JPS6335979B2 - - 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 photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc., they are highly sensitive and have a high signal-to-noise ratio [photocurrent (Ip)/ It has a high dark current (Id), has the spectral characteristics of the irradiated electromagnetic waves, has good photoresponsiveness, has the desired dark resistance value, is non-polluting to the human body during use, and The imaging device is required to have characteristics such as 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 a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as weather resistance and moisture resistance. There are points that can be further improved in terms of usage environment characteristics such as performance, and practical solid-state imaging devices, reading devices, electrophotographic image forming members, etc. need to be improved in terms of productivity and mass production. The reality is that it cannot be used effectively by taking into account the situation. For example, when applied to electrophotographic image forming members or solid-state imaging devices, it is often observed that residual potential remains during use, and when such photoconductive members are used repeatedly for a long time, There are many disadvantages such as accumulation of fatigue due to repeated use and so-called ghost development, which causes afterimages. Furthermore, according to many experiments conducted by the present inventors, for example, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member can be replaced with conventional Se, CdS, ZnO, or OPC such as PVCz or TNF. An electrophotographic image having a single-layer photoconductive layer made of a-Si, which has many advantages compared to (organic photoconductive members), but also has properties suitable for use in conventional solar cells. Even if the photoconductive layer of the forming member is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotographic methods;
The above tendency is remarkable in a humid atmosphere.
It has been found that there are some problems that can be solved, such as in some cases, the charge cannot be retained at all until the development time. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to obtain desired electrical, optical, and photoconductive properties when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms An amorphous material containing halogen atoms as a matrix, 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 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 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
H _1-Y (however, 0.1≦X≦0.35, 0.65≦Y≦0.98), composed of amorphous material, 30 to 1000
It is characterized by having a layer thickness of 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, optical, photoconductive properties, and use environment characteristics. . In particular, when applied as an image forming member for electrophotography or an imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has good electrical properties even in a humid atmosphere. It is stable, has high sensitivity, and has a high signal-to-noise ratio, and has excellent resistance to light fatigue and repeated use. Furthermore, in the case of electrophotographic image forming members, it has a high density and clear halftones. Moreover, it is possible to obtain a high-quality visible image with 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. However, in the case of the present invention, even the a:Si:X layer with relatively low resistance (5×10 ⁹ Ωcm or more) can not be applied to electrophotographic image forming members as it is. 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 conductive, electrical, or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, Ir, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is subjected to a photoconductive treatment, and another layer is preferably provided on the electrically conductive 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 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 appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. Within this range, it is made as thin as possible. However, in such a case, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The intermediate layer 102 is a non-photoconductive amorphous material [a-( _SixC1 -x)y:H1-y abbreviated as a-( _SixC1-x ) _y :H1 _-y] that has silicon atoms and carbon atoms as a matrix and contains hydrogen atoms.
However, 0<x<1, 0<y<1], which effectively prevents carriers from flowing into the photoconductive layer 103 from the support 101 side and prevents the photoconductive layer 103 from being irradiated with electromagnetic waves. a photoconductive layer 103 of photocarriers occurring in the interior and moving towards the side of the support 101;
It has a function of easily allowing passage from the side to the support body 101 side. a-(Si _x C _1-x ) _y : Intermediate layer 10 composed of H _1-y
The shape No. 2 is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method or the sputtering method has advantages such as relatively easy control of manufacturing conditions for manufacturing a photoconductive member having silicon atoms, and ease of introducing carbon atoms and hydrogen atoms together with silicon atoms into the intermediate layer to be manufactured. The Tuttering method is preferably employed. Furthermore, in the present invention, the intermediate layer 102 may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the intermediate layer 102 by glow discharge, the raw material gas for forming a-(Si _x C _1-x ) _y :H _{1-y is}
If necessary, it is mixed with a dilution gas at a predetermined mixing ratio and 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. The support 1
It is sufficient to deposit a(Si _x C _1-x ) _y :H _1-y on 01. In the present invention, the raw material gas for forming a-(Si _x C _1-x ) _y :H _1-y is a gaseous substance containing at least one of Si, C, and H as a constituent atom, or Most of the gasified substances that can be gasified are used. When using a raw material gas containing Si as one of Si, C, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si and a raw material gas containing C and H may be mixed at a desired mixing ratio. or with a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and H. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, gases effectively used as raw material gases for forming the intermediate layer 102 include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. whose constituent atoms are Si and H. silicon hydride gas such as silanes, saturated hydrocarbons containing C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 1 to 4 carbon atoms, and 2 to 4 carbon atoms. Examples include acetylene hydrocarbons. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _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 the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these raw material gases, H
Of course, H ₂ is also effectively used as the raw material gas for introduction. To form the intermediate layer 102 by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are treated with various gases. This can be done by sputtering in an atmosphere. For example, if a Si wafer is used as a target, the raw material gas for introducing C and H is diluted with diluting gas as necessary, and introduced into a deposition chamber for sputtering to create a gas plasma of these gases. The Si wafer may be sputtered after forming the Si wafer. Alternatively, sputtering can be carried out in a gas atmosphere containing at least H atoms by using a target other than Si and C or by using a single target containing a mixture of Si and C. It is accomplished by doing so. As the raw material gas for introducing C or H, the raw material gas shown in the glow discharge example described above can be used as an effective gas also in the case of 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,
Preferable examples include Ne, Ar, and the like. The intermediate layer 102 in the present invention is carefully formed to provide the desired properties. In other words, materials whose constituent atoms are Si, C, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. and the properties between photoconductive and non-photoconductive properties,
Therefore, in the present invention, the preparation conditions are strictly selected so that non-photoconductive a-(Si _x C _1-x ) _y :H _1-y is formed. . a (Si _x C _1-x ) constituting the intermediate layer 102 of the present invention
_y : H _1-y indicates that the function of the intermediate layer 102 is the function of the support 101
The photoconductive layer 103 must be able to prevent carriers from being injected into the photoconductive layer 103 from the side, and easily allow the photocarriers generated in the photoconductive layer 103 to move and pass to the support 101 side. It is formed from a material that exhibits electrically insulating behavior. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, it has a mobility value with respect to the carrier that passes through the intermediate layer 102 smoothly.
−(Si _x C _1-x ) _y : H _1-y is created. a-(Si _x C _1-x ) _y : H _1-y with the above characteristics
An important factor in the production conditions for production is the temperature of the support during production. That is, on the surface of the support 101, a-(Si _x C _1-x ) _y :
When forming the intermediate layer 102 consisting of H _1-y , the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. a-(Si _x C _1-x ) _y having the property of:
The support temperature during layer formation is strictly controlled so that H _1-y can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the intermediate layer 102 is appropriately selected in an optimal range in accordance with the method of forming the intermediate layer 102. is executed, but
Normally 100℃~300℃ Preferably 150℃~250℃
It is desirable that this is the case. Middle layer 102
For forming each layer, each layer can be formed successively in the same system from the intermediate layer 102 to the photoconductive layer 103, and further, if necessary, the third layer formed on the photoconductive layer 103. The glow discharge method and sputtering method are advantageous because it is relatively easy to finely control the composition ratio of atoms and control the layer thickness compared to other methods. When forming the intermediate layer 102 using a layer forming method such as a-(Si _x C _1-x ) _y : It is one of the important factors that influences the properties of H _1-y . The discharge power conditions for effectively forming a-(Si _x C _1-x ) _y :H _1-y with good productivity to achieve the purpose of the present invention are as follows: Normal 1
~(300)W, preferably 2~(150)W. 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 hydrogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are as follows:
Similar to the manufacturing conditions of No. 02, this is an important factor in forming an intermediate layer that provides the desired properties to achieve the object of the present invention. The amount of 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 ~80 atomic%.
The content of hydrogen atoms is usually 2~
It is desirable that the hydrogen content be 35 atomic %, preferably 5 to 30 atomic %, and photoconductive members formed when the hydrogen content is in this range can be sufficiently applied as being excellent in practice. It is something. That is, if expressed as a-(Si _x C _1-x ) _y :H _1-y above, x is usually 0.1 to 0.35, preferably 0.15 to 0.30,
y is usually 0.98 to 0.65, preferably 0.95 to 0.70. The numerical range of the layer thickness of the intermediate layer 102 in the present invention is one of the important factors for effectively achieving the object of the present invention. If the layer thickness of the intermediate layer 102 is too thin, it will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the support 101 side, and if it is too thick, , the probability that photocarriers generated in the photoconductive layer 103 will pass to the side of the support 101 becomes extremely small, and therefore, in both cases, the object of the present invention cannot be effectively achieved. Intermediate layer 1 for effectively achieving the object of the present invention
The layer thickness of 02 is usually 30 to 1000 Å, preferably 50 to 600 Å. In the present invention, in order to effectively achieve the purpose, a photoconductive layer 10 laminated on an intermediate layer 102 is used.
3 is a-Si:X having the semiconductor properties shown below.
Consists of. 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 lightly doped with a so-called p-type impurity having a low acceptor concentration (Na). n-type a-Si:X... Contains only Doto.
Or one that contains both donor and acceptor and has a high concentration of donor (Nd). The donor concentration (Nd) is low in the n-type a-Si:X type. Lightly doped with so-called n-type impurities. i-type a-Si:X...NaNdO or NaNd. 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 better results, the dark resistance of the photoconductive layer 103 to be formed is preferably 5×10 ⁹ Ωcm or more, most preferably 10 ¹⁰ Ωcm.
It is desirable that the photoconductive layer 103 be formed as described above. In particular, this numerical condition 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 illuminance region, or a light guide conversion device. This is an important element when doing so. The layer thickness of the photoconductive layer of the photoconductive layer member in the present invention is appropriately determined according to the purpose of the application, such as a reading device, a solid-state imaging device, or an electrophotographic image forming member. . In the present invention, the layer thickness of the photoconductive layer is as follows:
The thickness relationship between the photoconductive layer and the intermediate layer can be appropriately determined as desired so that the functions of the photoconductive layer and the intermediate layer can be effectively utilized and the objects of the present invention can be effectively achieved. In normal cases, the layer thickness is preferably several hundred to several thousand times or more than the thickness of the intermediate layer. A specific value is usually 1 to 100μ, preferably 2 to 50μ. In the present invention, 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 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 raw material gas for introducing halogen 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, 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 made 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 halogen silicon gas, which is a raw material gas for Si generation, and a gas such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio. and the gas flow rate is a-
An intermediate layer 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. a-Si in contact with:
Although it is possible to form a photoconductive layer consisting of
A layer may 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, Si
In the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is This can be done by heating and evaporating the material 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, gaseous or gasifiable halides containing 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 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, the raw material gas for halogen introduction and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, a layer consisting of a-Si:X into which H is introduced is formed on the surface of the support having predetermined characteristics. Furthermore, B ₂ H ₆ , which also serves as impurity doping,
It is also possible to introduce a gas such as PH 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. In order to make the photoconductive layer n-type or p-type, a layer containing an n-type lower impurity, a p-type impurity, or both impurities is formed during layer formation by a glow discharge method, a reactive sputtering method, etc. This is achieved by controlling the amount of doping inside. In order to make the photoconductive layer p-type, suitable impurities doped into the photoconductive layer include elements of group A of the periodic table, such as B, Al, Ga, In, and Tl. In the case of n-type, elements of group A of the periodic table, such as N, P,
Preferred examples include As, Sb, Bi, and the like.
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. is preferable. From this point of view, considering the electrical and optical properties of the layer to be formed, for example, B, Ga, P, Sb
etc. is optimal. 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 impurities doped into the photoconductive layer is appropriately determined depending on the desired electrical and optical properties, and
In the case of impurities, typically 10 ^-6 to ^{10 -3} atomic%,
Preferably 10 ^-5 to 10 ^-4 atomic%, Group A of the periodic table
Usually 10 ^-8 to ^{10 -3} atomic%, preferably
It is desirable that it be 10 ^-8 to 10 ^-4 atomic%. FIG. 2 shows a schematic configuration diagram for explaining the configuration of another embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 is similar to the photoconductive member 100 shown in FIG. 1 except that an upper layer 205 having the same function as the intermediate layer 202 is provided on the photoconductive layer 203 It has a layered structure. That is, the photoconductive member 200 has a-(Si _x
C _1-x ) _y : Light composed of an intermediate layer 202 formed to have the same function using H _1-y and a-Si:X into which H is introduced as necessary. conductive layer 2
03 and an upper layer 205 disposed on the photoconductive layer 203 and having a free surface 204. When the upper layer 205 is used, for example, when the free surface 204 of the photoconductive member 200 is subjected to charging treatment to form a charge image, the charge that can be held on the free surface 204 is transferred to the photoconductive layer 203. photocarriers generated in the photoconductive layer 203 when irradiated with electromagnetic waves;
It has a function of easily allowing photo carriers or charged charges to pass through so as to cause recombination with the charged charges in the area irradiated with electromagnetic waves. The upper layer 205 is composed of a-(Si _x C _1-x ) _y :H _1-y having the same characteristics as the middle layer 202 .
Si _x C _1-x , a-Sia _{N 1-a} , (a-Sia _{N 1-a} ) _b :H _1-b ,
a-Si _c O _1-c , (a-Si _c O _1-c ) _d : Composed of silicon atoms and nitrogen atoms or oxygen atoms, which are the host atoms constituting the photoconductive layer such as H _1-d. Alternatively, it can also be composed of an amorphous material having these atoms as a matrix and containing a halogen atom, an inorganic insulating material such as Al ₂ O ₃ , or an organic insulating material such as polyester, polyparaxylylene, or polyurethane. However, the material constituting the upper layer 205 is a-(Si), which has the same characteristics as the intermediate layer 202 from the viewpoint of productivity, mass production, and electrical and usage environment stability of the formed layer. _x C _1-x ) _y : It is desirable to be composed of H _1-y or a-Si _x C _1-x that does not contain a hydrogen atom. In addition to the materials listed above, suitable materials for forming the upper layer 205 include silicon atoms and at least two atoms among C, N, and O, and halogen atoms or halogen atoms. Examples include amorphous materials containing hydrogen atoms and hydrogen atoms. Examples of the halogen atom include F, Cl, Br, etc. Among the above amorphous materials, those containing F are effective from the viewpoint of thermal stability. The selection of the material constituting the upper layer 205 and the determination of its layer thickness are carried out from the upper layer 205 side to the photoconductive layer 203.
When using the photoconductive member 200 in such a way as to irradiate electromagnetic waves that are sensitive to will be accomplished. 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 ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of starting materials for 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 ), dinitrogen monoxide (N ₂ O), and the like. 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, C ₂ H ₅ Cl, SF ₄ , SF ₆
Fluorinated sulfur compounds such as Si(CH ₃ ) ₄ , Si
Alkyl silicides such as (C ₂ H ₅ ) ₄ and SiCl (CH ₃ ) ₃ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These starting materials for forming the upper layer 205 include predetermined atoms as constituent atoms of the upper layer 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, it is determined as desired depending on the material constituting the layer, the layer formation conditions, etc. The layer thickness of the upper layer 205 in the present invention is as follows:
Usually, the thickness is preferably 30 to 1000 Å, preferably 50 to 600 Å. If a certain type of electrophotographic process is employed when the photoconductive member of the present invention is used as an electrophotographic imaging member, the free surface of the photoconductive member has a layer configuration as shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer on top. In this case, the surface coating layer is, for example,
If an electrophotographic process such as the NP method described in Publications No. 23910 and No. 43-24748 is applied, it must be electrically insulating and have a low ability to retain static charge when subjected to charging treatment. Although it is required to have sufficient thickness and a certain level of thickness, for example, if an electrophotographic process such as the Carlson process is to be applied, it is desirable that the bright and dark potentials after electrostatic image formation be very small. The surface coating layer is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer must not have any adverse chemical or physical effects on the photoconductive layer or the top layer, and must not be in electrical contact with the photoconductive layer or the top layer. Wearability, moisture resistance, abrasion resistance,
It is formed in consideration of cleaning properties, etc. Typical materials effectively used for forming the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Organic insulators such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride 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 0.7 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, it is usually 10μ or less, and conversely, when it is required to function as an electrical insulating layer, it is usually It is considered to be 10μ or more. However, the layer thickness value that differentiates the protective layer from 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) 302 whose surface had been cleaned was firmly fixed to a fixing member 303 at a predetermined position in the glow discharge deposition chamber 301 . The substrate 302 is heated with an accuracy of ±0.5° C. by a heater 304 inside the fixing 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 312 is fully opened, and the chamber 301 is closed.
The inside was evacuated to a vacuum level of approximately 5×10 ^-6 torr.
Thereafter, the input voltage to the heater 304 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 309, then the outflow valves 313, 319, 331, 337, and the inflow valves 315, 321, 333, 339 were fully opened, and the insides of the flow meters 314, 320, 332, and 338 were also sufficiently degassed and vacuumed. . Auxiliary valve 30
9, Valve 313, 319, 331, 337, 3
After closing 15,321,333,339, H _2
SiH4 gas (purity 99.999%) diluted to 10vol% with
Valve 335 of cylinder 336, valve 341 of C ₂ H ₄ gas cylinder 342 diluted to 10 vol% with H ₂
and set the pressure on the outlet pressure gauges 334, 340 to 1.
Kg/cm ² and gradually open the inflow valves 333 and 339 to enter the flow meters 332 and 338.
SiH ₄ gas and C ₂ H ₄ gas were introduced. Subsequently, the outflow valves 331 and 337 were gradually opened, and then the auxiliary valve 309 was gradually opened. At this time SiH ₄
The inflow valves 333 and 339 were adjusted so that the ratio of gas flow rate to C ₂ H ₄ gas flow rate was 1:9. Next, while watching the reading on the Pirani gauge 310, adjust the opening of the auxiliary valve 309 so that the inside of the chamber 301 is 1×.
Auxiliary valve 309 was opened until 10 ^-2 torr was reached. After the internal pressure of the chamber 301 becomes stable, the main valve 312
gradually close the Pirani gauge 310 until the indication is
The aperture was narrowed down to 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, and that the shutter is closed, the high frequency power source 308 is turned on and the electrode 30 is turned on.
3,307, high frequency power of 13.56MHz was applied to generate a glow discharge in the chamber 301, resulting in an input power of 3W. a-(Si _x C _1-x ) on the substrate under the above conditions.
_y : In order to deposit H _1-y , the conditions were maintained for 1 minute to form an intermediate layer. After that, turn on the high frequency power supply 308.
In the off state and with the glow discharge stopped,
After closing the outflow valves 331 and 337 and further closing the auxiliary valve 309, the main valve 312 was fully opened to remove gas from the chamber 301 and create a vacuum of 5×10 ⁻⁷ torr. Next, the valve 317 of the (SiF ₄ ) gas (purity 99.999%) cylinder 318 containing 10 vol% of H ₂ gas _,
32 B ₂ H ₆ gas cylinders diluted to 500 volppm with
4 valve 323 is opened, the outlet pressure gauge 316,
Adjust the pressure of 322 to 1Kg/cm ² and open the inflow valve 31.
5, 321 gradually open and flow meter 31
SiF ₄ gas and B ₂ H ₆ gas were flowed into 4,320. Subsequently, the outflow valves 313 and 319 were gradually opened, and then the auxiliary valve 309 was gradually opened. At this time, the SiF ₄ gas flow rate and B ₂ H ₆ gas flow rate ratio is
The inflow valves 315 and 321 were adjusted so that the ratio was 70:1. Next, while watching the reading on the Pirani gauge 310, adjust the opening of the auxiliary valve 309 until the inside of the chamber 301 reaches 1×10 ^-2 torr.
I opened 09. After the internal pressure of the chamber 301 became stable, the main valve 312 was gradually closed and the opening was throttled until the reading on the Pirani gauge 310 reached 0.5 torr.
After confirming that the gas inflow is stable and the internal pressure is stable, and that the shutter 307 is closed, turn on the high frequency power supply 308 and apply 13.56MHz high frequency power between the electrodes 303 and 307. A glow discharge was generated in the charging chamber 301, and the input power was 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power supply 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 313, 319 and Inflow valve 31
5, 321, 333, and 339, and fully open the main valve 312 to reduce the inside of the chamber 301 to 10 ^-5 torr or less, then close the main valve 312 and open the main valve 312.
The inside of the chamber was brought to atmospheric pressure using a leak valve 311, 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 exposed to 6.0KV.
Corona charging was performed for 0.2 seconds, and a light image was immediately irradiated. The optical image is created using a tungsten lamp light source.
A light intensity of 0.8 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) onto the surface of the member. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the image forming member was corona charged for 0.2 seconds at 5.5 KV using a charging exposure experiment device, and then imagewise exposed at a light intensity of 0.8 lux・sec, and then a charging developer was immediately applied. When cascaded onto the surface of the component and then transferred and fixed onto transfer paper,
An extremely clear image was obtained. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 2 The glow discharge holding time when forming an intermediate layer on a molybdenum substrate was as shown in Table 1 below.
Except for various changes, image forming members indicated by Sample No. ~ were prepared under the same conditions and procedures as in Example 1, and were placed in the same charging exposure experimental apparatus as in Example 1. When images were formed, the results shown in Table 1 below were obtained. As can be seen from the results shown in Table 1, in order to achieve the object of the present invention, the thickness of the intermediate layer must be between 30 Å and 100 Å.
It is necessary to form within the range of .

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes ×: Impossible
Intermediate layer film deposition rate: 1Å/sec
Example 3 The conditions were exactly the same as in Example 1, except that the flow rate ratio of SiH ₄ and C ₂ H ₄ in the intermediate layer was varied as shown in Table 2 when forming the intermediate layer on the molybdenum substrate. The image forming members shown in Samples No. 9 to 15 were prepared according to the above procedure, and were installed in the same charged exposure experimental apparatus as in Example 1 to perform the same image formation. The results shown are obtained. In addition, sample No.
Table 3 shows the results of analyzing only the intermediate layers Nos. 11 to 15 by electron microprobe method and hydrogen gas mass spectrometry method generated by heating. As can be seen from the results shown in Tables 2 and 3, x, which is related to the composition ratio of Si and C in the intermediate layer, must be
It is necessary to form it in the range of 0.50 to 0.1.

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

[Table] Example 4 After forming an intermediate layer according to the same conditions and procedures as in Example 1, the valve 335 of the cylinder 336 and the valve 341 of the cylinder 342 were closed to remove the gas in the chamber 301 ^. Vacuum was applied to ⁷ torr. After that, the auxiliary valve 309, the outflow valves 331, 33
7. After closing the inflow valves 333 and 339,
_SiF4 gas containing 10vol% _H2 gas (99.999% purity)
Open the valve 317 of the cylinder 318, adjust the pressure of the outlet pressure gauge 316 to 1 kg/cm ² , and open the inlet valve 3.
Gradually open 15 and enter the flow meter 314.
SiF ₄ gas was introduced. Subsequently, the outflow valve 3
13 was gradually opened, and then the auxiliary valve 309 was gradually opened. Next, the opening of the auxiliary valve 309 was adjusted while observing the reading on the Pirani gauge 310, and the auxiliary valve 309 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 312 was gradually closed and the opening was throttled until the reading on the Pirani gauge 310 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 307 is closed, and then the high frequency power source 308 is turned on and 13.56 MHz high frequency power is applied (between the electrodes 307 and 303). A glow discharge was generated within the battery, resulting in an input power of 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 304 is turned off,
The high frequency power supply 308 is also turned off, and the substrate temperature is 100℃.
℃, close the outflow valve 313 and inflow valve 315, and fully open the main valve 312 to reduce the temperature inside the chamber 301 to 10 ^-5 torr or less.
The main valve 312 was closed, and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, 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 prepared in Example 1.
When we formed an image on transfer paper following the same procedure as above, we found that it was better to form an image using corona discharge.
The image quality was superior to images formed by corona discharge and was extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 5 After forming an intermediate layer on a molybdenum substrate for 1 minute and forming a photoconductive layer for 5 hours under the same conditions and procedures as in Example 1, the high frequency power source 308 was turned on.
In the off state, the glow discharge is stopped.
Close the outflow valves 313, 319 and again.
The outflow valves 331 and 337 were opened 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 3W, the same as when forming the intermediate layer. After continuing the glow discharge for 2 minutes to form an upper layer on the photoconductive layer, the heating heater 304 is turned off, and the high frequency power source 308 is also turned off.
After setting the off state and waiting for the substrate temperature to reach 100°C, open the outflow valves 331, 337 and the inflow valve 3.
33 and 339 were closed and the main valve 312 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less.The main valve 312 was then closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. The image forming member thus obtained was placed in the same charging exposure experiment apparatus as in Example 1, and was heated at 6.0 KV.
Corona charging was performed for 0.2 seconds, and a light image was immediately irradiated. Light guidance uses a tungsten lamp light source,
A light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the 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 6 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1,
The deposition chamber was evacuated to 5×10 ⁻⁷ torr, and SiF ₄ gas was introduced into the chamber in the same manner as in Example 1. after that
32 B ₂ H ₆ gas cylinders diluted with H ₂ to 500 volppm
4 through the inflow valve 321 to the flow meter 320 at a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 322), and by adjusting the outflow valve 319, the reading of the flow meter 320 becomes equal to the flow rate of SiF ₄ gas. The opening of the outflow valve 319 was determined to be 1/15 and stabilized. Subsequently, the shutter 307 was closed and the high frequency power supply 308 was turned on again to restart the glow discharge. The input power at that time was 60W.
After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power source 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 304 is turned off.
13, 319 and inflow valves 315, 321, and fully open the main valve 312, the chamber 301
After reducing the internal pressure to 10 ^-5 torr or less, the main valve 312
The chamber 301 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 10μ. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1. The image quality was excellent and extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 7 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1,
The deposition chamber was evacuated to 5×10 ⁻⁷ torr, and SiF ₄ gas was introduced into the chamber in the same manner as in Example 1. after that
330 PF ₅ gas cylinder diluted to 250 volppm with _H2
Gas is supplied to the flow meter 326 through the inflow valve 327 at a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 328), and by adjusting the outflow valve 325, the reading of the flow meter 326 becomes 1 kg/cm 2 of the flow rate of SiF ₄ gas. The opening of the outflow valve 325 was set so that the angle was /60, and the opening was stabilized. Subsequently, the shutter 307 was closed and the high frequency power supply 308 was turned on again to restart the glow discharge. The input voltage at that time was 60W.
After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power source 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 3
13, 325 and inflow valves 315, 327, and fully open the main valve 312, the chamber 301
After reducing the internal pressure to 10 ^-5 torr or less, the main valve 312
The chamber 301 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 11μ. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1. The image quality was excellent and extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. 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 heated 5× by the same operation and procedure as in Example 1.
After creating a vacuum of 10 ^-6 torr and maintaining the substrate temperature at 200°C, the auxiliary valve 309 and then the outflow valve 3
43 and the inflow valve 345 were fully opened, and the inside of the flow meter 344 was also sufficiently degassed and vacuumed. After closing the auxiliary valve 309 and valves 343 and 345, open the valve 347 of the Si(CH ₃ ) ₄ gas (purity 99.999%) cylinder 348 diluted to 10 vol% with H ₂ and set the pressure on the outlet pressure gauge to 1 Kg/cm. ² , and the inflow valve 345 was gradually opened to allow Si(CH ₃ ) ₄ gas to flow into the flow meter 344. Subsequently, the outflow valve 343 was gradually opened. Next, the opening of the auxiliary valve 309 was adjusted while observing the reading on the Pirani gauge 310, and the auxiliary valve 309 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 312 was gradually closed and the opening was throttled until the reading on the Pirani gauge 310 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 308 is turned ON, and 13.56 MHz high frequency power is applied between the electrodes 303 and 307 to generate a glow discharge in the chamber 301. , with an input power of 3W.
After maintaining the same conditions for 1 minute to form an intermediate layer, the high frequency power source 308 is turned off and the glow discharge is stopped, and after a while, the outflow valve 343,
Close the inlet valve 345 and then add 10vol% _H2
Valve 317 of SiF ₄ gas cylinder 318, with H ₂
324 B ₂ H ₆ gas cylinders diluted to 500 volppm
Open the valve 323 of the outlet pressure gauge 322, 3.
Adjust the pressure of 16 to 1Kg/cm ² and open the inflow valve 31.
5, 321 gradually open and flow meter 31
SiF ₄ gas and B ₂ H ₆ gas were respectively introduced into the 4,320 chamber. Subsequently, the outflow valves 313, 319 were gradually opened. SiF ₄ gas flow rate and B ₂ H ₆ at this time
Outlet valve 31 so that the gas flow ratio is 70:1.
3,319 apertures were defined and stabilized. Nao room 30
The valve adjustment operation was carried out in the same manner as when forming the intermediate layer so that the internal pressure in No. 1 was 0.5 torr. Subsequently, the high frequency power supply 308 was turned on again to restart the glow discharge. The input power at that time is
The power was increased to 60W compared to before. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power supply 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 313, 319 and the inflow valves 315 and 321, and the main valve 312 is fully opened to reduce the inside of the chamber 301 to 10 ^-5 torr or less. Then, the main valve 312 is closed and the inside of the chamber 301 is set to atmospheric pressure by the leak valve 311, 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 9μ. The image forming member thus obtained is
It was installed in a charged exposure experimental device, corona discharge was performed for 0.2 seconds at 6.0 KV, 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. Further, even when the corona charge polarity was changed to 1 and the developer polarity was changed to 2, a good and clear image was obtained in the same manner as in Example 1. Example 9 SiF ₄ gas cylinder 3 containing 10 vol% of H ₂ in advance
After changing the SiF ₄ gas (purity 99.999%) cylinder diluted to 5 vol% with Ar gas to a SiF 4 gas (purity 99.999%) cylinder, an intermediate layer was provided on the molybdenum substrate in the same manner as in Example 1, and the chamber 30
After removing the gas in 1, open the valve 317 of the SiF ₄ gas (purity 99.999%) cylinder 318 diluted to 5 vol% with Ar gas, and the outlet pressure gauge 316 indicates that 1
The outlet pressure was adjusted to Kg/ ^cm2 . Next, inflow valve 3
15 gradually and into the flow meter 314.
SiF ₄ gas is inflowed and then outflow valve 313
was gradually opened, and furthermore, the auxiliary valve 309 was opened. Adjust the outflow valve 313 while detecting the internal pressure of the chamber 301 with the Pirani gauge 310.
The inflow amounted to 10 ^-4 torr. After the flow rate became stable in this state, the main valve 312 was gradually closed and the opening was narrowed until the indoor pressure reached 1×10 ⁻² torr. Open the shutter 307 and flow meter 31
After confirming that 4 is stable, turn on the high frequency power supply 308.
was turned on, and AC power of 13.56 MHz; 100 W was input between the target 305 and the fixed member 303. Matching was performed under these conditions to continue stable discharge, and a layer was formed. After continuing the discharge in this way for 3 hours, the high frequency power supply 308 is turned on.
The state was turned off, and the power to the heating heater 304 was also turned off. Wait for the board temperature to drop below 100℃,
After closing the outflow valve 313 and the auxiliary valve 309, the main valve 312 was fully opened to remove the gas from the room. Thereafter, the main valve 312 was closed and the leak valve 311 was opened to leak the inside of the deposition chamber 301 to atmospheric pressure, and then the substrate was taken out. When the thus obtained image forming member was imaged on transfer paper according to the same procedure as in Example 1,
The image quality formed by corona discharge was superior to that formed by corona discharge, and the image was extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 10 The intermediate layer and the upper layer were varied as shown in Table 4 below, the photoconductive layer was formed under the same conditions and procedures as in Example 1, and 40 samples were prepared as image forming members. (n is the number of the middle layer, m is the number of the upper layer)
was created. Charging, exposure and transfer were performed for both polarities in the same manner as in Example 1.
In either case, there was no dependence on charging polarity, and extremely clear toner images were obtained.

【table】

【table】

【table】 [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 FIG. 3 is a diagram of an apparatus for manufacturing the photoconductive member of the present invention. FIG. 2 is a schematic explanatory diagram showing an example. 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 , _the intermediate layer is ( _Si
0.35, 0.65≦Y≦0.98), and has 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.