JPH0411860B2 - - 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.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc., highly sensitive,
It has a high signal-to-noise ratio (photocurrent (Ip)/dark current (Id)) and absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, especially for the emission and wavelength characteristics of semiconductor lasers, which have recently made remarkable progress in development. The solid-state imaging device must have matched absorption spectrum characteristics, have fast photoresponsiveness, have the desired dark resistance value, be non-polluting to the human body during use, and furthermore, solid-state imaging devices must have a certain afterimage. Characteristics such as being able to easily process within a certain amount of 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 in which an afterimage occurs due to the accumulation of 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. is known to exist. Furthermore, compared to the short wavelength side of the visible light region, the absorption coefficient in the longer wavelength region is relatively smaller than that in the long wavelength region, and there remains room for improvement in matching with semiconductor lasers. Therefore, while efforts are being made to improve the properties of the a-Si material itself, when designing photoconductive members, efforts are made to obtain the desired electrical, optical, and photoconductive properties as described above. There is a need. The present invention has been made in view of the above points, and includes a
-As a result of intensive and comprehensive research on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we found that Si has a silicon atom as its base material and 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 a- Si (H, A photoconductive member manufactured with a designed layered structure is not only usable for practical purposes, but also surpasses conventional photoconductive members in most respects;
This is based on the discovery that it has particularly excellent properties as a photoconductive member for electrophotography and that it has excellent absorption spectrum properties on the long wavelength side. 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 photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member for electrophotography that has a long lifespan, does not cause any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member for electrophotography that has high photosensitivity in the entire visible light range, excellent matching with a semiconductor laser, and fast photoresponsiveness. 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 for electrophotography, which has sufficient performance and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. The photoconductive member for electrophotography of the present invention includes a support for the photoconductive member for electrophotography (hereinafter referred to as "photoconductive member"), and a free carrier is prevented from flowing out from the free surface side on the support. or a layer thickness composed of an amorphous material having a function of blocking the inflow of surface potential, containing at least one type of atom selected from carbon atoms, nitrogen atoms, and oxygen atoms, and having silicon atoms as its base material. A surface barrier layer of 30 Å to 5 μ, provided in contact with the layer, generates photocarriers that can be moved by electromagnetic irradiation, contains at least one of hydrogen atoms or halogen atoms, and has silicon atoms as a matrix. A charge generation layer with a thickness of 0.3 to 5μ, which is composed of an amorphous material and contains 1×10 ^-1 to 10 atomic% of impurities that control the conductivity type, and photocarriers generated in the layer are efficiently injected. at least one of hydrogen atoms or halogen atoms provided in contact with the charge generation layer so as to
It is characterized by being laminated with a charge transport layer made of an amorphous material having a thickness of 3 to 100 μm and having silicon atoms as its base material. A photoconductive member designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. . In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has stable electrical properties even in a humid atmosphere. With high sensitivity,
It has a high signal-to-noise ratio, is extremely resistant to light fatigue, 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;
Conversely, a-Si(H,X) with high photosensitivity has a dark resistance of 10 ⁸
Ωm is as low as described above, and in any case, the photoconductive layer with the conventional layer structure could not be applied to an electrophotographic image forming member, whereas in the case of the present invention, the specified Because of the layered structure, even an a-Si ( ^H , Low but high sensitivitya
-Si(H,X) can also be used satisfactorily, a-Si(H,X)
Restrictions from the characteristics aspect of can be alleviated. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member of the present invention. The photoconductive member 100 shown in FIG.
2. A surface barrier layer 103 provided in direct contact with the photoconductive layer 102, and the photoconductive layer 102 includes a charge transport layer 104 and a charge generation layer 1.
This is the most basic example of the present invention, and has a functionally separated layer structure. 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, Nb, 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 metal, Conductivity is imparted to the surface. 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. 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, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the photoconductive member 100 shown in FIG. 1, the charge transport layer 104 provided on the support 101 is composed of a-Si(H,X) having the semiconductor properties shown below. p-type a-Si(H,X)...Contains only acceptor. Or one that contains both a donor and an acceptor and has a high concentration of acceptor (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 charge transport layer 104 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. In the present invention, the charge transport layer 104 made of a-Si (H, It will be done. For example, in order to form a charge transport layer composed of a-Si (H, A raw material gas for introducing atoms is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a-Si (H, What is necessary is to form a layer consisting of X). In addition, when forming by sputtering method, for example, in an atmosphere of an inert gas such as Ar, He, etc. or a mixed gas based on these gases.
When sputtering a target made of Si, 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 effectively used. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of handling during layer formation work and good Si generation efficiency. 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. 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 charge transport layer 104 containing halogen atoms according to the glow discharge method, basically Si
Silicon halide gas, which is the raw material gas for generation, and
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber in which the charge transport layer 104 is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. By forming
The charge transport layer 104 can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of a silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. It's okay. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to form a charge transport layer made of a-Si (H, Sputtering is carried out 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 electrobeam 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. Furthermore, 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 gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective starting materials for forming the charge transport layer. It can be mentioned as. 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 layer when forming the charge transport layer. is used as a suitable raw material for halogen introduction. In order to structurally introduce hydrogen atoms into the charge transport 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 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. The charge generation layer 10 has predetermined characteristics by
A charge transport layer 104 made of a-Si(H,X) is formed on the 4th surface. 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 charge transport layer of the photoconductive member to be formed or (H+
The amount of X) is usually 1 to 40 atomic %, preferably 5 to 30 atomic %. The amount of H and/or All you have to do is control the force. In order to make the charge transport layer n-type, p-type, or i-type, n-type impurities, p-type impurities,
Alternatively, this can be achieved by doping both impurities into the layer to be formed while controlling their amounts. As impurities to be doped into the charge transport layer, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferably used to make the charge transport layer p-type. It will be done. In the case of n-type, suitable elements 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 constituting the charge transport 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, Ca, P, Sb, etc. are optimal. In addition, it is also possible to control the n-type by interstitial doping with Li or the like by thermal diffusion or implantation, for example.
The amount of impurity doped into the charge transport layer is
It is determined as appropriate depending on the desired electrical and optical properties, but for n ^- type, i-type, and p ^- type, from non-doped to impurities from group A of the periodic table.
All you have to do is dope it to ×10 ^-3 atomic%,
To make it p-type, add 5x impurities from group A of the periodic table.
10 ^-3 to 1×10 ^-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 thickness of the charge transport layer 104 is determined as desired so that photocarriers generated in the charge generation layer 105, which will be described later, are efficiently injected and the injected photocarriers are efficiently transported in a predetermined direction. Therefore, it can be determined as appropriate, but usually it is 3 to 100μ, preferably 5 to 50μ. In the present invention, in order to effectively achieve the object, the charge generation layer 105 laminated on the charge transport layer 104 has the following so-called semiconductor characteristic a heavily doped with impurities that control the conductivity type. −
Composed of Si(H,X). p ⁺ type a-Si ⁽ H, Alternatively, it contains both a donor and an acceptor, and the acceptor has a high concentration (Na),
As a relative value, p-type impurity is 1×10 ^-1 ~
Contains 10 atomic%. n ⁺ type a-Si ⁽ H,
Or it contains both donor and acceptor, and the concentration of donor (Nd) is high and the relative value n
Contains type impurities of 1×10 ^-1 to 10 atomic%. The charge generation layer 105 in the photoconductive member 100 of the present invention has the function of mainly absorbing light irradiated during electrostatic image formation and generating photocarriers, but as described above, By containing 1×10 ^-1 to 10 atomic% of impurities that control the conductivity type, the characteristics of the charge generation layer in photoconductive materials are satisfied, and the photosensitivity on the long wavelength side is dramatically increased compared to conventional examples. It can be improved. Therefore, for example, a laser that oscillates light in a long wavelength range, such as an AlGaAs semiconductor laser (oscillation light of 0.8 μm to 0.7 μm), can be used as the light source. Of course, the charge generation layer 105 in the present invention generates a sufficient amount of photocarriers even with light in shorter wavelengths than these wavelength ranges, so a light source that emits light in such wavelength ranges may be used. can also be used. Furthermore, since the charge transport layer 104 is composed of a-Si(H,X) having normal spectral sensitivity characteristics,
Generates light in the normal visible light range. For example, when a halogen lamp, tungsten lamp, fluorescent lamp, etc. is used as a light source, the light emitted from the light source is mainly absorbed by the charge transport layer 104, and photocarriers are not generated in the layer 104. Therefore, even in this case, the photoconductive member of the present invention can be used satisfactorily. The photoconductive member of the present invention has sufficient photosensitivity and quick photoresponsiveness for light in the normal visible light range, long wavelength range of the visible light range, and even longer wavelength range. Therefore, a light source with a wide range of wavelengths can be used. In the present invention, the amount of impurities contained in the charge generation layer 105 can normally be within the numerical range shown above, but more preferably 5×
A range of 10 ^-1 to 10 atomic % is desirable because it produces even greater effects. The thickness of the charge generation layer 105 in the present invention is usually 0.3 to 5 .mu.m, preferably 0.5 to 2 .mu.m. The surface barrier layer 103 prevents free carriers in the charge generation layer 105 from flowing out or prevents the surface barrier layer 10 from flowing out.
3. It has a function of preventing surface charges imparted to the surface from being injected into the layer, and is excellent in retaining surface charges. The surface barrier layer 103 is an amorphous material whose base material is silicon and which contains at least one type of atom 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- [Si _x
(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 surface barrier layer 103, carbon-based amorphous materials that can be effectively used in the present invention include a-Si _a C _1-a , a-(Si _b C _1-b ) _c H _1-c , a-(Si _d
C _1-d ) _e X _1-e , a-(Si _f C _1-f ) _g (H+X) _1-g , a-Si _h N _1-h , a-Si _i
N _1-i ) _j H _1-j , a-(Si _k N _1-k ) _l X _1-l , a-(Si _n N _1-n )
_o (H+X) _1-o , a- as an oxygen-based amorphous material
Si _p O _1-p ,a-(Si _p O _1-p ) _q H _1-q ,a-(Si _r O _1-r ) _s
X _1-s , a-(Si _t O _1-t ) _u (H+X) _1-u , etc., and further,
Among the above-mentioned amorphous materials, examples include amorphous materials containing at least two types of atoms among C, 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 have the characteristics required for the surface barrier layer 103 depending on the optimized design of the layer structure and the continuous formation of the charge transport layer 104 and charge generation layer 105 provided in contact with the barrier layer 103. The most suitable one is selected depending on the ease of operation, etc. In particular, from the viewpoint of properties, it is more preferable to select carbon-based or nitrogen-based amorphous materials. When the surface barrier layer 103 is made of the above-mentioned amorphous material, the layer formation method may be a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, etc. will be accomplished. 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. Barrier layer 10 in which carbon atoms, nitrogen atoms, oxygen atoms, or hydrogen atoms or 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 barrier layer 10.
The glow discharge method or the sputtering method is preferably employed because of the advantages of easy introduction into the liquid. Furthermore, in the present invention, the surface barrier layer 103 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 103 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 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. The support 1
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 raw material gases for forming the surface barrier layer 103 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. saturated hydrocarbons having 1 to 5 carbon atoms, carbon atoms Examples include ethylene hydrocarbons having 2 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 (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 103 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 , ClE ₅ , _BrE5 ,
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 ₈ ,
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 and SF ₆ , Si(CH ₃ ) ₄ , Si(C ₂ Alkyl silicides such as H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ may also be mentioned as useful. These surface barrier layer-forming substances are used to form a surface barrier layer so that silicon atoms, carbon atoms, and optionally halogen atoms and/or hydrogen atoms are contained in a predetermined composition ratio in the surface barrier layer formed. They are selected and used as desired when forming the barrier layer. For example, SiHCl ₃ which contains Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms and form a surface barrier layer with desired characteristics, SiCl ₄ ,
_{A- ( Si f}
A barrier layer consisting of C _1-f ) _g (X+H) _1-g can be formed. In the present invention, when employing a glow discharge method to form the surface barrier layer 103 with a nitrogen-based amorphous material, a material for forming the surface barrier layer listed above may be used as desired. In addition to that, the next raw material gas for introducing nitrogen atoms may be used. That is, starting materials that can be effectively used as raw material gases for introducing nitrogen atoms to form the surface barrier layer 103 include those containing N as a constituent atom, or those containing N as a constituent atom.
and H as constituent atoms, such as 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 nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and azides. In addition to the above, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned because they can also introduce halogen atoms in addition to nitrogen atoms. I can do it. When forming the surface barrier layer 103 using an oxygen-based amorphous material by a glow discharge method, the starting materials that serve as the raw material gas for forming the surface barrier layer 103 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 surface 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, 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. Either a raw material gas containing Si and a raw material gas containing O and H are mixed 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), 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 ), 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 mentioned above, when forming the surface barrier layer 103 by the glow discharge method, by selecting and using various starting materials for forming the surface barrier layer from among the above-mentioned materials, desired characteristics can be obtained. The surface barrier layer 103 made of a desired constituent material can be formed. Specifically, a good combination of starting materials when forming the surface barrier layer 103 by a glow discharge method includes, for example, Si(CH ₃ ) ₄ , SiCl ₂
Single gas such as (CH ₃ ) ₂ or SiH ₄ −N ₂ O system, SiH ₄ −
O ₂ (−Ar) system, SiH ₄ −NO ₂ system, SiH ₄ −O ₂ −N ₂
system, SiCl ₄ −CO ₂ −H ₂ system, SiCl ₄ −NO−H ₂ system,
SiH ₄ −NH ₃ system, SiCl ₄ −NH ₄ system, SiH ₄ −N ₂ system,
SiH ₄ −NH ₃ −NO system, Si(CH ₃ ) ₄ −SiH ₄ system, SiCl ₂
Examples include mixed gases such as (CH ₃ ) ₂ -SiH ₄ . To form the surface barrier layer 103 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 or halogen atoms However, the Si wafer may be sputtered by forming a gas plasma of these gases. Alternatively, sputtering can be carried out in a gas atmosphere containing at least H atoms or halogen atoms by using Si and C as separate targets or by using a single target containing Si and C. It is accomplished by doing. 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 103 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. Alternatively, it can be diluted as a sputtering gas by using separate targets for Si and Si ₃ N ₄ or by using a single target formed by mixing Si and Si ₃ N ₄ . This is done by sputtering in a 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 in the starting materials for forming the surface barrier layer shown in the example of glow discharge mentioned above, which can also be used in the case of sputtering. Can be used as an effective gas. To form the surface barrier layer 103 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 103 by a glow discharge method or a sputtering method is a so-called rare gas, for example.
Preferred examples include He, Ne, Ar, and the like. The surface barrier layer 103 in the present invention is carefully formed so as to provide the required properties as desired. 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. In terms of electrical properties, 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, so that a non-photoconductive, electrically insulating amorphous material is formed.
The conditions for its creation are strictly selected. An important element in the layer forming conditions for forming the surface barrier layer 103 made of the amorphous material having the above characteristics is the temperature of the support during layer forming. That is, when forming the surface barrier layer 103 made of the amorphous material on the surface of the charge generation layer 105, 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 103 is appropriately selected in an optimal range in accordance with the method of forming the surface barrier layer 103. 103 is carried out, typically at 50-300°C, preferably at
The temperature is preferably 100°C to 250°C.
The formation of the surface barrier layer 103 requires delicate control of the composition ratio of atoms constituting each layer and control of the layer thickness, which allows continuous formation from the photoconductive layer 102 to the surface barrier layer 103 in the same system. The glow discharge method and sputtering method are advantageous because they are relatively easy compared to other methods, but when forming the surface barrier layer 103 using these layer formation methods, ,
Similar to the support temperature described above, the discharge power and gas pressure during layer formation can be cited as important factors that influence the characteristics of the surface barrier layer 103 to be created. The discharge power conditions for effectively creating the surface barrier layer 103 with good productivity, which has the characteristics to achieve the purpose of the present invention, are usually 1 to 1.
300W, preferably 2-150W. Also, 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. Surface barrier layer 103 in the photoconductive member of the present invention
The amount of carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, and halogen atoms contained in the surface barrier layer 10
Similar to the production conditions in No. 3, this is an important factor in forming a surface barrier layer that provides the desired characteristics to achieve the object of the present invention. When the surface barrier layer 103 is composed of a-Si _a 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 to 75 atomic%, the representation of a is usually 0.1 to 0.4, preferably 0.2 to 0.35, optimally 0.25 to 0.3, a-(Si _b C _1-b ) _c H ₁ In the case of _-c , the carbon atom content is usually 30~
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 to 90 atomic%, preferably 50 to 90 atomic%, optimally 60 to 80 atomic%, and the content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is usually 1 to 1.
The content of hydrogen atoms is usually 19 atomic%, preferably 13 atomic% when both halogen atoms and hydrogen atoms are contained. In the representation of d, e, f, g, d and f are usually
0.1~0.47, preferably 0.1~0.35, optimally 0.15~
0.3, e, g is usually 0.8 to 0.99, preferably 0.82 to
0.99 The optimum value is 0.85 to 0.98. When the surface barrier layer 103 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%,
Preferably 35 to 55 atomic%, hydrogen atom content usually 2 to 35 atomic%, preferably 5 to 55 atomic%.
30 atomic% and expressed as i and 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-k ) _l X _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 surface barrier layer 103 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 to 0.40, preferably 0.33
~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 0.37q, 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 content of hydrogen atoms is usually 19 atomic% or less, preferably 13 atomic% or less, and r, s,
In the representation of t and u, r and s are usually 0.33 to 0.40,
Preferably 0.33 to 0.37t, u 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 103 include TiO ₂ ,
Ce ₂ O ₃ , ZrO ₂ , HfO ₂ , G _e O ₂ , _Ca O, B _e O,
P ₂ O ₅ , Y ₂ O ₃ , C _r2 O ₃ , Al ₂ O ₃ , M _g O, M _g O・
Preferred examples include Al ₂ O ₃ and SiO ₂ ·M _g O. Two or more of these may be used in combination to form the intermediate layer. The surface barrier layer 103 made of electrically insulating metal oxide can be 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 103 by sputtering, a wafer as a starting material for forming the surface barrier layer is used as a target, He,
This may be carried out by sputtering in a sputtering gas atmosphere such as Ne or 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 103 in the present invention is one of the important factors for effectively achieving the object of the present invention. The layer thickness of the surface barrier layer 103 is as follows:
Typically it is between 30 Å and 5 μ, preferably between 50 Å and 2 μ. FIG. 2 shows a schematic configuration diagram for explaining the configuration of another embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 has a lower barrier layer 206 between the support 201 and the charge transport layer 204, and is similar to the photoconductive member shown in FIG. 1 except for this point. It has a layered structure. The lower barrier layer 206 has the function of blocking injection of free carriers from the support 101 side to the charge transport layer 204 side, and of photocarriers generated in the charge generation layer 205 by electromagnetic wave irradiation. It has a function of easily allowing the photo carrier to be moved to the support body 101 side to pass through the lower barrier layer 206. The material constituting the lower barrier layer 206 is selected as desired from among the materials constituting the surface barrier layer 103 described above, and its formation is as follows:
This is done by the same method as for forming the surface barrier layer 103. The thickness of the lower barrier layer 206 is determined as desired depending on the selection of the constituent materials and the required properties so that the above function can be fully performed, but it is usually 30 to 1000 Å, preferably 50~600Å
It is desirable that this is the case. Example 1 Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, an electrophotographic image forming member was prepared 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 craftite (99.999%).
It is installed above. These are shutter 3
Covered by 08. The substrate 302 is
It is heated with an accuracy of ±0.5° C. by a heater 304 inside the fixed member 303. Temperature was measured directly on the back side of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 331 is fully opened to create a vacuum of approximately 5×10 ^-7 torr (at this time, all valves in the system are closed). , auxiliary valve 329 and outflow valve 3
24, 325, 326, 327, 328 are opened and flow meters 337, 338, 339, 340,
After the inside of 341 is sufficiently degassed, the outflow valve 32
4,325,326,327,328 and auxiliary valve 329 were closed. After that, turn on the heater 304.
The input voltage was turned on, the input voltage was increased, and the input voltage was varied while detecting the board temperature until it stabilized at a constant value of 250℃. Next, SiH ₄ gas (99.999% purity) diluted to 10 vol% with H ₂ in valve 314H ₂ of cylinder 309
Open the valve 316 of the B ₂ H ₆ gas cylinder 311 diluted to 500vppm, and check the outlet pressure gauges 332 and 33.
Adjust the pressure of 4 to 1Kg/cm ² and open the inflow valve 319,
Gradually open 321 and check the flow meter 337,3
SiH ₄ /H ₂ gas B ₂ H ₆ /H ₂ gas was flowed into the chamber. Subsequently, the outflow valves 324 and 326 were gradually opened, and then the auxiliary valve 329 was gradually opened. At this time, SiH ₄ /H ₂ gas flow rate and B ₂ H ₆ /H ₂
The inlet valves 319 and 321 were adjusted so that the gas flow ratio was 500:1. Next, the opening of the auxiliary valve 329 was adjusted while observing the reading on the Pirani gauge 342, and the auxiliary valve 329 was opened until the inside of the chamber 301 reached 1×10 ⁻² torr. After the internal pressure of the chamber 301 became stable, the main valve 331 was gradually closed and the opening was throttled until the reading on the Pirani gauge 342 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 308 is closed, and then the high frequency power source 343 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 303 and 308 to cause glow inside the chamber 301. A discharge was generated and the input power was 10W. The glow discharge was continued for 10 hours to form a charge transport layer with a thickness of about 15 μm. The high frequency power source 343 was turned off, the discharge was temporarily stopped, and the valve 331 was once fully opened. next
SiH ₄ /H ₂ gas flow rate and S ₂ H ₆ /H ₂ gas flow rate ratio is 1:
2, adjust the opening of the auxiliary valve 329 so that the inside of the chamber 301 is 1×
It was kept at 10 ^-2 torr. After the internal pressure of the chamber 301 became stable, the main valve 331 was gradually closed and the opening was throttled until the reading on the Pirani gauge 342 reached 0.2 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the high frequency power source 343 is turned on and high frequency power is applied between the electrodes 303 and 308.
A glow discharge was generated in the chamber 301 with an input power of 10W. In this manner, the glow discharge was continued for about 40 minutes to form a charge generation layer of about 1 μm. After the discharge was stopped, the valves 324 and 326 were closed, and the valve 329 and the valve 331 were fully opened to exhaust the chamber 301 to 5×10 ⁻⁷ torr. Shutter 308
will be opened at this time. The substrate temperature was adjusted to 150°C and stabilized. Next, the input voltage of the heater 804 is lowered, the valve 318 of the argon (99.999% purity) gas cylinder 313 is opened, and the reading of the outlet pressure gauge 336 is adjusted to 1 Kg/cm ² , and then the inflow valve 323 is opened. Then, the outflow valve 328 was gradually opened to allow argon gas to flow into the chamber 301. the outflow valve 32 until the reading on the Pirani gauge 342 is 5×10 ^-4 torr.
8 was gradually opened, and after the flow rate became stable in this state, the main valve 331 was gradually closed, and the opening was narrowed until the indoor pressure reached 1×10 ⁻² torr.
With the shutter 308 open, the flow meter 34
After confirming that 1 is stable, turn on the high frequency power supply 34.
3 was turned on, and 13.56 MHz, 100 W AC power was input between targets 305, 306 and fixed member 303. Under these conditions, the layers were formed while performing matching so that stable discharge could continue.
Discharge was continued in this manner for about 10 minutes to form a surface barrier layer of 900 Å. The heating heater 304 is turned off, the high frequency power supply 343 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 324, 326 and the inflow valves 319, 321 are closed, and the main valve 3 is turned off.
31 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less, the main valve 331 was closed, the inside of the chamber 301 was brought to atmospheric pressure by 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 is performed at 5.5KV, and exposure is performed by scanning with a 780nm semiconductor laser fed with an image signal, and the light intensity is 5μJ.
It was hot. Immediately thereafter, a good toner image was obtained on the photoconductive member surface by cascading a chargeable 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, high-density images with excellent resolution and good gradation reproducibility were obtained. Further, even after image formation was repeated 50,000 times, no deterioration in the image characteristics was observed. In addition, cylinder 810 contains SiF (containing 10 vol% H ₂ ),
817 is filled with _N2 . These gases are some of the gas species used in the following examples. Example 2 In forming a charge generation layer, SiH ₄ /H ₂ and B ₂ H ₆ /
When a photoconductive member was prepared under the same conditions and procedures as in Example 1, except that the content of B in the layer was varied by changing the flow rate ratio of H ₂ , and A photoconductive member was prepared under the same conditions and procedures as in Example 1, except that in forming the charge generation layer, the thickness of the charge generation layer was varied by changing the glow discharge time. In this case, each sample was placed in the same charging exposure apparatus as in Example 1 to form an image, and the image quality was evaluated, and the results shown in Table 1 below were obtained.

[Table] Example 3 A photoconductive member (layer structure is the same as shown in FIG. 2) under exactly the same conditions as Example 1 except that a lower barrier layer was further provided at the interface between the support and the charge transport layer.
was created. The lower barrier layer has a glow discharge time of 5
The surface barrier layer was formed under exactly the same conditions as in Example 1, except that the surface barrier layer was formed for 1 minute.
Its thickness was approximately 500 Å. When an image was formed using this photoconductive member using the same charging exposure device as in Example 1, a high-quality image with even higher contrast than in Example 1 was obtained. Example 4 When creating the charge generation layer, instead of using _B2H6 gas diluted to _500vppm with _H2 , 500vppm of _H2 was used.
A photoconductive member was produced under exactly the same conditions as in Example 3, except for using PH ₃ gas diluted to 50%.
The layer structure in this case is shown in FIG. The photoconductive member thus obtained was placed in the charging exposure apparatus used in Example 1. For image formation
Corona charging is performed at 6KV, and exposure is performed by scanning with a 780nm semiconductor laser fed with an image signal, and the amount of light is 10μJ. The toner image on the photoconductive member is created by cascading a charged developer onto the photoconductive member surface immediately after exposure.
A good transferred image could be obtained on the transfer paper using 5.5KV corona charging. Example 5 Tables 2 to 4 show examples in which the conditions for forming the surface barrier layer and the lower barrier layer were changed based on the layer structure shown in FIG. In the example mentioned here, the charge generation layer and the charge transport layer are exactly the same as those mentioned in Example 1.

【table】

【table】

【table】

【table】

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are schematic layer structure cross-sectional views for explaining the layer structure of preferred embodiments of the photoconductive member of the present invention, and FIG. 3 is a case in which the photoconductive member of the present invention is prepared. FIG. 2 is a schematic explanatory diagram for explaining a typical example of the device. 100,200...Photoconductive member, 101,20
1...Support, 102,202...Photoconductive layer, 1
03,203...Surface barrier layer, 104,204...
...charge transport layer, 105,205...charge generation layer,
206...lower barrier layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a support having a function of preventing the outflow of free carriers or the inflow of surface potential from the free surface side, and comprising carbon atoms on the support. , a surface barrier layer having a thickness of 30 Å to 5 μ and made of an amorphous material having silicon atoms as a matrix and containing at least one type of atom selected from nitrogen atoms and oxygen atoms, provided in contact with the layer; generated by electromagnetic wave irradiation, containing at least either a hydrogen atom or a halogen atom,
The impurity, which is composed of an amorphous material with silicon atoms as its base material and controls the conductivity type, is 1×10 ^-1 ~10 atomic.
%, and at least one of hydrogen atoms or halogen atoms provided in contact with the charge generation layer so that photocarriers generated in the layer are efficiently injected. A layer thickness of 3 to 3 containing either one of the two and having silicon atoms as the matrix
A photoconductive member for electrophotography, characterized in that a charge transport layer made of an amorphous material with a thickness of 100μ is laminated thereon. 2. The photoconductive member for electrophotography according to claim 1, wherein the barrier layer on the surface contains at least either a hydrogen atom or a halogen atom. 3. Directly sandwiched between the support and the charge transport layer, which prevents the injection of free carriers from the support side to the charge generation layer side, and when irradiating the electromagnetic waves, Claim 1, further comprising a lower barrier layer having a function of allowing photo carriers generated in the charge generation layer to pass toward the support. A photoconductive member for electrophotography as described in . 4. Claim 3, wherein 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 electrophotographic photoconductive member described above. 5 Claim 3 in which the lower barrier layer contains at least either hydrogen atoms or halogen atoms
A photoconductive member for electrophotography as described in 2. 6. The photoconductive member for electrophotography according to claim 2, wherein the lower barrier layer is made of an electrically insulating metal oxide. 7. The photoconductive member for electrophotography according to claims 3 to 6, wherein the lower barrier layer has a layer thickness of 30 Å to 1000 Å. 8. The photoconductive member for electrophotography according to claim 1, wherein the charge transport layer exhibits i-type semiconductor characteristics. 9. The photoconductive member for electrophotography according to claim 1, wherein the charge generation layer exhibits p ⁺ type semiconductor characteristics. 10. The photoconductive member for electrophotography according to claim 1, wherein the charge generation layer exhibits n ⁺ type semiconductor characteristics. 11. When the charge generation layer exhibits p ⁺ type semiconductor characteristics, the charge transport layer exhibits n ^- type, n-type or i-type semiconductor characteristics. Element. 12. When the charge generation layer exhibits n ⁺ type semiconductor characteristics, the charge transport layer exhibits p-type, p ^- type, or i-type semiconductor characteristics. Element.