JPS6341060B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on light (here, light in a broad sense, ultraviolet light,
The present invention relates to photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, gamma rays, etc. As photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc., highly sensitive,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], has spectral characteristics of the electromagnetic waves to be irradiated, has good photoresponsiveness, and has a desired dark resistance value.
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 a-Si) is a photoconductive material that has recently attracted attention.
No. 2855718 describes its application as an electrophotographic image forming member, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. However, conventional photoconductive members having 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, reading devices, image forming members for electrophotography, etc. should be developed by taking into account productivity and mass production. 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, There are many inconveniences, such as the accumulation of fatigue due to repeated use and the 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 can be used as a material constituting the photoconductive _layer of an electrophotographic image forming member. 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 material used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms Amorphous material containing halogen atoms, so-called halogen-containing amorphous silicon (hereinafter referred to as a-
A photoconductive member designed and manufactured to form a layer in which a specific intermediate layer is interposed between a photoconductive layer consisting of Si (denoted as X) and a support supporting the photoconductive layer is practically sufficient. 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 is extremely resistant to light stress and does not exhibit deterioration phenomena even after repeated use. The main objective 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 covers substantially the entire 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 methods 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 is provided between the support and the photoconductive layer from the support side. an intermediate layer having a function of preventing carriers from being injected 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; The photoconductive member is characterized in that the intermediate layer is made of an amorphous material whose constituent elements are silicon atoms, nitrogen atoms, and halogen atoms, and has a layer thickness of 30 to 1000 Å. . A photoconductive member designed to have the layer structure described above can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. . 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. . Also, when applied to an electrophotographic imaging 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 at most. In contrast, in the case of the present invention, even a relatively low resistance (5×10 ⁹ Ωcm or more) a-Si: Since it can constitute a photoconductive layer for electrophotography, it has relatively low resistance but high sensitivity.
Si:X can also be used satisfactorily, and restrictions from the characteristics of a-Si:X can be alleviated. The 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 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,
It has a layer structure consisting of the intermediate layer 102 and a photoconductive layer 103 provided in direct contact with it, and is the most basic example of the present invention. The support 101 may be conductive, electrical, or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, 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, ceramics, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, 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, Iu ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr,
The surface is treated with a metal such as Mo, Ir, Nb, Ta, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired, but for example,
If the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying. The thickness of the support is determined as appropriate so that the desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the thickness of the support may be determined appropriately so that the photoconductive member has sufficient flexibility. It is made as thin as possible within the range. However, in such cases, the thickness is usually 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-(Si _x N _1-x ) containing silicon atoms and nitrogen atoms as a matrix and halogen atoms (denoted as X).
y: Abbreviated as X _1-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 It has a function of easily allowing the photo carrier moving toward the substrate 101 to pass from the side of the photoconductive layer 103 to the side of the support 101. The intermediate layer 102 composed of a-(Si _x N _1-x )y:X _1-y can be formed by glow discharge method, sputtering method, ion implantation method, ion plating method, or electron beam method. etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control manufacturing conditions for manufacturing a photoconductive member having the following properties. The glow discharge method or the sputtering method is preferably employed because of the advantages of easily introducing nitrogen atoms and halogen atoms together with silicon atoms into the intermediate layer to be produced. 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. To form the intermediate layer 102 by the glow discharge method, the raw material gas for forming a-(Si _x N _{1 -x} )y: The mixture is introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and into the introduced gas atmosphere,
By generating a glow discharge first, a gas plasma is formed and a-(Si _x N _1-x )y is formed on the support 101.
All you have to do is deposit X _1-y . In the present invention, the raw material gas for forming a-(Si _x N _1-x )y:X _1-y is a gaseous substance containing at least one of Si, N, 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, N, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing N as a constituent atom, and a raw material gas containing Alternatively, a raw material gas containing Si and a raw material gas containing N and X may be mixed at a desired mixing ratio. Can be used by mixing. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing N 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
N _1-x )y:X _1-y , but 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, starting materials that can be used as raw material gases that can be effectively used to form the intermediate layer 102 include those in a gaseous state or substances that can be easily gasified at room temperature and normal pressure. I can do it. Examples of starting materials for forming such an intermediate layer include nitrogen, nitrides, nitrogen compounds such as fluorinated nitrogen and azides, simple halogens, hydrogen halides,
Examples include interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, nitrogen (N ₂ ), nitrogen compounds such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ )
etc., halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl, and HBr; halogen compounds include BrF, ClF, ClF ₃ , ClF ₅ , BrF ₅ , _BrF3 ,
IF ₇ , IF ₅ , ICl, IBr, silicon halide
SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br, SiCl ₂ Br ₂ ,
SiClBr ₃ , SiCl ₂ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , silicon hydride includes silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. I can do it. These starting materials for forming the intermediate layer are selected such that the intermediate layer to be formed contains silicon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. They are selected and used as desired during formation. For example, SiH ₄ or Si ₂ H ₆ can easily contain silicon atoms and hydrogen atoms and form an intermediate layer with desired characteristics, and N ₂ or NH ₃ can contain nitrogen atoms. SiF ₄ , SiH ₂ F ₂ , SiHCl ₃ , SiCl ₄ as substances containing halogen atoms,
A _- Si _{x N 1 -x} :
An intermediate layer consisting of +H can be formed. Alternatively, SiF ₄ , etc., which can contain silicon atoms and halogen atoms, and N ₂ , etc., which can contain nitrogen atoms, at a predetermined mixing ratio, and if necessary, He, Ne, It is also possible to form an intermediate layer made of a-Si _x N _1-x :F by introducing it together with a rare gas such as Ar into an apparatus system for forming an intermediate layer to generate a glow discharge. To form the intermediate layer 102 by the sputtering method, a high-purity single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer formed by mixing Si and Si ₃ N ₄ is used as a target. , these may be carried out by sputtering in various gas atmospheres containing halogen and, if necessary, hydrogen as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing N and The Si wafer may be sputtered by forming plasma. Alternatively, by using Si and Si ₃ N ₄ as separate targets or by using a single target formed by mixing Si and Si ₃ N ₄ , a gas containing at least halogen atoms can be produced. This is done by sputtering in an atmosphere. As the raw material gas for introducing N, X, and H if necessary, the starting material for forming the intermediate layer shown in the glow discharge example mentioned above is also used as an effective material in the sputtering method. can be done. 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 so that its required characteristics can be reproduced as desired. In other words, materials whose constituent atoms are Si, N, X, and optionally H can have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrical properties ranging from conductive to amorphous. In the present invention, non-photoconductive a-(Si _{xN1 -x} )y:X1 _-y
The conditions for its creation are carefully selected so that it is formed. a-(Si _x
N _{1-x )} y: This is because it easily allows movement and passage to the support body 101 side.
It is formed to exhibit electrically insulating behavior. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, 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 N _1-x )y: An important factor in the production conditions for X _1-y is the temperature of the support during production. That is, a-(Si _x N _1-x ) is formed on the surface of the support 101.
When forming the intermediate layer 102 consisting of y:X _1-y ,
The temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, a-(Si _x
The temperature of the support during layer formation is strictly controlled so that N _1-x )y: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.
It is possible to continuously form the photoconductive layer 103 from the photoconductive layer 103 to the third layer formed on the photoconductive layer 103 if necessary, and it is possible to finely control the composition ratio of atoms constituting each layer. Although it is advantageous to employ a glow discharge method or a sputtering method because the thickness can be controlled relatively easily compared to other methods, the intermediate layer 102 can be formed using these layer forming methods. In this case, the discharge power and gas pressure during layer formation are set to a-(Si _x N _1-x ) similar to the support temperature described above.
This can be cited as an important factor that influences the characteristics of yX _1-y . The discharge power conditions for effectively producing a-(Si _x N 1 _{- x} )y: It is 10-300W, preferably 20-100W. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.01 to 5 Torr when layer formation is performed using the glow discharge method.
When forming a layer by sputtering at a pressure of about 0.1 to 0.5 Torr, it is usually 10 ^-3 to 5×
10 ^-2 Torr, preferably about 8×10 ^-3 to 3×10 ^-2 Torr. The amounts of nitrogen 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 for achieving success. The amount of nitrogen atoms contained in the intermediate layer 102 in the present invention is usually 30 to 60 atomic%, preferably
It is desirable that the amount is 40 to 60 atomic%. The content of halogen atoms is usually 1 to 20 atnmic%, preferably 2 to 15 atnmic%, and photoconductive members produced when the halogen content is in this range are actually used. It can be fully applied to surfaces. 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 N _1-x )y: If expressed as X _1-y , x is usually 0.43
~0.60, preferably 0.49~0.43, y usually 0.99~
0.80, preferably 0.98 to 0.85. When both a halogen atom and a hydrogen atom are included, the same a-(Si _x N _1-x )y: (H+X) _1-y as before
If expressed as follows, the numerical range of x and y in this case is almost the same as in the case of a-(Si _x N _1-x )y: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 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: A write-read bleed of the so-called p-type impurity with a low acceptor concentration (Na) in the X... type. 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 the so-called n-type impurity, which has a low donor concentration (Nd) in the X... type. i-type a-Si:X...NaNdO or,
NaNd stuff. In the present invention, by providing the intermediate layer 102, a-Si:X 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 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 it be formed. 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 suitably 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 photoconductive layer composed of a-Si:X is formed by a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. . For example, in order to form a photoconductive layer consisting of a-Si:X by a glow discharge method, Si can be generated.
A raw material gas for introducing halogen is introduced into a deposition chamber whose interior can be reduced in pressure together with a raw material gas for Si generation, and a glow discharge is generated in the deposition chamber, and a -Si:X
What is necessary is to form a layer consisting of. In addition, when forming by sputtering method, for example, when sputtering a target formed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, The halogen introduction gas may be introduced into the deposition chamber for sputtering. As the Si generation 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 ₈ , 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 and good Si generation efficiency. Many halogen compounds are effective as the raw material gas for halogen introduction used in the present invention, such as halogen gas, halogenide,
Preferred examples include gaseous or gasifiable halogen compounds such as interhalogen compounds. Furthermore, silicon compounds containing halogen, which can generate Si and halogen at the same time, are in a gaseous state, or can be gasified, can also be mentioned as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF 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 photoconductive layer made of a-Si:X can be formed on a predetermined support. When manufacturing the photoconductive layer 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 amount. By introducing these gases into a deposition chamber for forming a photoconductive layer consisting of a-Si:X at a mixing ratio and a gas flow rate of , a glow discharge is generated to form a plasma atmosphere of these gases. , in contact with an intermediate layer formed on a predetermined support, a
Although a photoconductive layer consisting of -Si:X can be formed, a layer may also be formed by further 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. To form a photoconductive layer made of a-Si:X by a reactive sputtering method or an ion plating method, a target made of Si is used in the case of a sputtering method, and the target is placed in a predetermined manner. Sputtering is performed in a gas plasma atmosphere of This can be carried out by heating and evaporating the flying evaporated material by (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, and halides containing hydrogen as one of their constituents, which are in a gaseous state or can be gasified, can also be cited as effective. These hydrogen-containing halides are suitable for halogen introduction in the present invention because they introduce H, which is extremely effective for controlling electrical or photoelectric properties, at the same time as halogen is introduced into the layer during layer formation. used as raw material gas. In order to structurally introduce hydrogen into the photoconductive layer consisting 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 ₈ , 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 gas plasma atmosphere and sputtering the Si target, a support having predetermined characteristics can be formed. A layer consisting of a-Si:X into which H is introduced is formed on the surface. Furthermore, B ₂ H ₃ ,
It is also possible to introduce a gas such as PH ₃ or PF ₃ . In the present invention, the amount of X or the amount of (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. 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 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 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 n-type by interstitial doping with Li or the like by, for example, thermal diffusion or ion 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 the same 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 electrostatic 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 has the same characteristics as the intermediate layer 202, and optionally contains a-(Si _x
N _1-x ) y: In addition to consisting of X _1-y , a-Si _a C _1-a ,
a-(Si _a C _1-a ) b: H _1-b , a-(Si _a C _1-a ) b:
(H+X) _1-b , a-SicO _1-c , a-( _{SicO 1-c} )d:
H _1-d , a-(Si _c O _1-c ) d: (H+X) _1-d , a-Si _e
The photoconductive layer, such as N _1-e, is composed of a silicon atom and a nitrogen or oxygen atom, which are the host atoms, or a hydrogen atom (H) or/and a halogen atom ( It can also be composed of an amorphous material containing X), an inorganic insulating material such as Al ₃ O ₃ , or an organic insulating material such as polyester, polyparaxylylene, polyurethane, etc. 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 environment stability of the formed layer.
a-(Si _x N _1-x )y:X _1-y with the same characteristics as
or a-(Si _a C _1-a )b:X _1-b , a
−(Si _c N _1-c ) d: H _1-d , a−(Si _e N _1-e ) f:
X _1-f , a-(Si _g C _1-g )h: H _1-h or d-Si _x C _1-x , a-Si _z that does not contain a halogen atom or a hydrogen atom
Preferably, it consists of C _1-z . 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 and hydrogen atoms. Halogen atoms include F, Cl, Br
From the viewpoint of thermal stability, among the above amorphous materials, those containing F are effective. 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 is used in such a way as to irradiate electromagnetic waves that are sensitive to done carefully. The upper layer 205 can be formed using the same method as the intermediate layer 202, such as a glow discharge method or a reactive sputtering method. As the starting material used in forming the upper layer 205, in addition to the above-mentioned materials used in forming the intermediate layer, as a starting material for introducing carbon atoms, for example, a material having a carbon number of 1 to 5 is used. saturated hydrocarbons,
Ethylene hydrocarbon having 1 to 5 carbon atoms, 2 to 5 carbon atoms
Examples include acetylene hydrocarbons of No. 4. 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 ), putene-1 (C ₄ H ₈ ), putene-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 1, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , 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 are used to form the upper layer 205 in which predetermined atoms are formed as constituent atoms.
5, 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 series, SiH ₄ -NH ₃ series, SiCl ₄ -NH ₄ series,
SiH ₄ ―N ₂ system, SiH ₄ ―NH ₃ ―NO system, Si(CH ₃ ) ₄ ―
Mixed gases such as SiH ₄ series, SiCl ₂ (CH ₃ ) ₂ -SiH ₄ series, etc. can be used as a starting material for forming the upper layer 205 . 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 normal cases, the thickness is preferably 30 to 1000 Å, preferably 50 to 600 Å. If a certain type of electrophotographic process is employed when the photoconductive member of the present invention is used as an electrophotographic imaging member, the free surface of the photoconductive member in the layer configuration shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer. 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, Polychloroethylene trifluoride, polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polybutene, polyvinyl butyral, polyurethane, polyparaxylylene, etc. Inorganic insulators such as organic insulators, silicon nitride, and silicon oxide, etc. may be mentioned. These synthetic resins or cellulose derivatives may be formed 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 , 10μ or more. However, the layer thickness differentiating between the protective layer and the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the designed structure of the imaging member.
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 (alumel-chromel). 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-
2,321,322 fully open, flow meter 3
The interiors of Nos. 16, 317, and 318 were also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 325, 32
After closing 6,327,320-2,321,322, SiF ₄ gas containing 10 vol% H ₂ (hereinafter referred to as SiF ₄ /H ₂
It is abbreviated as Purity 99.999%) Valve 3 of cylinder 311
30. Open the valve 331 of the _N2 gas (99.999% purity) cylinder 312, and check the outlet pressure gauges 335, 33.
Adjust the pressure of 6 to 1Kg/cm ² and open the inflow valve 320-
Open 2,321 to excess and install flow meter 31.
SiF ₄ /H ₂ gas and N ₂ 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 inflow valves 320 and 32 are adjusted so that the SiF ₄ /H ₂ gas flow rate and N ₂ gas flow rate ratio is 1:90.
1 was adjusted. 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 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 high frequency power supply 342.
Turn it ON and connect the induction coil 343 to 13.56MHz.
high-frequency power is applied to the chamber 30 of the coil section (upper chamber).
A glow discharge was generated within the battery, and the input power was 60W. 1 to deposit a layer on the substrate under the above conditions.
The conditions were maintained for minutes to form an intermediate layer. After that, the high frequency power supply 342 is turned off, and the outflow valve 326 is turned off with the glow discharge stopped.
closed and then diluted to 500vol ppm with _H2
B ₂ H ₆ gas (hereinafter abbreviated as B ₂ H ₆ /H _2. Purity 99.999
%) The valve 332 of the cylinder 313 was opened, the pressure of the outlet pressure gauge 337 was adjusted to 1 Kg/cm ² , and the inflow valve 322 was gradually opened to allow B ₂ H ₆ /H ₂ gas to flow into the flow meter 318. . Subsequently, the outflow valve 327 was gradually opened. At this time B ₂ H ₆ /H ₂
The inflow valves 320-2 and 322 were adjusted so that the gas flow rate and the SiF ₄ /H ₂ gas flow rate ratio were 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 mixture 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 Then, the inflow valves 320-2, 321, and 322 are closed, and the main valve 310 is fully opened to drain the inside of the chamber 301.
After reducing the pressure to 10 ^-5 torr or less, the main valve 310 was closed, 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 these 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 electrostatic exposure experimental apparatus 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
Intermediate layer film deposition rate: 1Å/sec
Example 3 When forming an intermediate layer on a molybdenum substrate
The SiF ₄ /H ₂ gas flow rate and N ₂ gas flow rate ratio are
Image forming members indicated by sample numbers ~ were prepared under the same conditions and procedures as in Example 1, except for making various changes as shown in the table, and the charging exposure experiment equipment was used in exactly the same manner as in Example 1. When similar image formation was carried out using the same method, the results shown in Table 2 below were obtained.
Sample No. ~ was analyzed by Augier electron spectroscopy, and the results shown in Table 3 were obtained. From the results in Tables 2 and 3, in order to achieve the purpose of the present invention, the composition ratio x of Si and N in the intermediate layer is
It must be formed within the range of 0.43 to 0.60.

【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, and then the SiF ₄ /H ₂ N ₂ gas inflow system was heated to 5×10 ^-6 torr by the same operation as in Example 1.
vacuum and then the auxiliary valve 340 and each outflow valve 325, 326 each inflow valve 320-
After closing 2,321, SiF ₄ /H ₂ gas cylinder 3
Open the valve 330 of No. 11 and the valve 331 of the N ₂ gas cylinder 312, and check the outlet pressure gauges 335, 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 /H ₂ gas and N ₂ 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 inflow valves 320-2 and 3 are adjusted so that the SiF ₄ /H ₂ gas flow rate and N ₂ gas flow rate ratio is 1:90.
21 was adjusted. 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 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. 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 the intermediate layer on the substrate while maintaining the conditions, the high frequency power source 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, 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, PH ₃ gas (hereinafter abbreviated as PH ₃ /H ₂ , purity 99.999%) diluted with H ₂ to 250 vol ppm cylinder 314
The valve 333 was opened to adjust the pressure of the outlet pressure gauge 338 to 1 Kg/cm ^{2 ,} and the inflow valve 323 was gradually opened to allow PH ₃ /H ₂ gas to flow into the flow meter 319 . Subsequently, the outflow valve 328 was opened to them. At this time, PH ₃ /H ₂ gas flow rate and SiF ₄ /H ₂
Inlet valve 320 so that the gas flow ratio is 1:60
-Adjusted 2,323. 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 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is reduced to 10 ^-5 torr or less. After that, 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 heated. I took it out. In this case, the total thickness of the formed layer is approximately
It was 11μ. The image forming member thus obtained is
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, the image quality was superior to that formed by corona discharge and was extremely clear. It was hot. 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, when subsequently forming a photoconductive layer, the B ₂ H ₆ /H ₂ gas flow rate was set to 1/15 of the SiF ₄ /H ₂ gas flow rate. An intermediate layer and a photoconductive layer were formed on a molybdenum substrate under the same conditions and procedures as in Example 1. 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 to images formed by corona discharge, and they were 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 using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 8 ITO was deposited to a thickness of 1000 Å by electron beam evaporation and placed on the fixing member 303 of the same device as in Example 1 (FIG. 3) with the ITO deposition surface facing downward. 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. ,327,3
29 and inflow valve 320-2, 322, 324
Fully open, flow meters 316, 318, 32
The interior of 0-1 was also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 326, 327, 329, 31
After closing 7,318,320-2, 10vol with _H2
% diluted NH ₃ gas (hereinafter abbreviated as NH ₃ /H _2. Purity 99.999%) cylinder 315 valve 334,
Open the valve 330 of the SiF ₄ /H ₂ gas cylinder 311, adjust the pressure on the outlet pressure gauge to 1Kg/cm ² , and gradually open the inflow valves 320-2, 324 to allow SiF ₄ /H into the flow meters 316, 320-1. ₂ gas,
NH ₃ /H ₂ gas was introduced. Subsequently, the outflow valves 325, 329 and then the auxiliary valve 340 were gradually opened. At this time, the SiF ₄ /H ₂ gas flow rate and
The inflow valves 320-2 and 324 were adjusted so that the NH ₃ /H ₂ gas flow ratio was 1:20. 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 chamber 301 is stabilized, the main valve 3
10 was gradually closed, and the aperture was narrowed until the reading on the Pirani gauge 341 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the switch of the high frequency power supply 342 is turned on and 13.56 MHz high frequency power is applied to the induction coil 343 to supply the inside of the chamber 301 in the coil section (upper part of the room). A glow discharge was generated and the input power was 60W. After forming the intermediate layer under the same conditions for 1 minute, the high frequency power source 342
When the is turned off and the glow discharge is stopped,
After a while, the outflow valve 329 and the inflow valve 32
4 was closed, and 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 set to 60W, the same as when forming the intermediate layer.
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 3
25 and inflow valves 320-2, 324,
The main valve 310 is fully opened and the inside of the chamber 301 is
After reducing the pressure to below 10 ^-5 torr, the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 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 is placed in a charging exposure experiment device,
Corona charging was performed at 5.5 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. 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 (alumel-chromel). Next, after confirming that all valves in the system were closed, the main valve 429 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, 415, 416, 411,
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 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, check the auxiliary valve 427.
The auxiliary valve 427 was opened until the pressure inside the chamber 401 reached 1×10 ⁻⁴ torr. After the internal pressure of the chamber 401 became stable, the main valve 429 was gradually closed and the opening was throttled until the Pirani gauge 430 indicated 1×10 ⁻² torr. Shutter 40 by operating the shutter rod 403
8, and after confirming that the flow meters 425 and 424 are stable, turn on the high frequency power supply 431.
13.56MHz between the target 404 made of polycrystalline high purity Si ₃ N ₄ and the fixing member 406.
100W AC power was input. Under these conditions, the layers were formed while performing matching so that stable discharge could continue. Continue discharging in this way for 2 minutes.
A 100 Å thick a-Si _x N _1-x :F was formed. Thereafter, the high frequency power source 431 was turned off to temporarily stop the discharge. After closing the cylinder valves 412 and 413 and fully opening the main valve 429 to create a vacuum in the chamber 401 and flow meters 424 and 425 to 10 ^-5 torr, the auxiliary valve 427 and the outflow valve 41 are closed.
8,419, inlet valves 415,416 were closed. SiF ₄ gas cylinder 410 containing 10vol% _H2
It was changed to SiF ₄ /H ₂ gas (99.999%). Inflow valve 416, outflow valve 419, auxiliary valve 427
After opening the chamber 401 and evacuating the inside of the chamber 401 to 5×10 ^-7 torr, close the inflow valve 416 and outflow valve 419, open the valve 413 of the cylinder 410, adjust the pressure of the outlet pressure gauge 422 to 1 Kg/cm ² , and then valve 41
Gradually open 6 and enter the flow meter 425.
SiF ₄ /H ₂ gas was introduced. Subsequently, the outflow valve 419 was gradually opened. Then 500vol with _H2
Open the valve 414 of the B ₂ H ₆ /H ₂ gas cylinder 411 diluted to ppm, and the pressure on the outlet pressure gauge 423 is 1.
Kg/cm ² , and the inflow valve 417 was gradually opened to allow B ₂ H ₆ /H ₂ 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 41 are adjusted so that the SiF ₄ /H ₂ gas flow rate and B ₂ H ₆ /H ₂ gas flow rate ratio is 70:1.
7 was adjusted. Next, while paying close attention to the reading on the Pirani gauge 430, check the auxiliary valve 427 and the main valve 4.
29 was adjusted and the aperture was narrowed down until the reading on the Pirani gauge 430 was 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, operate the shutter rod 403 to double as the shutter electrode 4
08, then turn on the switch of the high frequency power source 437, and turn on the electrode 407 and shutter 40.
13.56MHz high frequency power was applied to room 401.
A glow discharge was generated inside the device, resulting in an input power of 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 407 is turned off,
After waiting for the substrate temperature to reach 100°C, the outflow valves 419, 420 and the inflow valves 415, 41
6,417 was closed and the main valve 429 was fully opened to bring the inside of the chamber 401 to 10 ^-5 torr or less.The main valve 429 was then 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 irradiated with a light intensity of 0.8 lux·sec 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 50KV 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, the high frequency power source 431 and heating heater 407 were turned off, and the outflow valves 418 and 419 and the inflow valve 415 were turned off. , 416, wait until the substrate temperature reaches 100℃, and then close 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, and the target 404 was changed from a high-purity SiN ₄ target to a high-purity polycrystalline silicon target. 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 valve 427 and the outflow valves 418, 419 to fully deaerate the inside of the flow meters 424, 425, and then open the outflow valves 418, 419 and the auxiliary valve 4.
27 closed. The heater 4 heats the substrate 402 again.
07 was turned on and the substrate temperature was maintained at 200°C.
Then, open the valve 413 of the SiF ₄ gas (purity 99.999%) cylinder 410 and the valve 412 of the Ar gas cylinder 409, adjust the pressure of the outlet pressure gauges 422, 421 to 1 Kg/cm ² , and inflow valves 416, 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 are gradually opened,
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 indication 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 the discharge for 3 hours to form a photoconductive layer, 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 the inflow Valve 415,4
16 and fully open the main valve 429.
After reducing the inside of the chamber 401 to 10 ^-5 torr or less, the main valve 429 is closed and the inside of the chamber 401 is closed with a leak valve 428.
The substrate was taken out at atmospheric pressure. 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 5.5 KV for 0.2 seconds, and immediately exposed to 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 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 6.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 11 Six image forming members were formed using the same operations and conditions as in Example 1, and were firmly fixed to a fixing member 406 in the apparatus shown in FIG. 4 with the photoconductive layer facing down.
A substrate 402 was used. Upper layers A to F to be formed on the photoconductive layer were formed on each substrate under the conditions shown in Table 4, and six image forming members having each upper layer were formed. When forming the upper layer A by the sputtering method, the target 404 is a polycrystalline silicon target with a partially laminated graphite target, and when forming the upper layer E, an Ar gas cylinder 409 is used. Changed to _N2 gas cylinder diluted to 50% with Ar. In addition, when forming the upper layer B by the glow discharge method, the Ar gas cylinder 409 is replaced with the SiH ₄ gas cylinder diluted to 10 vol% with H ₂ and the B ₂ H ₆ gas cylinder 411.
into a _C2H4 gas cylinder diluted to _10vol % with _H2 ,
When forming the upper layer C, a B ₂ H ₆ gas cylinder 41 is used.
When forming the upper layer D in the Si(CH ₃ ) ₄ cylinder in which 1 is diluted to 10 vol% with H ₂ , the B ₂ H ₆ gas cylinder 411 is mixed with C ₂ H in the same way as in the formation of the upper layer B. ₄ gas cylinder, Ar gas cylinder 409, H ₂ 10vol%
When forming the upper layers F and G in the SiF ₄ gas cylinder containing SiF 4 gas cylinder 410, the SiF ₄ gas cylinder 410 was heated with H ₂ for 10

[Table] The SiH ₄ gas cylinder diluted to vol% and the Ar gas cylinder 409 were replaced with N ₂ gas cylinder and NH ₃ gas cylinder diluted with H ₂ to 10 vol%. Six image forming members each having the same intermediate layer and photoconductive layer as in Example 1 and upper layers A to F shown in Table 4 were subjected to image formation under the same operations and conditions as in Example 1 to form a transfer paper. When the toner image was transferred to a 3D printer, an extremely clear toner image was obtained. Example 12 Six image forming members were prepared using the same operations and conditions as in Example 8, and were firmly fixed to a fixing member 406 with the photoconductive layer facing down in the apparatus shown in FIG. did. The upper layer formed on the photoconductive layer was formed in the same manner as in Example 11. Six image forming members having upper layers A to F shown in Table 4 were each subjected to the same operations as in Example 1,
When an image was formed under these conditions and transferred to transfer paper, an extremely clear toner image was obtained. Example 13 Six image forming members were formed using the same operations and conditions as in Example 10, and were firmly fixed to a fixing member 406 with the photoconductive layer facing down in the apparatus shown in FIG. It was set to 402. Six image forming members each having upper layers A to F shown in Table 4, each having an upper layer formed on the photoconductive layer formed in the same manner as in Example 11, were imaged under the same operating conditions as in Example 1. When the toner images were formed and transferred to transfer paper, extremely clear toner images were obtained that were independent of charging polarity.

[Brief explanation of drawings]

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 being injected 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; The photoconductive member is characterized in that the intermediate layer is made of an amorphous material whose constituent elements are silicon atoms, nitrogen atoms, and halogen atoms, and has a layer thickness of 30 to 1000 Å. Photoconductive member. 2. The upper surface of the photoconductive layer is made of an amorphous material that has silicon atoms as its base material and includes at least one of hydrogen atoms and halogen atoms, and at least one of carbon atoms, nitrogen atoms, and oxygen atoms. A photoconductive member according to claim 1, having a top layer of 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.