JPS628782B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, a document reading device, etc., it is highly sensitive,
High SN ratio [photocurrent (I _p )/dark current (Id)]
The solid-state imaging device must have absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, have fast photoresponsiveness, have a desired dark resistance value, and be non-polluting to the human body during use. In this case, characteristics such as being able to easily process afterimages within a predetermined time are required. 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 a photoconductive layer 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, making it suitable for practical solid-state imaging devices, reading devices, and electrophotography that can be used in a wide range of applications. Image forming members etc. have productivity,
The reality is that it cannot be used effectively considering 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. The above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, it may not be possible to retain the electrostatic charge at all until the development time.There are some points that can be solved. The existence of this proves that 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 member 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), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] A-Si (H, X) is used as a generic notation for The photoconductive member produced by this method is not only usable for practical use, but also superior in most respects to conventional photoconductive members, especially when used in electrophotography. This is based on the discovery that it has extremely excellent properties as a conductive member. 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 maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient electrophotographic properties and excellent 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 includes a support, a photoconductive layer, and a surface barrier provided on these, that is, on the surface side, and having a function of preventing charged charges from being injected from the surface into the photoconductive layer. It consists of layers. moreover,
The photoconductive layer is made of silicon as a matrix and is made of an amorphous material containing hydrogen atoms, halogen atoms, or hydrogen atoms and halogen atoms; ) is composed of an amorphous material containing At those interface regions, a barrier or void layer is formed, said barrier layer being able to block the injection of electrons into said photoconductive layer, while allowing the passage of carriers generated by electromagnetic radiation. It is something to do. It has been found that the barrier 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 negative polarity charging is preferably 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 fatigue, has excellent repeatability, has high density, and has clear halftones.
Moreover, it is possible to obtain a high-quality visible image with high resolution. Furthermore, when applied to electrophotographic image forming members, a-Si (H, X) with high dark resistance has low photosensitivity, and conversely, a-Si (H, The photoconductive layer has a low resistance of around 10 ⁸ Ωcm, and in any case, it could not be applied to an electrophotographic image forming member if the photoconductive layer had a conventional layer structure, but in the case of the present invention, Due to its specified layer structure, a ^- Si (H,
Since even X) can be used as a material constituting a photoconductive layer for electrophotography, a-Si (H,
Restrictions from the characteristics of Si(H,X) can be alleviated. In order to prevent dark decay of potential during charging, it is also possible to further provide a lower barrier layer on the support and adopt a structure in which the support, lower barrier layer, photoconductive layer, and surface barrier layer are laminated in this order. . In this case, the lower barrier layer effectively prevents free carriers from flowing from the support side to the photoconductive layer side during charging, and prevents photocarriers generated in the photoconductive layer from flowing into the support side during electromagnetic irradiation. An amorphous silicon material containing a metal oxide such as Al ₂ O ₃ , carbon, or nitrogen is preferably used. 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.
2. It has a layer structure consisting of a surface barrier layer 103 provided on and in direct contact with the photoconductive layer 102. 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, on its surface,
NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V,
Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +
Conductivity is imparted by providing a thin film consisting of SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
Conductivity is imparted to the surface by providing a thin film of metal such as Ti or Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. 1 is used for electrophotography. If used as an 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, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
Usually, it is 10μ or more. The surface barrier layer 103 has a function of preventing surface charges from being injected into the photoconductive layer 102 when its surface is subjected to charging treatment. The surface barrier layer 103 is made of an amorphous material (a-
Bx (HyX _1-y ) _1-x where 0<x<1, 0<y<1)
The photoconductive layer 102 has a function of preventing surface charges from being injected into the photoconductive layer 102 when the surface thereof is subjected to charging treatment. Formation of the surface barrier layer 103 composed of a-Bx(HyX _1-y ) _1-x can be preferably performed by the glow discharge method described below. That is, B ₂ H ₆ and BF ₃ (or BCl ₃ ) are used as raw material gases, and if necessary, they are mixed with dilution gas at a predetermined mixing ratio.
The photoconductive layer 10 is introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge.
The above-mentioned amorphous material may be deposited on 2. Further, if necessary, the surface barrier layer 103 may contain group atoms (e.g. Be), group atoms (e.g.
It is also possible to dope with Si, C), etc. a-Bx (HyX _1-y ) _1-x on the surface of the photoconductive layer 102
When forming the surface barrier layer 103, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. a−Bx(HyX _1-y ) _1-
The temperature of the support during layer formation is strictly controlled so that _x can be created as desired. In order to effectively achieve the purpose of the present invention, the support temperature when forming the surface barrier layer 103 is usually 20 to 350°C, preferably 150°C to
A temperature of 300°C is desirable. The discharge power conditions for effectively producing a-Bx (HyX _1-y ) _1-x with good productivity, which have the characteristics to achieve the purpose of the present invention, are usually as follows.
2W to 100W, preferably 10W to 50W. Surface barrier layer 103 in the photoconductive member of the present invention
The amount of hydrogen atoms and halogen atoms contained in
This is an important factor in forming a surface barrier layer with desired properties. The sum of the amounts of hydrogen atoms and halogen atoms contained in the surface barrier layer 103 in the present invention is usually 1 to 1.
It is desirable that the content be 50 atomic %, preferably 5 to 40 atomic %. That is, the previous a-Bx
(HyX _1-y ) If you represent x in _1-x , x is usually
0.99-0.5, preferably 0.95-0.6. Further, the value of y is usually 0.98 to 0.2, preferably 0.9 to 0.4. The numerical range of the layer thickness of the surface barrier layer 103 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 103 is too thin, it will not be able to sufficiently prevent the injection of surface charges from the surface to the photoconductive layer 102, and if it is too thick, it will fail again. In either case, the objective of the present invention cannot be effectively achieved. can no longer be achieved. The thickness of the surface barrier layer 103 to effectively achieve the object of the present invention is usually 30 Å to 1
μ is preferably 50 to 5000 Å, most preferably 50 to 1000 Å. In the present invention, in order to effectively achieve the purpose, a photoconductive layer 10 formed on a support 101 is used.
2 is a-Si(H,
X). p-type a-Si(H,X)...Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). The so-called p ^- form a-Si(H,X)... has a low acceptor concentration (Na).
Lightly doped with type impurities. 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 list them. In the present invention, the photoconductive layer 102 composed of a-Si (H, done by. For example, by the 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 made to have a reduced pressure, and a glow discharge is generated in the deposition chamber to generate a glow discharge on the surface of a predetermined support that has been previously installed at a predetermined position. a on top
A layer consisting of -Si(H,X) may be formed.
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 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 effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of handling during layer formation work and good Si generation efficiency. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be gasified. Further, silicon compounds containing halogen, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, and IBr. Preferred examples of 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, a silicon halide gas, which is a raw material gas for Si generation, and a silicon halide gas are used.
Gases such as Ar, H ₂ , He, etc. 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. By doing this, the photoconductive layer 102 can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is added to these gases. They may 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 EB method, etc., and passing the flying evaporates 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 the like, which are in a gaseous state or can be gasified,
Halides containing hydrogen atoms as one of their constituents can also be cited as effective starting materials for forming the photoconductive layer. 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 into the layer at the same time as halogen atoms are introduced into the photoconductive layer. is 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 a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for producing a-Si in a 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 estimation chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, a photoconductive layer of a-Si(H,X) is formed on the substrate. Furthermore, B ₂ H ₆ , which also serves as impurity doping,
It is also possible to introduce a gas such as PH ₃ or CPF 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, n-type impurities, p-type impurities,
Alternatively, both impurities can be doped into the layer while controlling their amounts. 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 and the like. In the case of n-type, suitable elements include elements of group V 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 constituting the photoconductive layer, but use materials that are as non-polluting as possible. Preferably. From this perspective,
Considering the electrical and optical properties of the layer to be formed,
For example, B, Ga, P, Sb, etc. are 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, but in order to make the photoconductive layer n ^- type, i-type, and p ^- type, from non-doped to Impurities in group A of the periodic table are 5x
It is sufficient to dope up to 10 ^-3 atomic%, and p
To form a mold, add 5× impurities from group A of the periodic table.
10 ^-3 to 3×10 ^-2 atomic% doping is sufficient. 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 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 3 to 100 μm. It is said to be 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, this numerical condition for the dark resistance value is required when the produced photoconductive member is used as an electrophotographic image forming member, 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 surface barrier layer is set 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. It is determined as desired in relation to the layer thickness with the layer 103, and in normal cases, it is several hundred to several hundred to the layer thickness of the surface barrier layer 103.
Preferably, the layer thickness is several thousand times or more. Next, FIG. 2 is a schematic configuration diagram schematically shown for explaining another configuration example of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 has a lower barrier layer 20 on a support 201 for the photoconductive member.
4. A photoconductive layer 202 provided in direct contact with the barrier layer 204 and a surface barrier layer 203
It is made up of. Therefore, in this structure, a lower barrier layer 204 is added to the layer structure described in FIG. The lower barrier layer 204 effectively blocks the inflow of free carriers from the support 201 side to the photoconductive layer 202 side, and is formed in the photoconductive layer 202 by electromagnetic wave irradiation during electromagnetic wave irradiation. It has a function of easily allowing the photocarrier moving toward the body 201 to pass from the photoconductive layer 202 side to the support body 201 side. The lower barrier layer 204 is an amorphous material whose base material is silicon and which contains 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. quality materials <these are collectively called a-[Six
(C, N, O) _{1 -x} ] _y (H, be done. In the present invention, preferred halogen atoms (X) are F, Cl, Br, and I, with F and Cl being particularly preferred. Specifically, as the amorphous material constituting the lower barrier layer 204, carbon-based amorphous material that can be effectively used in the present invention is, for example, a
-SiaC _1-a , a- (SibC _1-b ) _c H _1-c , a-
(SidC _1-d ) _e X _1-e , a-(SifC _1-f ) _g (H+X) _1-g ,
As nitrogen-based amorphous materials, a-SihN _1-h , a-
(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 ) _q H _1-q , a-
(SirO _1-r ) _s X _1-s , a-(SitO _1-t ) _u (H+X) _1-u
Furthermore, in the above amorphous material, C,
Examples include amorphous materials containing at least two types of atoms among N and O as constituent atoms (however, 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 determined by the characteristics required for the lower barrier layer 204 and the continuous formation of the photoconductive layer 202 and the surface barrier layer 203 stacked on the barrier layer 204 by optimizing the layer configuration. The most suitable one is selected depending on the ease of operation, etc. Particularly from the viewpoint of properties, it is more preferable to select carbon-based or nitrogen-based amorphous materials. When the lower barrier layer 204 is made of the above-mentioned amorphous material, the layer forming method may be a glow discharge method, a sputtering method, an ion implantation method,
This is done by ion plating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. A lower 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 the manufacturing conditions for manufacturing a photoconductive member having the structure are relatively easy to control.
The glow discharge method or the sputtering method is preferably employed because of the advantages of easy introduction into the process. 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 lower 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. The support body 2
The amorphous material described above may be deposited on 01. In the present invention, SiH ₄ and Si containing Si and H are effectively used as the raw material gas for forming the lower barrier layer 204 made of a carbon-based amorphous material. Silicon hydride gas such as silanes such as ₂ 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, carbon atoms Examples include ethylene hydrocarbons having 1 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, 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 ( _C3H6 ), _butene -1
(C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons such as 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,
Of course, H ₂ is also effectively used as the raw material gas for introducing H. Among the raw material gases for layer formation to configure the lower 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 , and 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 ₂ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀
Silanes, etc., etc. can be mentioned. In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ ,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Alkyl silicides such as Si(C ₂ H ₅ ) ₄ , SiCl(CH ₃ ) ₃ , SiCl ₂
Derivatives of silanes such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. 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. a-(SifC _1-f ) by introducing ₄ , SiH ₂ Cl ₂ , SiH ₃ Cl, etc. in a gaseous state at a predetermined mixing ratio into a device system for forming a barrier layer to generate a glow discharge. _g (X+H) _1-g
It is possible to form a barrier layer consisting of: In the present invention, when employing the glow discharge method to form the lower barrier layer 204 with a nitrogen-based amorphous material, a material selected from among the materials listed above for forming the 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, a starting material that can be effectively used as a raw material gas for introducing nitrogen atoms to form the lower barrier layer 204 has N as a constituent atom or a mixture of N and H.
_{Gaseous or _ _ _ _ _} Mention may be made of nitrogen compounds that can be gasified, such as nitrogen, nitrides and azides. In addition to this, nitrogen trifluoride (F ₃ N),
Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F ₄ N ₂ ). When forming the lower barrier layer 204 from an oxygen-based amorphous material by a glow discharge method, the starting materials that serve as the raw material gas for forming the lower barrier layer 204 include the above-mentioned materials. Starting materials for introducing oxygen atoms are added to those selected as desired from among the starting materials for forming the barrier layer. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, 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 or, by mixing a raw material gas containing Si as a constituent atom and a raw material gas containing O and H as constituent atoms at a desired mixing ratio,
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, starting materials for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrogen monoxide (NO), and nitrogen dioxide. (NO ₂ ), nitrogen monooxide (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 ), Si, O, and H as constituent atoms, such as disiloxane H ₃ SiOSiH ₃ , trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like. As described above, when forming the lower barrier layer 204 by the glow discharge method, a desired material having desired characteristics can be formed by selecting and using various starting materials for forming the barrier layer from among the materials described above. A lower barrier layer 204 can be formed of a constituent material. Specifically, a good combination of starting materials when forming the lower barrier layer 204 by a glow discharge method includes a single gas such as Si( _CH3 ) ₄ , _SiCl2 ( _CH3 ) _2, or _SiH4- . 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 −SiH ₄ system, SiCl ₂ (CH ₃ ) ₂ −
Examples include mixed gases such as SiH ₄ type gases. In order to form the lower barrier layer 204 made of a carbon-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer or 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 lower 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 targeting a wafer or a wafer containing a mixture of Si and Si ₃ N ₄ and sputtering the wafer in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
and a raw material gas for introducing halogen atoms, such as H ₂ and N ₂ or NH ₃ , diluted with diluting gas as necessary and introduced into a deposition chamber for sputtering,
The Si wafer may be sputtered by forming a gas plasma of these gases. In addition, by using Si and Si ₃ N ₄ as separate targets or by using a single target formed by mixing Si and Si ₃ N ₄ , it is possible to use rare gas as a sputtering gas. This is done by sputtering in a gas atmosphere or in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms. Possible raw material gases for introducing nitrogen atoms include the raw material gases for hydrogen atom introduction among the starting materials for barrier layer formation shown in the example of glow discharge mentioned above, which are also effective in the case of sputtering. It can be used as a natural gas. To form the lower barrier layer 204 made of an oxygen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer or a mixture of Si and SiO ₂ is used. This can be carried out by sputtering a conventional wafer or a SiO ₂ 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 hydrogen atoms and/or halogen 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 lower 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 lower barrier layer 204 in the present invention is carefully formed to provide the desired properties. In other words, a substance whose constituent atoms are Si, at least one of C, N, and O, and optionally H and/or , in terms of electrical properties, the properties range from conductivity to semiconductivity to insulation.
In addition, since each exhibits properties ranging from photoconductive properties to non-photoconductive properties, in the present invention, the preparation conditions are selected so that a non-photoconductive amorphous material is formed. is carried out strictly. The amorphous material constituting the lower barrier layer 204 of the present invention has the function of blocking the injection of free carriers from the support 201 side to the photoconductive layer 202 side, and preventing free carriers from being generated in the photoconductive layer 202. Since the photo carrier is easily allowed to move and pass through to the support body 201, it is formed to exhibit electrically insulating behavior. Further, when the photocarrier generated in the photoconductive layer 202 passes through the lower barrier layer 204, the lower barrier layer has a mobility value for the carrier passing through the lower barrier layer 204 smoothly. A barrier layer 204 is formed. An important element in the layer forming conditions for forming the lower barrier layer 204 made of the amorphous material having the above characteristics is the temperature of the support during layer forming. That is, when forming the lower barrier layer 204 made of the amorphous material on the surface of the support 201, 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 lower barrier layer 204 is appropriately selected in an optimum range in accordance with the method of forming the lower barrier layer 204. Formation of 204 is carried out, typically 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; Normally, 20 to 200℃,
The temperature is preferably 20 to 150°C. The lower barrier layer 204 can be formed continuously from the lower barrier layer 204 to the photoconductive layer 202 and further to the surface barrier layer 203 in the same system.
Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. When forming the lower barrier layer 204 using these layer forming methods, the characteristics of the lower barrier layer 204 created are influenced by the discharge power and gas pressure during layer forming, as well as the support temperature described above. This can be cited as an important factor. The discharge power conditions for effectively creating the lower barrier layer 204 with good productivity, which have the characteristics to achieve the purpose of the present invention, are usually 1 to 1.
300W, preferably 2-150W. Furthermore, the gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8×
It is desirable that it be about 10 ^-3 to 0.5 Torr. Lower 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 lower 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 lower barrier layer 204 is composed of a-SiaC _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-(SibC _1-b ) _c H _1-c , the carbon atom content is usually 30 to 0.3.
90 atomic%, preferably 40-90 atomic%, optimally 50-80 atomic%, hydrogen atom content usually 1-40 atomic%, preferably 2-80 atomic%.
35 atomic%, optimally 5-30 atomic%, b, c
If it is expressed as
0.1-0.35, optimally 0.15-0.3, c usually 0.60
~0.99, preferably 0.65-0.98, optimally 0.7-0.95
and a-(SidC _1-d ) eX _1-e or a-
(SifC _1-f ) _g (H+X) _1-g , the carbon atom content is usually 40 to 90 atomic%, preferably 50 to 90 atomic%, optimally 60 to 80 atomic%.
%, the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 20 atomic%, preferably 1 to 18 atomic%, optimally 2 to 15 atomic%.
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually
19 atomic%, preferably 13 atomic%, d,
When displaying e, f, and g, d and f are usually 0.1 to
0.47, preferably 0.1-0.35, optimally 0.15-0.3,
e and g are usually 0.8 to 0.99, preferably 0.85 to 0.99,
The optimum value is 0.85 to 0.98. When the lower 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, 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
%, preferably 35 to 55 atomic %, and the hydrogen atom content is usually 2 to 35 atomic %, preferably 5 atomic %.
It is assumed to be ~30 atomic%, and if expressed as i and j, then i
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-k ) lX _1-l or a-(Si _n N _1-n ) _o (H
+X) When composed of _1-o , the nitrogen atom content is usually 30 to 60 atomic%, preferably 40 to
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 lower 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% of silicon atoms.
67 atomic%, preferably 63 to 67 atomic%,
o is usually 0.33-0.40, preferably 0.33-0.
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%, 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 combined content of halogen atoms or halopane atoms and hydrogen atoms is usually 1 to
20 atomic%, preferably 2 to 15 atomic%, and when both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic%.
Hereinafter, it is preferably 13 atomic% or less, r,
In the representation of s, t, and u, r and s are usually 0.33~
0.40, preferably 0.33 to 0.37, t, u usually
0.80 to 0.99, preferably 0.85 to 0.98. In the present invention, the electrically insulating metal oxide constituting the lower barrier layer 204 includes TiO ₂ ,
_Ce2O3 , _ZrO2 , _HfO2 , _GeO2 , _GaO , BeO,
P ₂ O ₅ , Y ₂ O ₃ , Cr ₂ O ₃ , Al ₂ O ₃ , MgO, MgO・
Preferred examples include Al ₂ O ₃ and SiO ₂ ·MgO. Two or more of these may be used in combination to form the lower barrier layer 204. The lower barrier layer 204 made of electrically insulating metal oxide is formed by vacuum evaporation method, CVD method, etc.
(chemical vapor deposition) method, glow discharge decomposition method, sputtering method, ion implantation method, ion plating method, electron beam method, etc. 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 lower barrier layer 204 by a sputtering method, a wafer as a starting material for forming the barrier layer is used as a target for He, Ne, Ar,
This may be carried out by sputtering in a gas atmosphere for sputtering such as. When using the electron beam method, it is sufficient to place the starting material for forming the lower barrier layer in a deposition boat and irradiate it with an electron beam to deposit it.
A device that prevents carriers from flowing into the photoconductive layer 202 from the support 201 side and easily allows photocarriers generated in the photoconductive layer 202 to move and pass to the support 201 side. Therefore, it is formed to exhibit electrically insulating behavior. The numerical range of the layer thickness of the lower 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 lower barrier layer 204 is too thin, it will not be able to sufficiently prevent free carriers from flowing from the support 201 side toward the photoconductive layer 202; If it is thicker than this, the probability that the photocarrier generated in the photoconductive layer 202 will pass to the side of the support 201 becomes extremely small, and therefore, in any case, the object of the present invention can be effectively achieved. It will no longer be possible. In view of the above points, the thickness of the lower barrier layer 204 to effectively achieve the object of the present invention is usually 30 to 1000 Å, preferably 50 to 600 Å. 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 0.5 mm thick, 10 cm square molybdenum (substrate) 302 whose surface was cleaned 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 inside the fixing member 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 to create a vacuum of about 5×10 ^-7 torr (at this time, all valves in the system are closed). Auxiliary valve 32
9 and outflow valves 324, 325, 326, 3
27,328 is opened and the flow meter 337,3
After the inside of 38, 339, 340, 341 is sufficiently degassed, the outflow valve 324, 325, 326, 3
27,328 were closed. Heater 30 here
4 is turned ON and the substrate temperature is set to 250℃. Then _SiH4 gas diluted to 10vol% with _H2 (purity
99.999%) Valve 314 of cylinder 309, with H ₂
Open the valve 315 of the _B2H6 gas cylinder 310 diluted to 100vppm, and check the outlet pressure gauges 332 _, 33.
Adjust the pressure of 3 to 1Kg/cm ² and open the inflow valve 319,
Gradually open 320 and check the flow meter 337,3
SiH ₄ gas and B ₂ H ₆ gas were flowed into 38. Subsequently, the outflow valves 324 and 325 are gradually opened,
Then, the auxiliary valve 329 was gradually opened. At this time, the SiH ₄ /H ₂ gas flow rate and the B ₂ H ₆ /H ₂ gas flow rate ratio are
Inflow valves 319, 320 so that the ratio is 100:1
adjusted. Next, adjust the opening of the auxiliary valve 329 while watching the reading on the Pirani gauge 342,
The auxiliary valve 329 was opened until the pressure inside the chamber 301 became 1×10 ⁻² torr. After the internal pressure of chamber 301 stabilizes,
The main valve 331 was gradually closed and the opening was throttled until the Pirani gauge 342 indicated 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the high frequency power supply 343 is turned on while the shutter 308 is closed.
Turn on the switch and connect the electrodes 303 and 30.
13.56MHz high-frequency power was applied to room 301.
A glow discharge was generated within the battery, and the input power was 10W. The layer thickness is about 15μ by sustaining glow discharge for about 10 hours.
A photoconductive layer was formed. After that, turn off the high frequency power supply 343,
Discharge was once stopped, valves 314, 315, 319, 320, and 324, 325 were closed, and valve 331 was fully opened. After the inside of the chamber 301 is sufficiently vacuum degassed, the valve 329 is temporarily closed. Next, the valve 316 of the BF ₃ gas cylinder 311 diluted to 5 vol% with Ar and the
Gradually open the valve 318 of the _B2H6 gas cylinder 313 diluted to 5vol%, adjust the pressure of the outlet pressure gauges 334 _and 336 to 1Kg/ ^cm2 , and open the inflow valve 3.
Gradually open 21,323 and check the flow meter 33.
BF ₃ /Ar gas and B ₂ H ₆ /Ar gas were flowed into No. 9,341. Subsequently, the outflow valves 326, 32
8 was gradually opened, and then the auxiliary valve 329 was gradually opened. At this time, EF ₃ /Ar gas flow rate and
The inflow valves 321 and 323 were adjusted so that the B ₂ H ₆ /Ar gas flow ratio was 1:1. Next, adjust the opening of the auxiliary valve 329 to
1 was maintained at 1×10 ^-2 torr. After the internal pressure of the chamber 301 becomes stable, the main valve 331 is gradually closed.
The aperture was closed until the reading on the Pirani gauge 342 was 0.2 torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 343.
High frequency power was applied between the electrodes 303 and 308 in the ON state, and a glow discharge was generated in the chamber 301 with an input power of 25W. A surface barrier layer was formed by connecting glow discharge for about 5 minutes in this manner. The thickness of the surface barrier layer thus formed is approximately 400 Å. Finally, turn off the heater 304,
The high frequency power supply 343 is also turned off, the outflow valve 326 and the inflow valve 321 are closed, and the main valve 331 is fully opened to reduce the inside of the chamber 301 to 10 ^-5 torr or less, and then the main valve 331 is closed and the substrate temperature is 50°C. After waiting for the temperature to rise to 100°C, the inside of the chamber 301 was brought to atmospheric pressure using the leak valve 330, and the substrate was taken out. The photoconductive member thus obtained was placed in an experimental charging exposure apparatus. Corona charging was performed at 6KV and image exposure was performed. A halogen lamp was used as the light source, and the light intensity was about 1 ux·sec. Immediately thereafter, a good toner image was obtained on the photoconductive member surface by cascading a charged voltage developer (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, the charging polarity was reversed, that is, corona charging was performed at 6 KV, image exposure was performed, and then a cascade phenomenon was performed using a charging developer, but a good image could not be obtained. Example 2 The molybdenum substrate 302 was fixed using the same equipment as in Example 1 and the same procedure. Next, after confirming that all valves in the system are closed, the main valve 331 is fully opened to create a vacuum of about 5×10 ^-7 torr (at this time, all valves in the system are closed). Auxiliary valve 329
and outflow valves 324, 325, 326, 32
7,328 is opened and flow meter 337,33
After the inside of 8, 339, 340, 341 is sufficiently deaerated, the outflow valve 324, 325, 326, 32
7,328, were closed. Next, argon (99.999% purity) gas cylinder 31
After the valve 317 of No. 2 is opened and the reading of the outlet pressure gauge 335 is adjusted to 1 Kg/cm ² , the inflow valve 322 is opened and argon gas is introduced into the deposition chamber 30.
1. The outflow valve 327 is gradually opened until the Pirani gauge 342 indicates 5×10 ^-4 torr. After the flow rate stabilizes in this state, the main valve 331 is gradually closed and the indoor pressure is reduced to 1×10 -4 torr. The aperture was narrowed down to ^-2 torr. Next, open the shutter 308 and after confirming that the flow meter 340 is stable, turn on the high frequency power supply 343 and turn on the targets 305, 3.
13.56MHz, 100W between 06 and fixed member 303
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 lower barrier layer with a thickness of 100 Å. After that, high frequency power supply 34
3 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 322 is closed and the main valve 331 is fully opened to vent the gas in the deposition chamber 301.
Vacuum was applied to 5×10 ⁻⁵ torr. Then heater 3
The input of 04 was turned on, and the input voltage was varied while detecting the board temperature, until it stabilized at a constant value of 250°C. Furthermore, the auxiliary valve 329, then the outflow valve 327, and the inflow valve 322 were fully opened, and the inside of the flow meter 340 was also sufficiently degassed and vacuumed. Subsequently, a photoconductive layer and a surface barrier layer were formed in exactly the same manner as in Example 1. The photoconductive member thus prepared was placed in the same experimental charging exposure apparatus as in Example 1, and image formation, development, and transfer were performed in the same manner as in Example 1.
A clear image with good gradation reproducibility and higher density than in Example 1 was obtained. Moreover, the repeatability was also good. Furthermore, an attempt was made to form an image with the charging polarity reversed in the same manner as in Example 1, but no good image was obtained. Example 3 A photoconductive member was formed in exactly the same manner as in Example 1 except for changing the thickness of the surface barrier layer. 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] ○Excellent △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, 101,20
1...Support, 102,202...Photoconductive layer, 1
03,203...Surface barrier layer, 204...Lower barrier layer.

Claims (1)

[Scope of Claims] 1. A photoconductive layer composed of an amorphous material based on silicon atoms and containing at least one of hydrogen atoms or halogen atoms, on a support, and a carrier extending from the surface into the photoconductive layer. A photoconductive member in which a surface barrier layer that functions to prevent implantation is laminated in this order, the surface barrier layer being made of an amorphous material containing boron atoms as a matrix and containing hydrogen atoms and halogen atoms. A photoconductive member characterized by: 2. The photoconductive member according to claim 1, wherein the sum of the amount of hydrogen atoms and the amount of halogen atoms contained in the surface barrier layer is 1 to 50 atomic %. 3. The photoconductive member according to claim 1, wherein the surface barrier layer has a thickness of 30 Å to 1 μ. 4. Claims 1 to 3 further comprising a lower barrier layer at the interface between the support and the photoconductive layer, which functions to prevent injection of carrier from the support into the photoconductive layer. The photoconductive member described in . 5. Claim 4, wherein the lower barrier layer is made of an amorphous material containing silicon atoms as a matrix and at least one kind of atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms. The photoconductive member described in . 6 Claim 5 in which the lower 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 lower barrier layer is made of an electrically insulating metal oxide.