JPS6346409B2 - - 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. Highly sensitive photoconductive materials are used as photoconductive materials for forming photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc.
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body 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. As a photographic image forming member, application to a photoelectric conversion/reading device is described in JP-A-55-39404. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor 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 stability over time, and practical solid-state imaging devices, reading devices, and electrophotographic images can be used in a wide range of applications. The reality is that forming members and the like cannot be used effectively in consideration of productivity and mass production. For example, when applied to image forming members for electrophotography, it is often observed that residual potential remains during use, and such photoconductive members may become fatigued due to repeated use if used repeatedly for a long time. There have been many disadvantages, such as the so-called ghost phenomenon caused by the accumulation of residual images. Furthermore, for example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional Se, CdS, ZnO, PVCz, TNF, etc. Although it has many advantages compared to OPC (organic photoconductive material), a-Si has been given characteristics for use in conventional solar cells.
Even when the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, compared to ordinary electrophotography. There are problems that can be solved, such as the fact that the method is difficult to apply, and in a humid atmosphere, the above-mentioned tendency is remarkable, and in some cases, it may not be possible to retain the electrical charge at all until the development time. It is known that it exists. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is. 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 an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X),
A photoconductive layer composed of so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter a-Si(H,X) is used as a generic term for these). Photoconductive members manufactured with a specified layer structure and designed to have a layer configuration in which a specific barrier layer (intermediate layer) is provided between the photoconductive layer and the support that supports the photoconductive layer are suitable for practical use. Not only can it be used satisfactorily, but it also surpasses conventional photoconductive members in most respects, and has particularly excellent properties as a photoconductive member for electrophotography. It is based on the findings that 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, 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 maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. An object of the present invention is to provide a photoconductive member having sufficient electrophotographic properties. 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 comprises a support, a photoconductive layer, and an intermediate layer provided between these and having the function of preventing carrier from being injected into the photoconductive layer from the support side. Further, the photoconductive layer is made of an amorphous material containing silicon as a matrix and hydrogen atoms or halogen atoms, or hydrogen atoms and halogen atoms, and the intermediate layer is made of an amorphous material containing boron as a matrix and halogen atoms. It is configured. Barriers or depletion layers are formed in their interfacial regions, the intermediate layer being able to prevent the injection of electrons from the support side into the photoconductive layer and by electromagnetic irradiation into the photoconductive layer. This allows the resulting carrier to pass through. It has been found that the intermediate layer according to the invention can prevent the injection of electrons into the photoconductive layer, but not the injection of holes into the photoconductive layer. Therefore, the photoconductive member of the present invention has a specific polarity, and when charging the surface of the member, only positive charging is suitably used. A photoconductive member designed to have the layer structure described above can solve all of the problems described above, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. . In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio, is extremely resistant to light damage, has excellent repeatability, and can obtain high-quality visible images with high density, clear halftones, and high resolution. Furthermore, when applied to electrophotographic imaging members, a-Si(H,X) with high dark resistance has low photosensitivity;
On the other hand, a-Si(H,X), which has high photosensitivity, has a dark resistance.
In any case, the photoconductive layer of the conventional layer structure could not be applied to an electrophotographic image ^forming member, but in the case of the present invention, the specific Even a-Si ( ^H , Low but high sensitivitya
-Si(H,X) can also be used sufficiently, a-Si(H,X)
Restrictions from the characteristics aspect of can be alleviated. 〓In order to prevent dark decay of the potential during charging, a surface barrier layer is further provided on the photoconductive layer, and the support, intermediate layer, photoconductive layer,
It is also possible to adopt a structure in which the surface barrier layers are laminated in this order. In this case, the surface barrier layer effectively blocks the flow of charged charges from the surface side to the photoconductive layer side during charging, and also prevents the photocarrier generated in the photoconductive layer and the charged charges from flowing during electromagnetic wave irradiation. An amorphous silicon material that functions to allow recombination and contains a metal oxide such as Al ₃ O ₃ , carbon, or nitrogen is preferably used as will be described in detail later. 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. A photoconductive member 100 shown in FIG. 1 has an intermediate layer 103 and a photoconductive layer 102 laminated on a support 101 for the photoconductive member. The support 101 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr., stainless steel, Al, Cr, Mo, Au,
Examples include metals such as Nb, Ta, V, Ti, Pt, and 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. . 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, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. conductivity is imparted to the The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and if desired,
Although its shape is determined, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is desirable to have an endless belt shape or a cylindrical shape in the case of 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. It is made as thin as possible within this 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 103 is composed of boron atoms and halogen (X=
When _{the surface} of the photoconductive member 100 is subjected to charging treatment, It has a function of preventing free carriers from being injected into the photoconductive layer 102 from the support 101 . The intermediate layer 103 composed of a-B _x X _1-x can be formed preferably by the glow discharge method described below. That is, for example, as a raw material gas,
Using BF ₃ and BCl ₃ , they are mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is subjected to glow discharge. The amorphous material may be deposited on the support 101 by generating gas plasma. In addition, if necessary, in the intermediate layer 103,
Group atoms (e.g. Be), group atoms (e.g. Si, C)
It is also possible to dope etc. Support 101
When forming the intermediate layer 103 made of a _- B _x The temperature of the support during layer formation is strictly controlled so that a-B _x X _1-x having the following properties 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 103 is usually 20 to 350°C, preferably 150 to 300°C. . The numerical range of the thickness of the intermediate layer 103 in the present invention is one of the important factors for effectively achieving the object of the present invention. When the layer thickness of the intermediate layer 103 is too thin, the photoconductive layer 1 is removed from the support 101.
If the thickness is too thick, the ability to prevent carrier injection into the photoconductive layer 102 will decrease again, or A problem arises in that the probability that the photo carriers generated in this process will pass through to the support is extremely low. 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 03 is usually 30 Å to 1 μ,
The thickness is preferably 50 to 5000 Å, most preferably 50 to 1000 Å. In the present invention, in order to effectively achieve the purpose, the photoconductive layer 10 formed on the intermediate layer 103 is
2 is composed of a-Si:H having the semiconductor properties shown below. p-type a-Si:H... Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). P ^- type a-Si (H, N-type a-Si(H,X): Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd). An n ^- type a-Si (H, i-type a-Si(H,X)...NaNdO or NaNd. In the present invention, specific examples of the halogen atom (X) contained in the photoconductive layer 102 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. In the present invention, the photoconductive layer 102 made of a-Si (H, done by. For example, by glow discharge method,
In order to form a photoconductive layer composed of a-Si (H,
A raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and a predetermined support that has been installed at a predetermined position in advance is used. A layer made of a-Si(H,X) may be formed on the surface.
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, A gas for introducing hydrogen atoms and/or halogen atoms may be introduced into the deposition chamber for sputtering. As the Si-generating raw material gas used in the present invention, silicon hydride (silanes) in a gaseous state or in the process of gasification, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₆ , Si ₄ H ₁₀ , etc., can be effectively used. SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of handling during layer formation work and good Si production efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives in gaseous or gasified form. Preferred examples include the halogen compounds obtained. Furthermore, silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or contain gasifiable halogens, can also be cited 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 silicon compounds containing halogens, so-called halogen-substituted silane derivatives 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 102 containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for Si generation, and Ar,
Gases such as H ₂ and He are introduced into the deposition chamber where the photoconductive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, the photoconductive layer 102 can be formed on the intermediate layer 103 formed on a predetermined support, but these gases may further contain hydrogen atoms in order to introduce hydrogen atoms. A predetermined amount of silicon compound gas may also be mixed to form a layer. 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 (H, Sputtering is performed in a predetermined gas plasma atmosphere, and 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 heated using a resistance heating method or an electron beam method ( This can be done by heating and evaporating the flying evaporates using a method such as the EB method and passing them through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good. 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 ,
Halogen-substituted silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other halides containing gaseous or gasifiable hydrogen atoms as one of their constituents are also effective starting materials for forming the photoconductive layer. I can list many. These halides containing hydrogen atoms are used in the present invention because hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer during formation of the photoconductive layer. Used as a suitable raw material for halogen introduction. In order to structurally introduce hydrogen atoms into the photoconductive layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be carried out by causing a discharge by causing silicon hydride gas such as Si ₃ H ₃ or Si ₄ H ₁₀ to coexist with a silicon compound for producing a-Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms 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 photoconductive layer made of a-Si(H,X) is formed on the surface of the intermediate layer 103 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 or PF ₃ . In the present invention, the amount of H or X contained in the photoconductive layer of the photoconductive member to be formed or (H+X)
The amount of is usually 1 to 40 atomic%, preferably 5
It is desirable that it be ~30 atomic%. The amount of H and/or All you have to do is control the force. In order to make the photoconductive layer n-type, p-type, or i-type, an n-type impurity, a p-type impurity, or both impurities are added to the formed layer during layer formation by a glow discharge method, a sputtering method, etc. This is achieved by controlling the amount of doping. In order to make the photoconductive layer i-type or p-type, impurities doped into the photoconductive layer include elements of group A of the periodic table, such as B, Al, Ga, In,
Preferred examples include Tl, etc. In the case of making it an n-type, suitable examples include elements of group A of the periodic table, such as N, P, As, Sb, and Bi. Since the amount of these impurities contained in the layer is on the order of ppm, it is not necessary to pay as much attention to their pollution properties as the main materials that make up the electroconductive layer, but it is important to use materials that are as non-polluting as possible. Preferably. From this point of view, B, Ga, P, Sb, etc. are optimal, taking into consideration the electrical and optical characteristics of the layer to be formed. In addition, it is also possible to control the material to be n-type by, for example, interstitial doping with Li or the like by thermal diffusion or implantation. The amount of impurities to be doped into the photoconductive layer is appropriately determined depending ^on the desired electrical and optical ^properties . Impurities in group A of the periodic table are 5x
It is sufficient to dope within a range of up to 10 ^-3 atomic%, and to make it p-type, dope with an impurity from group A of the periodic table in an amount ranging from 5 x 10 ^-3 to 3 x 10 ^-2 atomic %. Good. In order to make the material n-type, it is desirable to dope it with an impurity belonging to group A of the periodic table in an amount of 5×10 ^-3 atomic % or less. The layer thickness of the photoconductive layer is determined as desired so that photocarriers are efficiently generated in the photoconductive layer and efficiently transported in a predetermined direction;
The thickness is usually 3 to 100μ, preferably 5 to 50μ. In the present invention, by providing the surface barrier layer 103, the photoconductive layer 102 can be used even if it has a relatively low resistance. The dark resistance of the photoconductive layer 102 is preferably 5×10 ⁹ Ωcm or more, most preferably
It is desirable that the photoconductive layer 102 be formed to have a resistance of 10 ¹⁰ Ωcm or more. In particular, the numerical condition for this dark resistance value is to dope the prepared impurity of group A of the periodic table to 5×10 ^-3 atomic%, and to make it p-type, dope the impurity of group A of the periodic table. Impurities from 5×10 ^-3 to 3×
10 ^-2 atomic% doping is sufficient. To make it n-type, impurities in group A of the periodic table should be added by 5×
It is desirable to dope in an amount of 10 ^-3 atomic % or less. The layer thickness of the photoconductive layer is appropriately determined as desired so that photocarriers are efficiently generated in the photoconductive layer and efficiently transported in a predetermined direction, and is usually 3 to 100 μm, preferably 5 μm. ~50μ. In the present invention, by providing the intermediate layer 103, the photoconductive layer 102 can be used even if it has a relatively low resistance. The dark resistance of the photoconductive layer 102 is preferably 5×10 ⁹ Ωcm or more, optimally 10 ¹⁰ Ωcm.
It is desirable that the photoconductive layer 102 be formed as described above. In particular, this numerical condition for the dark resistance value is required when the produced photoconductive member is used as an image forming member for electrophotography, a highly sensitive reading device or imaging device used in a low illuminance region, or a photoelectric conversion device. This is an important element in some cases. The layer thickness of the photoconductive layer 102 of the photoconductive member in the present invention is appropriately determined according to the purpose of the application, such as a reading device, an imaging device, or an electrophotographic image forming member. In the present invention, the layer thickness of the photoconductive layer 102 is set such that the thickness of the intermediate layer is such that the function of the photoconductive layer 102 and the function of the barrier layer are each effectively utilized and the object of the present invention is effectively achieved. The layer thickness is determined as desired in relation to the layer thickness of the intermediate layer 103, and in normal cases, the layer thickness is preferably several hundred to several thousand times or more than the layer thickness of the intermediate layer 103. It is. Next, FIG. 2 is a schematic configuration diagram schematically shown for explaining another configuration example of the photoconductive member of the present invention. A photoconductive member 200 shown in FIG. 2 is composed of an intermediate layer 203, a photoconductive layer 202, and a surface barrier layer 204 on a support 201 for the photoconductive member. Therefore, in this configuration, a surface barrier layer 204 is added to the layer configuration described in FIG. When the surface of the photoconductive member 200 is subjected to charging treatment, the surface barrier layer 204 covers the photoconductive layer 2 from the surface side.
The photoconductive layer 202 has a function of effectively blocking the inflow of charges into the photoconductive layer 202 and allowing recombination of the photocarriers generated in the photoconductive layer 202 and the surface charges during the electromagnetic wave irradiation. be. The surface barrier layer is an amorphous material having silicon as its base material and containing at least one kind of atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms, and at least one of hydrogen atoms or halogen atoms as necessary. Materials <These are collectively referred to as a- [Six (C,
N, O) _1-x ) _y (H, X) _1-y (however, 0
<x<1,0<y<1)> or made of electrically insulating metal oxide. In the present invention, preferred halogen atoms (X) are F, Cl, Br, and I, with F and Cl being particularly preferred. Specifically, as an amorphous material constituting the surface barrier layer 204, which is effectively used in the present invention, for example, a carbon-based amorphous material such as a
-SiaC _1-a , a- (SibC _1-b ) _c H _1-c , a-
_{( SidC 1 - d ) e}
(SiiN _1-i ) _j H _1-j , a― (SikN _1-k ) _l X _1-l , a―
(SimN _1-n ) _o (H+X) _1-o , as an oxygen-based amorphous material a-SioO _1-p , a-(SipO _1-p )qH _1-q , a
-(SirO _1-r ) _s X _1-s , a-(SitO _1-t ) _u (H+X) _1-
Further , in the above amorphous material, C,
Examples include amorphous materials containing at least two types of atoms among N and O as constituent atoms (provided that 0<a, b, c, d, e, f, g, h, i, j,
k, l, m, n, o, p, q, r, s, t, u<
1). These amorphous materials are appropriately selected depending on the properties required for the surface barrier layer 204 and the ease of continuous production of the intermediate layer 203 and photoconductive layer 202, etc., depending on the optimized design of the layer structure. selected. Particularly from the viewpoint of properties, it is more preferable to select carbon-based or nitrogen-based amorphous materials. When the surface barrier layer 204 is made of the above-mentioned amorphous material, a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, etc. are used to form the layer. Ru. 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. A surface barrier layer 2 in which carbon atoms, nitrogen atoms, oxygen atoms, or hydrogen atoms and halogen atoms are formed as necessary in addition to silicon atoms, and it is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having the structure.
The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily introduced into the 04.04. Furthermore, in the present invention, the lower barrier layer 204 may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the surface barrier layer 204 by the glow discharge method, the raw material gas for forming the amorphous material 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 201 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. Then, the amorphous material may be deposited on the photoconductive layer 202. In the present invention, SiH ₄ and Si ₂ containing Si and H as constituent atoms are effectively used as raw material gases for forming the surface barrier layer 204 made of a carbon-based amorphous material. Silicon hydride gas such as silanes such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., saturated hydrocarbons containing C and H as constituent atoms, e.g. 1 to 5 carbon atoms, 1 carbon atom -5 ethylene hydrocarbons, C2-4 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-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
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. Among the raw material gases for layer formation to configure the surface barrier layer 204 from a carbon-based amorphous material containing halogen atoms, the raw material gases for introducing halogen atoms include:
Examples include simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, and HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , ClF ₅ ，
BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₃ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ ,
Examples of silicon hydride include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₆ ,
Silanes such as Si ₄ H ₁₀ , etc. can be mentioned. In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ Cl, CH ₃ Br, CH ₃ I, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ may also be mentioned as useful. These barrier layer forming substances are used to form a barrier layer so that the formed barrier layer contains silicon atoms, carbon atoms, and optionally halogen atoms and hydrogen atoms in a predetermined composition ratio. They are selected and used as desired. For example, SiHCl _{3 and} SiCl contain Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form a barrier layer with desired characteristics. ₄ , SiH ₂ Cl ₂ ,
Alternatively, a-(SifC _1-f ) _g(X+H)1 can be obtained by introducing SiH ₃ Cl or the like in a gaseous state at a predetermined mixing ratio into the system for forming a barrier layer to generate a glow discharge. A barrier layer consisting of _-g can be formed. In the present invention, when employing a glow discharge method to form the surface barrier layer 204 with a nitrogen-based amorphous material, a material selected from among the above-mentioned substances for forming a barrier layer may be used as desired. What is necessary is to select one, and in addition to that, use the next raw material gas for introducing nitrogen atoms.
That is, starting materials that can be effectively used as raw material gases for introducing nitrogen atoms to form the surface barrier layer 204 include those containing N as a constituent atom or containing N and H.
For example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ )
Mention may be made of gaseous or gasifiable nitrogen compounds such as nitrides and azides.
In addition, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned because they can introduce halogen atoms in addition to nitrogen atoms. I can do it. When forming the surface barrier layer 204 using an oxygen-based amorphous material using a glow discharge method, the starting materials that serve as the raw material gas for forming the surface barrier layer 204 include the above-mentioned materials. A starting material for introducing oxygen atoms is added to a starting material selected from among starting materials for forming a barrier layer as desired.The starting material for introducing oxygen atoms has at least an oxygen atom as a constituent atom. Most gaseous substances or gasified substances that can be gasified may be used. For example, when using a raw material gas containing Si as a constituent atom, a raw material gas containing Si as a constituent atom, a raw material gas containing O as a constituent atom, and a raw material gas containing H or and X as a constituent atom as necessary. or mix a raw material gas containing Si at a desired mixing ratio with a raw material gas containing O and H at a desired mixing ratio. mosquito,
Alternatively, a raw material gas containing Si as a constituent atom and Si, O
It is possible to use a mixture of a raw material gas having three constituent atoms: and H. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing O as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), disiloxane H ₃ SiOSiH ₃ , trisiloxane whose constituent atoms are Si, O, and H
Examples include lower siloxanes such as H ₃ SiOSiH ₂ SiH ₃ and the like. As mentioned above, the barrier layer 2 is formed by the glow discharge method.
04, a surface barrier layer 204 made of a desired constituent material having desired characteristics can be formed by selecting and using various starting materials for forming the barrier layer from among the materials listed above. I can do it. Specifically, a good combination of starting materials when forming the surface barrier layer 204 by a glow discharge method includes a 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
Examples include mixed gases such as Si (CH ₃ ) ₄ -SiH ₄ series, SiCl ₂ (CH ₃ ) ₂ -SiH ₄ series, etc. To form the surface barrier layer 204 made of a carbon-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer, a C wafer, or a mixture of Si and C is used. This can be carried out by sputtering the wafers in various gas atmospheres, using them as targets. For example, if a Si wafer is used as a target, the raw material gas for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X) may be diluted with a diluent gas as necessary. The Si wafer may be sputtered by introducing the gas into a deposition chamber and forming a gas plasma of these gases. Alternatively, a gas containing at least a hydrogen atom (H) or a halogen atom (X) can be produced by using separate targets for Si and C or by using a single target containing a mixture of Si and C. This is done by sputtering in an atmosphere. As the raw material gas for introducing carbon atoms, hydrogen atoms, or halogen atoms, the raw material gases shown in the glow discharge example described above can be used as effective gases also in the case of the sputtering method. To form the surface barrier layer 204 made of a nitrogen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer or Si ₃ N ₄ is used.
This can be carried out by sputtering a wafer or a wafer containing a mixture of Si and Si ₃ N ₄ in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms can be replaced with hydrogen atoms or/and
A raw material gas for introducing halogen atoms, such as H ₂ or NH ₃ , is diluted with a diluent gas as necessary and introduced into a sputtering deposition chamber, and these gases are used to form gas plasma. Then, the Si wafer may be sputtered. Alternatively, Si and Si ₃ N ₄ can be used as separate targets, or by using a single target formed by mixing Si and Si ₃ N ₄ , it can be used as a sputtering gas. This is done by sputtering in a dilute gas atmosphere or in a gas atmosphere containing at least H atoms and/or X atoms. Possible raw material gases for introducing N atoms include the raw material gases for introducing N atoms among the starting materials for forming the barrier layer shown in the glow discharge example mentioned above.
It can also be used as an effective gas in sputtering. To form the surface barrier layer 204 made of an oxygen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer or SiO ₂
This can be carried out by targeting a wafer, a wafer containing a mixture of Si and SiO ₂ , or an SiO ₂ wafer, and sputtering the wafer in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing H atoms and/or X atoms as constituent elements. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, the diluent gas used when forming the surface barrier layer 204 by a glow discharge method or a sputtering method is a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. The surface barrier layer 204 in the present invention is carefully formed to provide the desired properties. That is, a substance whose constituent atoms are at least one of Si, C, N, and O, and optionally H or/and X, has a structure ranging from crystalline to amorphous depending on its preparation conditions. Electrically, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, The preparation conditions are strictly selected so that a non-photoconductive amorphous material is formed. The amorphous material constituting the surface barrier layer 204 of the present invention has the function of preventing charges from flowing into the photoconductive layer 202 from the surface side when the surface of the photoconductive member 200 is subjected to charging treatment. Since it has the function of effectively blocking electromagnetic waves and allowing recombination of the photocarriers generated in the photoconductive layer 202 during electromagnetic wave irradiation with the surface-charged charges, it is an electrical insulator. Formed to indicate sexual behavior. In addition, the photocarrier generated in the photoconductive layer 202 and the surface charge are easily recombined, so that the carrier can pass through the surface barrier layer 204 smoothly. A surface barrier layer 204 is formed as having a value. An important factor in the layer formation conditions for forming the surface barrier layer 204 made of the amorphous material having the above characteristics is the temperature of the support during layer formation. That is, when forming the surface barrier layer 204 made of the amorphous material on the surface of the photoconductive layer 202, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, the temperature of the support during layer formation is strictly controlled so that the amorphous material having the desired properties can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the surface barrier layer 204 is appropriately selected in an optimal range in accordance with the method of forming the surface barrier layer 204. Formation of 204 is carried out, usually at temperatures between 100°C and 300°C, preferably between 150°C and 250°C, in the case of systems containing hydrogen or halogen atoms and without hydrogen or halogen atoms. In the case of a system, the temperature is usually 20 to 300°C, preferably 20 to 150°C. The formation of the surface barrier layer 204 involves delicate control of the composition ratio of atoms constituting each layer, which allows the intermediate layer 203, photoconductive layer 202, and surface barrier layer 204 to be formed in succession in the same system. It is advantageous to adopt a glow discharge method or a sputtering method because the thickness can be controlled relatively easily compared to other methods, but the surface barrier layer 204 can be formed using these layer formation methods. In this case, the discharge power and gas pressure during layer formation can be cited as important factors that influence the characteristics of the surface barrier layer 204 to be created, as well as the support temperature described above. The discharge power conditions for effectively creating the surface barrier layer 204 having the characteristics for achieving the purpose of the present invention with good productivity are usually 1 to 1.
300W, preferably 2-150W. The gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8×10 ^-3
It is desirable to set it to approximately 0.5 Torr. Surface barrier layer 204 in the photoconductive member of the present invention
The amounts of carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, and halogen atoms contained in the surface barrier layer 20
Similar to the manufacturing conditions in No. 4, this is an important factor in forming a barrier layer that provides the desired characteristics to achieve the object of the present invention. When the surface barrier layer 204 is composed of a-S _ia C _1-a , the content of carbon atoms is usually 60 to 90 atomic%, preferably 65 to 90 atomic%, based on silicon atoms.
80 atomic%, optimally 70-75 atomic%, 0.1-0.4 in a representation, preferably 0.2-0.35, optimally
0.25 to 0.3, and when composed of a-(Si _b C _1-b ) _cH1-c , the carbon atom content is usually 30 to 0.3.
The content of hydrogen atoms is 90 atomic%, preferably 40 to 90 atomic%, optimally 50 to 80 atomic%,
Usually 1 to 40 atomic%, preferably 2 to 35 atomic%,
Optimally 5 to 30 atomic%, expressed in b and c, b is usually 0.1 to 0.5, preferably 0.1 to 0.35, optimally 0.15 to 0.3, and c is usually 0.60 to 0.99, preferably 0.65 to 0.98, optimally 0.7 to 0.95, a-
(Si _d C _1-d ) _e X _1-e or a-(Si _f C _1-f ) _g (H+X) _1-g
, the carbon atom content is usually 40
~90 atomic%, preferably 50-90 atomic%, optimally 60-80 atomic%, and the combined content of halogen atoms and hydrogen atoms is usually 1-90 atomic%.
20 atomic%, preferably 1 to 18 atomic%, optimally 2 to 15 atomic%, and when both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic% or less, preferably 13atomic
% or less, and in the display of d, e, f, g, d,
f is usually 0.1 to 0.47, preferably 0.1 to 0.35, optimally 0.15 to 0.3, and e and g are usually 0.8 to 0.99, preferably 0.85 to 0.99, optimally 0.85 to 0.98. When the surface barrier layer 204 is made of a nitrogen-based amorphous material, first of all, in the case of a-Si _h N _1-h , the content of nitrogen atoms is usually 43 to 43 to silicon atoms.
60 atomic %, preferably 43 to 50 atomic %, h usually 0.43 to 0.60, preferably 0.43 to 0.50. When composed of a-(Si _i N _1-j ) _j H _1-j , the nitrogen atom content is usually 25 to 55 atomic%,
The content of hydrogen atoms is preferably 35 to 55 atomic%, usually 2 to 35 atomic%, preferably 5 to 55 atomic%.
30 atomic% and expressed as i, j, i is usually 0.43 to 0.6, preferably 0.43 to 0.5, j is usually 0.65 to 0.98, preferably 0.7 to 0.95, and a-(Si _k N _1-ic )X _1-l or a-(Si _n N _1-n )
When composed of n(H+X) _1-o , the nitrogen atom content is usually 30 to 60 atomic%, preferably 40 to 60 atomic%.
The content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 60 atomic%.
20 atomic%, preferably 2 to 15 atomic%,
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic% or less,
It is preferably 13 atomic% or less, and k, l, m,
In the representation of n, k and l are usually 0.43 to 0.60, preferably 0.43 to 0.49, and m and n are usually 0.8 to 0.99, preferably 0.85 to 0.98. When the surface barrier layer 204 is made of an oxygen-based amorphous material, first, in a-Si _p O _1-p , the content of oxygen atoms is 60 to 60% relative to silicon atoms.
67 atomic%, preferably 63 to 67 atomic%,
In terms of O, it is usually 0.33 to 0.40, preferably 0.33 to 0.40.
It is assumed to be 0.37. In the case of a-(Si _p O _1-p ) _q H _1-q , the content of oxygen atoms is usually 39 to 66 atomic%, preferably 42 to 66 atomic%.
64 atomic%, the hydrogen atom content is usually 2 to 35 atomic%, preferably 5 to 30 atomic%,
In terms of p and q, p is usually 0.33 to 0.40, preferably 0.33 to 0.37, and q is usually 0.65 to 0.98, preferably 0.70 to 0.95. a-(Si _r O _1-r ) _s X _1-s , or a-(Si _t O _1-t ) _u
(H+X) When composed of _1-u , the content of oxygen atoms is usually 48 to 66 atomic%, preferably 51 to
66 atomic%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 1.
20 atomic%, preferably 2 to 15 atomic%,
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic% or less,
It is preferably 13 atomic% or less, and r, s, t,
In the representation of u, r and s are usually 0.33 to 0.40, preferably 0.33 to 0.37, and t and u are usually 0.80 to 0.99.
It is preferably 0.85 to 0.98. In the present invention, the electrically insulating metal oxides constituting the surface barrier layer 204 include TiO ₂ ,
Ce ₂ O ₃ , ZrO ₂ , HfO ₂ , GeO ₂ , CaO, BeO,
P ₂ O ₅ , Y ₂ O ₃ , Cr ₂ O ₃ , AL ₂ O ₃ , MgO, MgO・
AL ₂ O ₃ , SiO ₂ .MgO, etc. can be mentioned as preferable examples. Two or more of these may be used in combination to form the intermediate layer. The surface barrier layer 204 made of electrically insulating metal oxide is formed by vacuum evaporation, CVD (chemical
This is accomplished by a vapor deposition method, a glow discharge decomposition method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are appropriately selected and employed depending on factors such as manufacturing conditions, load on equipment capital, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. For example, to form the surface barrier layer 204 by the sputtering method, He, Ne,
This may be carried out by sputtering in a sputtering gas atmosphere such as Ar. When using the electron beam method, the starting material for forming the surface barrier layer may be placed in a vapor deposition boat and irradiated with an electron beam to perform vapor deposition. The numerical range of the layer thickness of the surface barrier layer 204 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 surface barrier layer 204 is too thin, it will not be able to effectively block the inflow of charges from the surface side to the photoconductive layer 202 when charging treatment is performed on the surface; If it is thick enough, the photoconductive layer 20 will be damaged by electromagnetic wave irradiation during electromagnetic wave irradiation.
The function of permitting the recombination of the photocarriers generated in 2 and the surface charges cannot be performed satisfactorily, and therefore, in any case, the object of the invention cannot be achieved effectively. In view of the above points, the thickness of the surface barrier layer 204 to effectively achieve the object of the present invention is usually 30 Å to 5 μ, preferably 50 Å to 2 μ. Example 1 Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, a photoconductive member having the layered structure shown in FIG. 1 was produced by the following operations. A molybdenum (substrate) 302 having a surface cleaned and having a thickness of 0.5 mm and a square size of 10 cm was firmly fixed to a fixing member 303 at a predetermined position in the deposition chamber 301 . Targets 305 and 306 are polycrystalline high purity silicon (99.999%) and high purity graphite (99.999%).
It is installed above. Shutter 308 is closed. The substrate 302 is heated with an accuracy of ±0.5° C. by a heater 304 in a fixed part 303. Temperature measured with thermocouple (almeru cromel)
The backside of the substrate was directly measured by the method. Next, after confirming that all valves in the system are closed, the main valve 331 is fully opened and evacuated to approximately 5×10 torr (all valves in the system are closed at this time), and the auxiliary valves 329 and Outflow valves 324, 325, 326, 327 are opened and flow meters 337, 338, 339, 3
After the inside of 40 is sufficiently degassed, the outflow valve 32
4,325,326,327, were closed. Here, the heater 304 is turned on and the substrate temperature is set to 250°C. Next, open the valve 316 of the BF ₃ gas cylinder 311 diluted to 5 vol% with Ar, and
Adjust the pressure of 4 to 1Kg/cm ² and gradually open the inflow valve 321 to allow BF ₃ / into the flow meter 339.
Ar gas was introduced. Subsequently, the outflow valve 32
6 was gradually opened, and then the opening of the auxiliary valve 329 was adjusted to maintain the inside of the chamber 301 at 1×10 ⁻² torr.
After the internal pressure of the chamber 301 is stabilized, the main valve 331 is closed.
gradually close the Pirani gauge 342 until the indication on Pirani gauge 342 is
The aperture was narrowed down to 0.2 torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 34.
Turn on the switch 3 and connect the electrodes 303 and 30.
Input high frequency power between chambers 8 and 25W input power to chamber 3.
Glow discharge was generated in 01. The intermediate layer was formed by continuing the glow discharge for about 6 minutes in this manner. The thickness of the intermediate layer formed in this way is approximately 450
It is Å. After that, the high frequency power supply 343 is turned OFF to temporarily stop the discharge, and the valves 316 and 3
21 and 326 were further closed, and the valve 331 was fully opened. After the inside of the chamber 301 is sufficiently vacuum degassed, the valve 329 is closed, and then the SiH ₄ gas (purity 99.999%) diluted to 10 vol% with H ₂ is added to the valve 314 of the cylinder 309, and the B diluted with H ₂ to 100 vppm. ₂ H ₆
Open the valve 315 of the gas cylinder 310, adjust the pressure of the outlet pressure gauges 332, 333 to 1 Kg/cm ² ,
The inflow valves 319 and 320 were gradually opened to allow SiH ₄ gas and B ₂ H ₆ gas to flow into the flow meters 337 and 338. Subsequently, the outflow valve 324,3
25 was gradually opened, and then the auxiliary valve 329 was gradually opened. At this time, the SiH ₄ /H ₂ gas flow rate and
The inflow valves 319 and 320 were adjusted so that the B ₂ H ₆ /H ₂ gas flow rate ratio was 100:1. Next, while watching the reading on the Pirani gauge 342, adjust the opening of the auxiliary valve 329 so that the inside of the chamber 301 is 1×.
Auxiliary valve 329 was opened until 10 ^-2 torr.
After the internal pressure of the chamber 801 stabilizes, the main valve 33
1 gradually close, and the indication of Pirani gauge 342 is
The aperture was narrowed down to 0.5 torr. Confirm that the gas inflow is stable and the internal pressure is stable, then close the shutter 308.
Turn on the switch of high frequency power supply 343 while keeping it closed.
state, 13.56MHz between electrodes 303 and 308
A glow discharge was generated in the chamber 301 by inputting high-frequency power of 10 W, resulting in an input power of 10 W. The glow discharge was continued for about 10 hours to form a photoconductive layer with a thickness of about 15 μm. Finally, turn off the heater 304,
The high frequency power supply 343 is also turned off, the outflow valves 324, 325 and the inflow valves 319, 320 are closed, the main valve 331 is fully opened, and the chamber 30
After reducing the temperature inside 1 to below 10 ^-5 torr, the main valve 33
1 was closed, and after waiting for the substrate temperature to reach 50° C., the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 330, and the substrate was taken out. Cylinder 813, valve 818, inflow valve 823, outflow valve 823,
A gas supply system consisting of an outlet pressure gauge 836 and a flow meter 841 is a preliminary one. The photoconductive member thus obtained was placed in an experimental charging exposure apparatus. Corona charging was performed at 6KV and image exposure was performed. The light source uses a halogen lamp, and the amount of light is approximately
It was 1.2lux・sec. Immediately thereafter, a good toner image was obtained on the photoconductive member surface by cascading a chargeable developing agent (including toner and carrier) onto the photoconductive member surface. The toner image on the photoconductive member is
Transferred onto transfer paper with 5.0KV corona charging,
Clear images with excellent resolution and good gradation reproducibility were obtained. Further, even when image formation was performed repeatedly, no change occurred in the image quality when comparing the first and second times or subsequent times. Furthermore, no deterioration in image characteristics was observed even after the above process was repeated 50,000 times. On the other hand, although the charging polarity was reversed, that is, corona charging was performed at 6 KV, image exposure was performed, and cascade development was performed using a chargeable developer, but no good image was obtained. Example 2 An intermediate layer and a photoconductive layer were formed on a molybdenum substrate according to the same conditions and procedures as in Example 1. After that, the heater 304 and high frequency power supply 343 are turned on.
Turn it off and wait for the board temperature to reach 50℃, then
Outflow valves 324, 325 and inflow valve 31
After closing the main valve 331 and fully deaerating the chamber 301, argon (purity
99.999%) After opening the valve 317 of the gas cylinder 312 and adjusting the reading of the outlet pressure gauge 335 to 1 Kg/cm ² , the inflow valve 322 is opened.
Subsequently, the outflow valve 327 was gradually opened to allow argon gas to flow into the deposition chamber 301. The outflow valve 327 is gradually opened until the Pirani gauge 342 indicates 5×10 ^-4 torr, and after the flow rate stabilizes in this state, the main valve 331 is opened.
was gradually closed and the opening was throttled until the room pressure reached 1×10 ^-2 torr. Next, open the shutter 308, confirm that the flow meter 340 is stable, and then turn on the high frequency power supply 343.
Targets 305, 306 and fixing member 303
During this time, 1356MPH, 100W AC power was input.
Under these conditions, the layers were formed while performing matching so that stable discharge could continue. Discharge was continued in this manner for 1 minute to form a surface barrier layer with a thickness of Å. After that, the high frequency power supply 343 is turned off, and the outflow valve 327
and close the inflow valve 322 and main valve 331
After fully opening the chamber 301 to reduce the pressure within the chamber 301 to 10 ^-5 torr or less, the main valve 331 was closed and the chamber 301 was brought to atmospheric pressure by the leak valve 330, and the substrate was taken out. The photoconductive member prepared in this way was installed in the same experimental charging exposure apparatus as in Example 1),
When image formation, development, and transfer were carried out in exactly the same manner, a clear image with excellent resolution and good gradation reproducibility was obtained, even higher in density than in Example 1. Moreover, the repeatability was also good. Furthermore, an attempt was made to form an image by reversing the charging polarity in the same manner as in Example 1), but no good image was obtained. Example 3 Example 1 except for changing the thickness of the intermediate layer)
A photoconductive member was formed in exactly the same manner. When this photoconductive member was subjected to image formation by polar charging in the same manner as in Example 1), the results shown in Table 1 were obtained.

[Table] △ Good × Not good

[Brief explanation of the drawing]

1 and 2 are schematic illustrations for explaining the layer structure of preferred embodiments of the photoconductive member of the present invention, and FIG. 3 is an apparatus for producing the photoconductive member of the present invention. FIG. 2 is a schematic explanatory diagram for explaining. 100,200...Photoconductive member, 101,201
...Support, 102,202...Photoconductive layer, 103,
203...Intermediate layer, 204...Surface barrier layer.

Claims (1)

[Scope of Claims] 1. A support, a photoconductive layer made of an amorphous material based on silicon atoms and containing at least one of hydrogen atoms or halogen atoms, and an intermediate between the support and the photoconductive layer. and an intermediate layer which functions to prevent a carrier from being injected from the support side to the photoconductive layer side, wherein the intermediate layer has boron atoms as a matrix and contains halogen atoms. A photoconductive member comprising an amorphous material containing atoms. 2 The amount of halogen atoms contained in the intermediate layer is 1
The photoconductive member according to claim 1, wherein the photoconductive member is from 50 atomic % to 50 atomic %. 3. The photoconductive member according to claim 1, wherein the intermediate layer has a thickness of 30 Å to 1 μ. 4. The photoconductive layer according to claims 1 to 3, further comprising a surface barrier layer on the photoconductive layer that functions to prevent carriers from being injected from the surface into the photoconductive layer. Element. 5. According to claim 4, the surface barrier layer is made of an amorphous material containing silicon atoms as a matrix and at least one type of atom selected from carbon atoms, nitrogen atoms, and oxygen atoms. The photoconductive member described. 6 Claim 5 in which the surface barrier layer contains at least either hydrogen atoms or halogen atoms
The photoconductive member described in . 7. The photoconductive member according to claim 4, wherein the surface barrier layer is composed of an electrically insulating metal oxide.