter 31.
SiF ₄ gas and C ₂ H ₄ gas were flowed into 6,317.
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 C ₂ H ₄ gas flow rate ratio is 1:80.
The inflow valves 320-2 and 321 were adjusted so that Next, while watching the reading on the Pirani gauge 341, adjust the opening of the auxiliary valve 340, and
Auxiliary valve 3 until the inside of 01 becomes 1×10 ^-2 Torr.
I opened 40. 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°C, the high frequency power supply 342 is turned on as in Example 1, glow discharge is started with an input power of 60W, and the glow discharge is continued for 1 minute. After forming an intermediate layer on the substrate while maintaining the conditions, a high frequency power source is applied.
342 was turned off, and the outflow valve 326 was closed while the glow discharge was stopped. 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 set to 60W as before. After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heating heater 308 is turned off, the high frequency power supply 342 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 325 and Close the inflow valves 320-2 and 321, and close the main valve 31.
After fully opening the chamber 301 to bring the pressure below 10 ^-5 torr, the main valve 310 was closed and 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 formed layer is approximately
It was 15μ. Regarding this image forming member, Example 1
When an image was formed on a transfer paper under the same conditions and procedures as described above, the image quality was superior to that formed by corona discharge, and it was extremely clear. From this result, 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 and the outflow valve was opened with the glow discharge stopped. Close 326,
Next, open the valve 333 of the PH ₃ gas cylinder 314 diluted with H ₂ to 250 volppm and the outlet pressure gauge 33
8 was adjusted to 1 Kg/cm ² and the inflow valve 323 was gradually opened to allow PH ₃ gas to flow into the flow meter 319. Subsequently, the outflow valve 328 was gradually opened. At _this time, the inflow valves ₃₂₀ , 3
23 was adjusted. Next, in the same way as when forming the intermediate layer, Pirani gauge 3
Auxiliary valve 34 so that the instruction of 41 becomes 0.5torr
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 60W. 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.
OFF state, wait until the substrate temperature reaches 100°C, and then open the outflow valves 325, 328 and the inflow valve 3.
20-2, 321, and 323, and the main valve 310 is fully opened to reduce the pressure inside the chamber 301 to 10 ^-5 torr or less. Then, the main valve 310 is closed and the inside of the chamber 301 is set to atmospheric pressure by the leak valve 344, and the substrate is returned to the atmospheric pressure. I took it out. In this case, the total thickness of the layer formed was approximately 11μ. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1. The image quality was excellent and extremely clear. From this result, 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, the B ₂ H ₆ gas flow rate was changed when subsequently forming a photoconductive layer.
An intermediate layer and a photoconductive layer were formed on a molybdenum substrate under the same conditions and procedures as in Example 1, except that the flow rate was 1/15 of the SiF ₄ gas flow rate. 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. From this result, it was found that the photoreceptor obtained in this example had charge polarity dependence. However, its 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, a high frequency power source 342 was applied.
The outflow valve 327 was closed while the was turned off to stop glow discharge, and the outflow valve 326 was 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 was also 60W, the same as when forming the intermediate layer. After maintaining the glow discharge for 2 minutes to form an upper layer on the photoconductive layer, the heating heater 308 is turned off, the high frequency power supply 342 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve is turned off. 3
25, 326 and inflow valve 320-2, 32
1,322 was closed and the main valve 310 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less.The main valve 310 was then 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 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 optical image is generated using a tungsten lamp light source, 1.0 lux.
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 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 gradation reproducibility was obtained. Example 8 One side of a cleaned Corning 7059 glass (1 mm thick, 4 x 4 cm, polished on both sides) was coated with 1000 Å of ITO by electron beam evaporation.
The vapor-deposited material was placed in the same apparatus as in Example 1 (third
It was placed on the fixing member 303 (see figure) with the ITO deposition surface facing upward. Subsequently, the inside of the glow discharge deposition chamber 301 was made into a vacuum of 5×10 ^-6 torr by the same operation as in Example 1, and the substrate temperature was maintained at 150° C., and then the auxiliary valve 340 and then the outflow valve 325 were opened. ,32
7,329 and inflow valve 320-2,322,
324 fully open, flow meters 316, 31
The interior of 8,320 was also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 326, 327, 329,
After closing 317, 318, 320-2, in H ₂
SiCl( _CH3 ) ₃ gas diluted to 10vol% (purity
99.999%) Open the cylinder 315 valve 334 and adjust the pressure on the outlet pressure gauge to 1Kg/cm ² and inflow valve 32.
4 gradually open and enter the flow meter 320-1.
SiCl( _CH3 ) ₃ gas was introduced. Subsequently, the outflow valve 329 was gradually opened. Next, the opening of the auxiliary valve 340 was adjusted while observing the reading on the Pirani gauge 341, 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 became stable, the main valve 310 was gradually closed, and the opening was narrowed until the reading on the Pirani gauge 341 reached 0.5 torr. Confirm that the gas inflow is stable and the internal pressure is stable, then turn on the switch of the high frequency power supply 342 to the induction coil 343,
13.56MHz high frequency power is applied to generate a glow discharge in the chamber 301 of the coil section (upper part of the chamber), generating 20W.
The input power was set to . After forming the intermediate layer under the same conditions for 1 minute, the high frequency power source 342 is turned off,
After a while while the glow discharge was stopped, the outflow valve 329 and inflow valve 324 were closed and the substrate temperature was raised to 200°C. Next, SiF ₄ containing 10 vol% H ₂
Valve 334 of gas cylinder 311, with H _2
B2H6 gas _cylinder 313 diluted to 500volppm
Open the valve 332 and check the outlet pressure gauge 335, 3.
Adjust the pressure of 37 to 1Kg/cm ² and open the inflow valve 320.
- Gradually open 2,322 and flow meter 31
SiF ₄ gas and B ₂ H ₆ gas were respectively flowed into 6,318. Subsequently, the outflow valves 325, 327 were gradually opened. SiH ₄ gas flow rate and B ₂ H ₆ at this time
The inflow valve 32 is adjusted so that the gas flow ratio is 70:1.
An aperture of 0.322 was determined and stabilized. Furthermore, room 3
The valve adjustment operation was performed in the same manner as when forming the intermediate layer so that the internal pressure in 0.01 was 0.5 torr. After that, turn on the high frequency power supply 342 again.
state, and the glow discharge was restarted. The input voltage at that time was increased to 60W 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 after waiting for the substrate temperature to reach 100°C, the outflow valve 325,
327 and inflow valve 320-2, 322, 32
4 was closed and the main valve 310 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less.The main valve 310 was then 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, and corona charging was performed at 6.0 KV for 0.2 seconds.
A light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good 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 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 heated with an accuracy of ±0.5° C. by a heater 407 within a fixed member 406. 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. Then heater 4
The input voltage of 07 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 427, then the outflow valves 418, 419, 420 and the inflow valve 415,
Fully open 416 and 417, flow meter 42
The interior of 4,425,426 was also sufficiently degassed and vacuumed. Auxiliary valve 427, valves 418, 419,
After closing 420, 424, 425, 426,
SiF ₄ gas (99.999% purity) cylinder 410 and Ar
Valve 413 of valve 412 of gas cylinder 409
Open the outlet pressure gauges 422, 421 to 1.
Kg/cm ² , and the inflow valves 416 and 415 were gradually opened to allow SiF ₄ gas and Ar gas to flow into the flow meters 425 and 424, respectively. Subsequently, the outflow valves 419 and 418 were gradually opened, and then the auxiliary valve 427 was gradually opened. At this time
The inflow valves 416 and 415 were adjusted so that the ratio of SiF ₄ gas flow rate to Ar gas flow rate was 1:20. Next, while watching the reading on the Pirani gauge 430, adjust the opening of the auxiliary valve 427 so that the inside of the chamber 401 is 1×
Auxiliary valve 427 was opened until 10 ^-2 torr.
After the internal pressure of the chamber 401 is stabilized, the main valve 429 is closed.
gradually close the Pirani gauge 430.
The aperture was narrowed down to 0.5 torr. After opening the shutter 408 and confirming that the flow meters 425 and 424 are stable, the high frequency power supply 431 is turned on and the area ratio is 1:9.
AC power of 13.56 MHz and 100 W was input between targets 404 and 403 made of polycrystalline high-purity silicon and high-purity graphite, and 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 431
was turned off, and the discharge was temporarily stopped. Close the cylinder valves 412 and 413 and main valve 42
9 is fully opened to check the inside of the chamber 401 and the flow meter 42.
After evacuating the inside of 4,425 to 10 ^-5 torr, main valve 429 auxiliary valve 427 and outflow valve 4
18,419, inlet valves 415,416 were closed. SiF ₄ gas cylinder 410 containing 10vol% _H2
Changed to SiF ₄ gas (99.999%). Main valve 4
After opening the chamber 401 and evacuating the chamber 401 to 5×10 ^-7 torr, open the valve 413 of the cylinder 410 and adjust the pressure of the outlet pressure gauge 422 to 1 Kg/cm ² , and gradually open the inflow valve 416 to reduce the flow. meter 425
SiF ₄ gas was flowed into the chamber. Subsequently, the outflow valve 419 was gradually opened. Next, the valve 414 of the B ₂ H ₆ gas cylinder 411 diluted with H ₂ to 500 volppm
was opened, the pressure of the outlet pressure gauge 423 was adjusted to 1 Kg/cm ² , and the inflow valve 417 was gradually opened to allow B ₂ H ₆ gas to flow into the flow meter 426 . Subsequently, the outflow valve 420 was gradually opened, and then the auxiliary valve 427 was gradually opened. At this time, the inflow valves 416 and 417 were adjusted so that the ratio of SiF ₄ gas flow rate to B ₂ H ₆ gas flow rate was 70:1. Next, while watching the reading on the Pirani gauge 430, the openings of the auxiliary valve 427 and the main valve 429 were adjusted until the reading on the Pirani gauge 430 became 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 to inside the chamber 401. A glow discharge was generated and the input power was 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 407 is turned on.
OFF state, wait until the substrate temperature reaches 100°C, and then open the outflow valves 419, 420 and the inflow valve 4.
15, 416, 417 and close the main valve 42.
9 was fully opened to bring the inside of the chamber 401 to 10 ^-5 torr or less, the main valve 429 was closed, and the inside of the chamber 401 was brought to atmospheric pressure by the leak valve 428, and the substrate was taken out. In this case, the total thickness of the formed layer is approximately
It was 9μ. The image forming member thus obtained is
It was installed in a charging exposure experimental device, corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image is 0.8lux・sec using a tungsten lamp light source.
The amount of light 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 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. From the above results, it was found that the electrophotographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 10 After forming an intermediate layer on a molybdenum substrate for 2 minutes under the same conditions and procedures as in Example 9,
Turn on the high frequency power supply 342, turn off the heater 407, close the outflow valves 418, 419, and inflow valves 415, 416, wait until the substrate temperature reaches 100°C, and then open the auxiliary valve 427 and main valve 42.
9 closed. Subsequently, the leak valve 428 was opened to leak the inside of the deposition chamber 401 to atmospheric pressure, leaving only the high purity silicon target 404, excluding the target 403 made of high purity graphite from the targets 404 and 403. After that, the leak valve 428 is closed and the deposition chamber 40
1 to a vacuum of about 5×10 ^-7 torr, then open the auxiliary valves 427 and outflow valves 418, 419, and after sufficiently deaerating the insides of the flow meters 424, 425, the outflow valves 418, 419 and the auxiliary valve 427
closed. The heater 407 heats the substrate 402 again.
was turned on and the substrate temperature was maintained at 200℃. And valve 413 of SiF ₄ gas (purity 99.999%) cylinder 410 and valve 41 of Ar gas cylinder 409
2, and set the pressure of the outlet pressure gauges 422, 421 to 1.
Kg/cm ² , and the inflow valves 416 and 415 were gradually opened to allow SiF ₄ gas and Ar gas to flow into the flow meters 425 and 424, respectively. Subsequently, the outflow valves 419 and 418 were gradually opened, and then the auxiliary valve 427 was gradually opened. At this time
The inflow valves 416 and 415 were adjusted so that the ratio of SiF ₄ gas flow rate to Ar gas flow rate was 1:20. Next, while watching the reading on the Pirani gauge 430, adjust the opening of the auxiliary valve 427 so that the inside of the chamber 401 is 1×
Auxiliary valve 427 was opened until 10 ^-4 torr.
After the internal pressure of the chamber 401 is stabilized, the main valve 429 is closed.
Gradually close the Pirani gauge 430 so that the indication is 1x
The aperture was narrowed down to 10 ^-2 torr. After opening the shutter 408 and confirming that the flow meters 425 and 424 are stable, the high frequency power source 431 is turned on, and 13.56 MHz, 100 W AC power is applied between the polycrystalline high purity silicon target 404 and the fixing member 406. entered. Under these conditions, the layers were formed while performing matching so that stable discharge could continue. After continuing to discharge for 3 hours to form a photoconductive layer in this manner, the heating heater 407 is turned off, the high frequency power source 431 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 418, 419 and inflow valve 415,
416 and 417 and fully open the main valve 429 to reduce the inside of the chamber 401 to 10 ^-5 torr or less,
The main valve 429 was closed, and the inside of the chamber 401 was brought to atmospheric pressure by the leak valve 428, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 6.0 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 0.8 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image 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 11 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 results were as shown in Table 4 below. Various top layers were provided. Thereafter, charging, exposure and transfer were performed with respect to both polarities in the same manner as in Example 1, and a very clear toner image was obtained with no dependence on charging polarity.

【table】 [Brief explanation of the drawing]

FIGS. 1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the photoconductive member of the present invention, and FIGS. 3 and 4 each illustrate the manufacture of the photoconductive member of the present invention. FIG. 100,200...Photoconductive member, 101,20
1... Support, 102, 202... Intermediate layer, 10
3,203...Photoconductive layer, 104,204...Free surface, 205...Top 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 halogen atoms, and a photoconductive layer provided between these, from the support side into the photoconductive layer. an intermediate layer having a function of preventing carriers from flowing into the photoconductive layer 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 photoconductive member comprising: (Si _x C _1-x ) _y X _1-y or (Si _x C _1-x ) _y (H
+X) _1-y (However, 0.1≦x≦0.35, 0.80≦y≦0.99,
A photoconductive member comprising an amorphous material represented by (X represents a halogen atom) and having a layer thickness of 30 to 1000 Å. 2. On the upper surface of the photoconductive layer, an amorphous material made of silicon atoms and containing at least one of hydrogen atoms and halogen atoms and at least one of carbon atoms, nitrogen atoms, and oxygen atoms is formed. A photoconductive member according to claim 1 having a top layer. 3. The photoconductive member according to claim 1, which has 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 according to claim 1, wherein 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 is provided on the upper surface of the photoconductive layer.