JPS6242264B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is sensitive to electromagnetic waves such as light (light here in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.) and is used in the field of image formation. The present invention relates to an electrophotographic imaging member. Photoconductive materials constituting the photoconductive layer in electrophotographic imaging members include Se, Se-Te, CdS,
OPC materials such as ZnO, PVCz, and TNF are well known, but recently, for example, German Publication No. 2746967
As described in Publication No. 2855718, it has properties comparable to other photoconductive materials in terms of photosensitivity, spectral wavelength range, photoresponsivity, dark resistance, etc. In addition, amorphous silicon (hereinafter abbreviated as a-Si) is a promising photoconductive material because it can easily perform p-n control despite being amorphous and is non-polluting to the human body. It is attracting attention. As described above, a-Si has superior properties in many respects than other photoconductive materials, and its practical application as an electrophotographic image forming member is rapidly progressing, but it is still There are still some points that can be resolved. For example, in some cases, residual potential may remain during use, and if used repeatedly for a long time, fatigue may accumulate, causing ghost phenomena and white spots in transferred images. This may cause inconveniences such as. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. This phenomenon is particularly likely to occur when the support is a drum-shaped support commonly used in the field of electrophotography, and this phenomenon tends to occur in terms of stability over time. There are some points that can be resolved. On the other hand, 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,
Although it has many advantages compared to OPC (organic photoconductive materials) such as ZnO, PVCz, and TNF, it has a single-layer structure made of a-Si that has properties suitable for use in conventional solar cells. Even if the photoconductive layer of an electrophotographic image forming member having a conductive layer is subjected to charge management for electrostatic image formation, dark decay does not occur.
The above-mentioned tendency is extremely rapid, making it difficult to apply normal electrophotographic methods, and in a humid atmosphere, and in some cases, it may not be possible to retain any electrostatic charge until the development time. It has been found that there are points that can be solved. 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 comprehensive research and study on Si from the viewpoint of its adaptability and applicability as an electrophotographic image forming member, we found that silicon atoms are used as the base material, hydrogen atoms (H) or halogen atoms (X). An amorphous material (amorphous material) containing at least one of the following, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as a-Si as a generic term] Use (H,X)]
The electrophotographic image forming member obtained by specifying the layer structure of the amorphous layer, which is composed of Not only can it be used, but it is superior in most respects compared to conventional products, and has particularly excellent characteristics in terms of light sensitivity and image quality stability for electrophotography. It is based on the finding that there are 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 an electrophotographic image forming member in which no or almost no residual potential is observed. Another object of the present invention is to provide an electrophotographic imaging member that has high photosensitivity in the entire visible light range and quick photoresponsiveness. Another object of the present invention is to have sufficient charge retention ability during charging processing for electrostatic image formation, and to maintain its characteristics even in a humid atmosphere, to the extent that ordinary electrophotography can be applied very effectively. An object of the present invention is to provide an electrophotographic imaging member having excellent electrophotographic properties with almost no observed deterioration. 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 electrophotographic image forming member of the present invention includes an electrophotographic support having a surface made of aluminum oxide containing water in its chemical structure, and at least one of hydrogen atoms or halogen atoms, and a silicon atom as a matrix. The amorphous layer is made of an amorphous material that exhibits photoconductivity, and the amorphous layer has a layer region containing carbon atoms in at least a part of the layer region. The distribution of carbon atoms contained in the layer region is substantially uniform in a plane substantially parallel to the surface of the support, and is non-uniform in the thickness direction of the layer, such that the carbon atoms contained in the layer region are substantially uniform. More carbon atoms are distributed on the surface side where the support is provided than in the center of the layer region, and the content of carbon atoms in the entire layer region is 0.005 to 30 atomic%, and On the surface where it is provided or near the surface,
It is characterized by having a distribution peak whose value is in the range of 0.03 to 90 atomic%. An electrophotographic imaging member designed to have the configuration described above can solve all of the problems described above, and has extremely excellent electrical, optical, photoconductive properties, and usage environment characteristics. shows. In particular, 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 characteristics even in a humid atmosphere, has high sensitivity, and has high It has a high signal-to-noise ratio, has excellent resistance to light fatigue and repeated use, and can obtain high-quality visible images with high density, clear halftones, and high resolution. Furthermore, it has excellent mechanical and electrical contact and adhesion without lifting, peeling or layer cracking from the support, and there is no deterioration in initial properties even after repeated use for a long time. It has the following advantages. DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic image forming member of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member for electrophotography according to the present invention. A photoconductive member 100 shown in FIG. 1 includes a barrier layer 102 provided as necessary on an electrophotographic support 101 having a surface made of aluminum oxide containing water in its chemical structure; 1
01 or an amorphous layer 103 provided in direct contact with the barrier layer 102, the amorphous layer 103 has a layer region containing carbon atoms in at least a part thereof, and the layer The distribution of carbon atoms in the region is substantially uniform in a plane substantially parallel to the surface of the support 101, is non-uniform in the thickness direction of the layer, and is contained in the layer region. More carbon atoms are distributed on the surface side where the support 101 is provided than in the center of the layer region, and the carbon atom content Ct in the entire layer region is 0.005 to 30 atomic%.
, and the value is 0.03 to 0.03 on the surface of the layer region on the side where the support 101 is provided or near the surface.
The peak of the distribution amount is in the range of 90 atomic%. The support 101 has an aluminum oxide film containing water in its chemical structure on at least its surface, but such a film is most commonly processed and formed for use in electrophotography and then subjected to appropriate pretreatment. Al ₂ O ₃ H ₂ can be obtained by anodizing the surface of a pure aluminum or aluminum alloy substrate, then performing appropriate pretreatment as necessary, and then subjecting it to boiling water treatment or steam treatment. O or
It is obtained with the composition Al ₂ O ₃ .3H ₂ O. As the anodic oxidation treatment, a method that forms a film with excellent electrical dielectric strength is adopted, and examples thereof include an oxalic acid method, a sulfuric acid method, and a chromic acid method. For example, in the oxalic acid method, the electrolyte used is, for example, 1 to 3% oxalic acid or oxalate solution, 1 to 3%
% solution of malonic acid or its salts, 35 g of oxalic acid,
Examples include a solution in which 1 g of KMnO ₄ is dissolved in 1 g of water. The current density and voltage in this case are determined appropriately depending on the electrolytic solution used, the material to be treated, etc., but the current density is 3 to 20 Amp/d.
cm ² , and the voltage is about 40 to 120 Volts. Also, the temperature of the bathtub during anodizing is 10 to 30℃.
It is said to be in the range of about ℃. In the case of the sulfuric acid method, different characteristics can be obtained by changing the electrolyte concentration between 10 and 70%, keeping the voltage at 10 and 15 Volts, and changing the treatment time between 10 and 15 minutes. A film can be formed. In this case, the power consumption is 0.5 to 2KWh/
^m2 , and the processing temperature is about 15-30℃. For example, if you want to make a strong and hard film, use a solution of 5% sulfuric acid and 5% glycerin, and use 12 to 15 Volts.
You can process it for 20 to 40 minutes. Conversely, to obtain a highly flexible film, use 25% sulfuric acid and 20% glycerin.
% solution at 12°C to 30°C and at a voltage of 15Volts.
It is sufficient to process for 30 to 60 minutes. Furthermore, sulfuric acid 5-10%
It is also possible to use an electrolytic solution in which some amount of Al ₂ (SO ₄ ) ₃ is dissolved in a solution at a bath temperature of about 15 to 20°C. The power consumption in these cases is 1m ²
When obtaining a hard film, the amount per unit is about 2KWh, and when obtaining a soft film, it is about 0.5 to 1MWh. To maximize the electrical dielectric strength of the film formed, the concentration of the solution should be 60-77% H ₂ SO ₄ , 1 part glycerin to 15 parts volume of the solution should be added, and the temperature of the solution bath should be The temperature may be 20 to 30°C, the voltage may be approximately 12 Volts, and the current density may be 0.1 to 1.0 Amp/dm ² . The substrate anodized by the above method is subjected to appropriate pretreatment such as washing as necessary, and then boiling water treatment or steam treatment to form the final form of the film. will be applied. The boiling water treatment may be carried out by immersing the anodized substrate in water that has been desalted and adjusted to have a pH of 5 to 9 and heated to about 80 to 100°C. In the steam treatment method, the film is thoroughly washed with boiling water and then treated with a reducing aqueous solution such as TiCl ₃ , SnCl ₂ , FeSo ₄ to completely remove the components of the electrolyte adhering to the film. The anodized substrate may be kept in superheated steam of about 4 to 5.6 kg/cm ² for an appropriate period of time. In the present invention, Al-Mg-Si type and Al-Mg type aluminum alloy materials are used to form a film that has desired characteristics and good matching with the photoconductive layer formed thereon. , Al−Mg−Mn
system, Al-Mn system, Al-Mg system, Al-Mg-Si system, Al
-Mg-Mn system, Al-Cu-Mg system, Al-Cu-Ni system,
Al-Cu series, Al-Si series, Al-Cu series, Al-Cu-Zn
system, Al-Cu-Ni system, Al-Si system, Al-Cu-Si system,
Examples include Al-Mg-Si system. Specifically, for example, A51S, 61S, 63S, Aludur,
Legal, Anticorodal, Pantal, SilalV, RS,
52S, 56S, Hydronalium, BS-Seewasser,
4S, KS-Seewasser, 3S, 14S, 17S, 24S, Y
Examples include those commercially available under product standard names such as Alloy, NS, RS, Silumin, American Alloy, German Alloy, Kupfer-Silumin, and Silumin-Gamma. The thickness of the film chemically containing water provided on the surface of the support in the present invention depends on the characteristics of the photoconductive layer formed thereon, its constituent materials, layer thickness, etc. Although it is determined appropriately according to the desire, in normal cases, it is 0.05 to 10μ,
The thickness is preferably 0.1 to 5μ, most preferably 0.2 to 2μ. The barrier layer 102 effectively blocks free carriers from flowing from the support 101 side toward the amorphous layer 103 side, or from the amorphous layer 103 side toward the support body 101 side, and also prevents free carriers from flowing into the support body 101 side during electromagnetic wave irradiation. Formed in the amorphous layer 103 by electromagnetic wave irradiation, the support 10
It has a function of easily allowing the photo carrier moving toward the support 101 to pass from the amorphous layer 103 side to the support body 101 side. The barrier layer 102 has the above-mentioned functions, but by directly providing the amorphous layer 103 on the support 101, the barrier layer 102 has the interface formed between the support 101 and the amorphous layer 103. In the present invention, it is not necessary to provide the barrier layer 102 as long as the same function as that of the barrier layer 102 described above is fully exhibited. Furthermore, by containing a sufficient amount of carbon atoms in the surface layer region of the amorphous layer 103 on the side of the support 101, the barrier layer 1 can be formed in some regions of the amorphous layer 103.
It can have the same function as 02, and the carbon atom content in this case is usually 1.5 to 9.0 per 1 silicon atom in the layer region that exhibits this function. is desirable. The barrier layer 102 is an amorphous material having silicon as its base material and containing at least one kind of atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms, and at least one of hydrogen atoms or halogen atoms as necessary. Materials〈These are collectively referred to as a-[Si _x (C,
N, O) _1-x ] _y (H, X) _1-y (however, 0<
x<1,0<y<1)>, or an electrically insulating metal oxide or an electrically insulating organic compound. In the present invention, preferred halogen atoms (X) are F, Cl, Br, and I, with F and Cl being particularly preferred. Specifically, as an amorphous material constituting the barrier layer 102, for example, a-
Si _a C _1-a , a-(Si _b C _1-b ) _c H _1-c , a-(SidC _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 ) as a nitrogen-based amorphous material
jH _1-j ,a-(S _k N _1-k )lX _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. Furthermore, in the above amorphous material, at least two of C, N, and O Examples include amorphous materials containing atoms 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 barrier layer 102 and the barrier layer 1 depending on the optimized design of the layer configuration.
The most suitable one is selected depending on the ease of continuous production with the amorphous layer 103 stacked on 02, etc. Particularly from the viewpoint of properties, it is more preferable to select a carbon-based or nitrogen-based amorphous material. When the barrier layer 102 is made of the amorphous material mentioned above, 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, or the like. Ru. In order to form the barrier layer 102 by the glow discharge method, the raw material gas for forming the amorphous material is mixed with a dilution gas at a predetermined mixing ratio as necessary;
The support 101 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, thereby forming the support 101.
The amorphous material described above may be deposited thereon. In the present invention, SiH ₄ and Si ₂ containing Si and H as constituent atoms are effectively used as raw material gases for forming the barrier layer 102 made of a carbon-based amorphous material. Silicon hydride gas such as silanes such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., saturated hydrocarbons containing C and H as constituent atoms, e.g. 1 to 5 carbon atoms, 1 carbon atom -5 ethylene hydrocarbons, C2-4 acetylene hydrocarbons, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane ( _n - _C4H10 ) _, pentane ( _C5H12 ), ethylene hydrocarbons include ethylene ( _C2H4 ), propylene ( _C3H6 ) _, butene- ₁ ( _{C4H8 )} , butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylene hydrocarbons 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,
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 barrier layer 102 from a carbon-based amorphous material containing halogen atoms, raw material gases for introducing halogen atoms include, for example, simple halogen, hydrogen halide, and interhalogen compounds. , silicon halide, halogen-substituted silicon hydride, silicon hydride, and the like. Specifically, halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, and HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , ClF ₅ ，
BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F 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 1, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si
Alkyl silicides such as (C ₂ H ₅ ) ₄ and SiCl(CH ₃ ) ₃ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₂ , (CH ₃ ) ₂ and SiCl ₂ 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. ₄ , SiH ₂ Cl ₂ , _or SiH ₃ Cl in a gaseous state at a predetermined mixing ratio to generate a glow discharge _{. f} ) _g (X+H) _1-g
It is possible to form a barrier layer consisting of: When employing the glow discharge method to form the barrier layer 102 with a nitrogen-based amorphous material, select the desired material from the materials listed above for forming the barrier layer, and add Then, the next raw material gas for introducing nitrogen atoms may be used. That is, a starting material that can be effectively used as a raw material gas for introducing nitrogen atoms to form the barrier layer 102 is nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), gaseous or gasifiable nitrogen, nitrides and azides, etc. The following nitrogen compounds can be mentioned. In addition, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be mentioned because they can introduce halogen atoms in addition to nitrogen atoms. I can do it. When forming the barrier layer 102 using an oxygen-based amorphous material by a glow discharge method, the starting materials that serve as the raw material gas for forming the barrier layer 102 include the above-mentioned barrier layer. Starting materials for introducing oxygen atoms are added to those selected as desired from among the starting materials for formation. 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. or mix a raw material gas containing Si at a desired mixing ratio with a raw material gas containing O and H at a desired mixing ratio. mosquito,
Alternatively, a raw material gas containing Si as a constituent atom and Si, O
It is possible to use a mixture of a raw material gas having three constituent atoms: and H. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing O as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (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, the barrier layer 1 is
When forming the barrier layer 102, by selecting and using various starting materials for forming the barrier layer from among the above-mentioned materials, it is possible to form the barrier layer 102 made of a desired constituent material having desired characteristics. I can do it.
Specifically, favorable combinations of starting materials when forming the barrier layer 102 by the glow discharge method include:
For example, single gas such as Si( _CH3 ) ₄ , _SiCl2 ( _CH3 ) ₂ , _SiH4 - _N2O system, _{SiH4- O2} (-Ar) system, _SiH4-
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
Examples include mixed gases such as (CH ₃ ) ₄ -SiH ₄ and SiCl ₂ (CH ₃ ) ₂ -SiH ₄ . To form the barrier layer 102 made of a carbon-based amorphous material by the sputtering method, a monocrystalline or polycrystalline Si wafer or a C wafer or a mixture of Si and C is used. This can be carried out by sputtering a wafer as a target in various gas atmospheres. For example, if a Si wafer is used as a target, the source gas for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X) is
The Si wafer may be sputtered by diluting it with a diluting gas as necessary and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases. Alternatively, at least hydrogen atoms (H) can be removed by using a target other than Si and C or by using a single target containing Si and C.
Alternatively, it can be performed by sputtering in a gas atmosphere containing halogen atoms (X). 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 barrier layer 102 made of a nitrogen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer or a Si ₃ N ₄ wafer or a mixture of Si and Si ₃ N ₄ is used. This can be carried out by sputtering the wafers contained in 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 among the starting materials for forming the barrier layer shown in the glow discharge example mentioned above.
It can also be used as an effective gas in sputtering. In order to form the barrier layer 102 made of an oxygen-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer, a SiO ₂ wafer, or a mixture of Si and SiO ₂ is used. This can be carried out by sputtering a 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 H atoms and/or X atoms as constituent elements. As a raw material gas for introducing oxygen atoms,
The raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example described above is also used as an effective gas in the case of sputtering. In the present invention, the diluent gas used when forming the barrier layer 102 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. Barrier layer 102 in the present invention is carefully formed to provide the desired properties. That is, a substance whose constituent atoms are at least one of Si, C, N, and O, and optionally H or/and X, has a structure ranging from crystalline to amorphous depending on its preparation conditions. In terms of electrical properties, they exhibit properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties. Preparation conditions are carefully selected so that a photoconductive amorphous material is formed. The amorphous material constituting the barrier layer 102 of the present invention has the function of the barrier layer 102 as a free carrier from the support 101 side to the amorphous layer 103 side or from the amorphous layer 103 side to the support 101 side. A material that exhibits electrically insulating behavior because it prevents injection and easily allows photocarriers generated in the amorphous layer 103 to move and pass through to the support 101 side. is formed as. Further, when the photocarrier generated in the amorphous layer 103 passes through the barrier layer 102, the barrier has a mobility value with respect to the passing carrier to such an extent that the photocarrier passes through the barrier layer 102 smoothly. Layer 102 is formed. An important factor in the layer forming conditions for forming the barrier layer 102 made of the amorphous material having the above characteristics is the temperature of the support during layer forming. That is, when forming the barrier layer 102 made of the amorphous material on the surface of the support 101, the temperature of the support during layer formation is an important factor that influences the structure and characteristics 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 optimal range of the support temperature when forming the barrier layer 102 is selected as appropriate in accordance with the method of forming the barrier layer 102. Formation is carried out, typically between 100°C and 300°C, preferably at 150°C.
It is desirable that the temperature is between ℃ and 250℃. For forming the barrier layer 102, the barrier layer 102 is formed in the same system.
The amorphous layer 103 can be formed continuously from the amorphous layer 103 to the third layer formed on the amorphous layer 103 if necessary. 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 barrier layer 102 using these layer forming methods,
Similar to the support temperature described above, discharge power and gas pressure during layer formation can be cited as important factors that influence the characteristics of the barrier layer 102 to be created. The discharge power conditions for effectively creating the barrier layer 102 with good productivity, which has the characteristics to effectively 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. The amounts of carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, and halogen atoms contained in the barrier layer 102 in the photoconductive member of the present invention, as well as the conditions for forming the barrier layer 102, achieve the objective of the present invention. This is an important factor in forming a barrier layer with desired properties. When the barrier layer 102 is composed of a-SiaC _1-a , the carbon atom content is 0.1 to 0.4 in the representation of a.
Suitably 0.2 to 0.35, optimally 0.25 to 0.3,
In the case of a-(Si _b C _1-b ) _c H _1-c , the content of carbon atoms is expressed as b, c, where b is usually 0.1 to 0.5, preferably 0.1. ~0.35, optimally ~0.15
0.3, 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
When composed of X _1-e or a-(Si _f C _1-f ) _g (H +
In the display, d and f are usually 0.1 to 0.47, preferably 0.1 to 0.35, optimally 0.15 to 0.3, and e and g are usually 0.8 to 0.99, preferably 0.85 to 0.99, and optimally 0.85.
~0.98. (Si _f C _1-f )g(H+X) The hydrogen atom content in _1-g is usually less than 19 times that of halogen atoms, preferably
It is said to be 13 times or less. When the barrier layer 102 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 0.43 to 0.60 in h, preferably 0.43. ~0.50. When composed of a-(Si _i N _1-i ) _j H _1-j , the nitrogen atom content is expressed as i, j, where 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
₊
~0.60, preferably 0.43~0.49, m and n usually 0.8~
0.99, preferably 0.85 to 0.98. The content of hydrogen atoms in a-(SimN _1-n ) _o (H+X) _1-o is usually less than 19 times that of halogen atoms, preferably 13
It is considered to be less than double. When the barrier layer 102 is made of an oxygen-based amorphous material, first, in a-Si _p O _1-p , the content of oxygen atoms is usually 0.33 to 0.40, preferably 0.33 to 0.40 in terms of O. It is estimated to be between 0.33 and 0.37. In the case of a-(Si _p O _1-p ) _q H _1-q , when p and q are expressed, p is usually 0.33 to 0.40, preferably 0.33.
~0.37, q typically 0.65-0.98, preferably 0.70
~0.95. a-(Si _r O _1-r ) _s X _1-s , or a-(Si _t O _1-t ) _u (H
₊
0.33 to 0.40, preferably 0.33 to 0.37, and t and u are usually 0.80 to 0.99, preferably 0.85 to 0.98. The content of hydrogen atoms in a-(Si _t O _1-t ) _u (H+m) _1-u is usually 19 times or less that of halogen atoms, preferably
It is said to be 13 times or less. In the present invention, the electrically insulating metal oxides constituting the barrier layer 102 include TiO ₂ , Ce ₂ O ₃ ,
ZrO ₂ , HfO ₂ , GeO ₂ , CaO, BeO, P ₂ O ₅ ,
Y ₂ O ₃ , Cr ₂ O ₃ , Al ₂ O ₃ , MgO, MgO・Al ₂ O ₃ ,
Preferred examples include SiO ₂ .MgO. Two or more of these may be used in combination to form the barrier layer. Barrier layer 1 made of electrically insulating metal oxide
02 is formed by vacuum evaporation method, 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 electrobeam method, or the like. These manufacturing methods are appropriately selected and employed depending on factors such as manufacturing conditions, load on equipment, manufacturing scale, and desired characteristics of the photoconductive member to be produced. For example, the barrier layer 1 can be formed by a sputtering method.
To form 02, sputtering may be carried out in an atmosphere of a sputtering gas such as He, Ne, Ar, etc. using a wafer as a starting material for forming a barrier layer as a target. When using the electrobeam method, the starting material for forming the barrier layer may be placed in a vapor deposition boat and irradiated with an electron beam for vapor deposition. Since it serves to prevent the photocarriers generated in the amorphous layer 103 from moving and pass through to the support 101 side, it is considered to exhibit electrically insulating behavior. It is formed. The numerical range of the layer thickness of the barrier layer 102 is one of the important factors for effectively obtaining the required characteristics. If the layer thickness of the barrier layer 102 is sufficiently thin,
The function of preventing free carriers from flowing from the side of the support 101 toward the side of the amorphous layer 103 or from the side of the amorphous layer 103 toward the side of the support 101 becomes insufficient or insufficient. If it is thicker than a certain amount, the probability that photocarriers generated in the amorphous layer 103 will pass to the support 101 side becomes extremely small, and therefore, in any case, the purpose of the present invention cannot be effectively achieved. can no longer be achieved. In view of the above points, the thickness of the barrier layer 102 to effectively achieve the object of the present invention is usually 30 to 1000 Å, preferably 50 to 600 Å. In the present invention, in order to effectively achieve the purpose, an amorphous layer 10 provided on the barrier layer 102 is used.
3 is a-Si(H,
X), and carbon atoms are doped in the layer thickness direction in a distribution state as described below. 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). 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 atoms (X) contained in the amorphous layer 100 include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. In the photoconductive member 100 of the present invention, the distribution in the amorphous layer 103 is substantially uniform in a plane substantially parallel to the surface of the support 101, and in the thickness direction of the layer. It is non-uniform, and the carbon atoms contained in the layer region are more distributed on the surface side where the support 101 is provided than in the center of the layer region, and the value thereof is in the range of 0.03 to 90 atomic%. A layer region having a peak distribution amount on the surface of the support 101 or near the surface is formed. 2 to 8 show typical examples of the distribution of carbon atoms contained in the amorphous layer 103 in the thickness direction of the amorphous layer 103. In FIGS. 2 to 8, the vertical axis represents the amorphous layer 1
03, t ₀ is the interface position (lower surface position) between the support 101 or other material such as the barrier layer 102 and the amorphous layer 103, and t _s is the free surface 104.
Interface position of side amorphous layer 103 (upper surface position)
(in FIG. 1, the position of the free surface 104) and indicates that the layer thickness t increases from to to _ts , and the horizontal axis is the layer thickness direction of the amorphous layer 103. Distribution amount C of carbon atoms at any position of
, indicating that the amount of distribution is large in the direction of the arrow. In the example shown in FIG. 2, the distribution state of carbon atoms contained in the amorphous layer 103 in the layer 103 is a distribution amount C ₁ from the lower surface position t ₀ to t ₁ .
From the position t ₁ to the upper surface t _s , the distribution amount decreases in a linear function from the distribution amount C ₂ , and at the upper surface position t _s , the content of carbon atoms substantially decreases. has become 0. In the present invention, the fact that the carbon atom content is substantially 0 at a certain layer thickness position of the amorphous layer 103 as described above means that in that layer region, It indicates that the amount of carbon atoms is below the detection limit, and actually includes cases where carbon atoms are contained in an amount below the detection limit. At present, at our technological level,
The detection limit for the amount of carbon atoms is 10 atomic ppm relative to silicon atoms. Therefore, the fact that the carbon atom content is substantially 0 includes cases where the carbon atom content is less than 10 atomic ppm. In the example shown in FIG _. 2, the lower surface layer region of the amorphous layer ₁₀₃ is can have a sufficient barrier layer function. In the example shown in FIG. 3, the distribution amount C ₁ is constant from the lower surface position t ₀ to the position t ₁ , and gradually increases from the position t ₁ to the upper surface position t _s . The distribution state is that it draws a curve and gradually decreases. In the example shown in Figure 4, from t ₀ to t ₁ ,
The distribution amount C is constant at ₁ , the distribution amount decreases in a linear function from t ₁ to t ₂ , and the distribution amount C ₂ is constant between t ₂ and t _s . . Upper surface layer region (part between t ₂ and t _s in the figure)
If a sufficient amount of carbon atoms is contained in the distribution amount C ₂ to exhibit a barrier function, the upper surface layer region of the amorphous layer can sufficiently function as a barrier layer. In the case of the example shown in Fig. 4, the distribution amount C of carbon atoms on both surface sides of the amorphous layer is extremely large compared to the inside, and the distribution amount C of carbon atoms is extremely large in both surface layer regions of the amorphous layer. In this case, the function of the barrier layer can be fully performed. In the example shown in Fig. 5, from t ₀ to t ₂ the distribution state is similar to that shown in Fig. 3, but between t ₂ and t _s , the overall distribution state is selected so that the distribution amount increases rapidly and has a value of C ₂ . The example in Figure 6 has a distribution state similar to that of the example shown in Figure 3 from t ₀ to t ₃ , but between t ₃ and t ₂ , carbon atoms The content is
A substantially zero layer region is formed, and t ₂ and t _s
A large amount of carbon atoms are contained between the two to obtain a distribution amount _C2 . In the example shown in FIG. 7, between t ₀ and t ₁ , the distribution amount C ₁ is constant, and between t ₁ and t ₂ ,
An example is shown in which the distribution amount decreases linearly from the distribution amount C ₃ to the distribution amount C ₄ from the t ₁ side, and between t ₂ and t _s , the distribution amount increases again and takes a constant value C ₂ . . In the example shown in FIG. 8, a constant distribution amount C ₁ is taken between t ₀ and t ₁ , and a constant distribution amount C ₂ is taken between t ₂ and t _s . t ₂
The distance between and t ₁ is as follows from the t ₁ side to the center of the layer.
It gradually decreases and gradually increases from the center of the layer up to t ₂ , forming a distribution state in which the distribution amount C ₄ is obtained at t ₂ . In the present invention, as explained in FIGS. 2 to 8, there is a peak on the surface of the amorphous layer on the support side or in the vicinity of the surface that has a larger distribution in steps than in the center of the amorphous layer. In addition, if necessary, a layer region with an extremely higher content than the center of the layer may be formed on the surface region of the amorphous layer opposite to the support. be done. A layer region is formed at or near the lower surface of the amorphous layer so as to fully exhibit the function of the barrier layer. As mentioned above, the peak value of the distribution amount of the layer region is usually 0.03 to 90 atomic%, preferably 0.05 to 90 atomic%, and optimally 0.1 to 90 atomic%.
It is desirable that it be within the range of . In the photoconductive member of the present invention, the amorphous layer 103
As described above, the carbon atoms contained in the amorphous layer 103 have a non-uniform content distribution in the layer thickness direction, and are more concentrated in the central part of the amorphous layer than in the vicinity of the lower surface layer region. Although it can be contained in the amorphous layer so as to take a distribution state in which the distribution amount decreases as the amorphous layer 1 is formed,
The content of carbon atoms contained in the entire 03 is also one of the important factors in achieving the intended purpose of the present invention. In the present invention, the value of the total amount of carbon atoms contained in the amorphous 103 usually takes the above-mentioned value, and more preferably 0.005 to 0.005.
It is preferably selected from the range of 20 atomic%, most preferably from 0.005 to 10 atomic%. In the present invention, in order to form the amorphous layer 103 mainly composed of a-Si (H, It is done by a deposition method. For example, in order to form an amorphous layer by the glow discharge method, the internal pressure of the raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms is reduced, along with the raw material gas for Si generation that can generate Si. It is sufficient to introduce the a-Si(H, . In order to introduce carbon atoms into the layer to be formed, a raw material gas for introducing carbon atoms may be introduced into the deposition chamber at the time of forming the layer, in conjunction with the growth of the layer.
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. At this time, the method for introducing carbon atoms into the amorphous layer 103 is to introduce a raw material gas for introducing carbon atoms into the deposition chamber at the time of layer growth, or to When forming the layer, sputtering may be performed on a target for introducing carbon atoms, which has been provided in advance in the deposition chamber. In the present invention, SiH 4 , SiH ₄ ,
Gaseous or gasifiable silicon hydrides (silanes), such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., can be used effectively, especially in layer formation operations. SiH ₄ , due to its ease of handling and good Si generation efficiency,
Si ₂ H ₆ is preferred. In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer 103, such as halogen gas, halides, interhalogen compounds, and halogen-substituted gases. Preferred examples include gaseous or gasifiable halogen compounds such as silane derivatives. 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, an amorphous layer made of a-Si:X can be formed on a predetermined support. When manufacturing the amorphous layer 103 containing halogen atoms according to the glow discharge method, basically, silicon halide gas, which is a raw material gas for Si generation, and
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber to form an amorphous layer at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. By this, an amorphous layer 103 can be formed on a predetermined support, but in order to introduce hydrogen atoms, a silicon compound gas containing hydrogen atoms may also be added to these gases. A layer may be formed by mixing quantitatively. 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 an amorphous layer made of a-Si(H, 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 used by a resistance heating method or an electron beam method. This can be carried out by heating and evaporating the flying evaporated material by (EB method) or the like and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen 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. Carbon atoms contained in the amorphous layer to be formed in a desired distribution state in the layer thickness direction are formed by a glow discharge method, an ion plating method, or a reaction sputtering method. In this case, the raw material gas for introducing carbon atoms may be introduced into the deposition chamber for forming the layer at a desired flow rate in accordance with the growth of the layer during the formation of the layer. Furthermore, when forming an amorphous layer by a sputtering method, in addition to the above, a target for introducing carbon atoms is provided in the deposition chamber, and the target is sputtered as the layer grows. It's better to give it a ring. In the present invention, many carbon compounds that are in a gaseous state or can be easily gasified can be mentioned as those that can be effectively used as a raw material gas for introducing carbon atoms. As such a starting material, for example, a carbon number 1 containing C and H as constituent atoms.
-5 saturated hydrocarbons, 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 ₆ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylenic hydrocarbons include:
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. In addition to these, starting materials for introducing carbon atoms containing Si, C, and H as constituent atoms include Si(CH ₃ ),
Alkyl silicides such as Si(C ₂ H ₅ ) ₄ , SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ , SiCl CH ₃ , CCl ₄ , CHF ₃ ,
_{CH2F2 , CH3F , CH3Cl} , _CH3Br , _CH3I , _C2H5Cl
Halogen-substituted paraffinic hydrocarbons such as halogen-substituted paraffin hydrocarbons can also be cited as effective. In order to form the amorphous layer 103 into which carbon atoms are introduced by the sputtering method, the amorphous layer 1
When forming 03, a single-crystal or polycrystalline Si wafer is sputtered in an atmosphere of a raw material gas for introducing carbon atoms, or a single-crystalline or polycrystalline Si wafer and a C wafer or Si and This can be carried out by sputtering using a wafer containing a mixture of C as a target. For example, if a Si wafer is used as a target, the same raw material gas as described above for glow discharge is used as a raw material gas for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X). The Si wafer may be sputtered by diluting it with a diluting gas as necessary and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases. Alternatively, at least hydrogen atoms (H) can be removed by using a target other than Si and C or by using a single target containing Si and C.
Alternatively, it can be performed by sputtering in a gas atmosphere containing halogen atoms (X). In the present invention, oxygen atoms can be introduced into the amorphous layer 103 in addition to carbon atoms in order to obtain effects similar to those obtained by introducing carbon atoms. When forming the amorphous layer 103 by the glow discharge method, starting materials that serve as raw material gas for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ),
Examples include carbon monoxide (CO), carbon dioxide (CO ₂ ), and lower siloxanes such as disiloxane H ₃ SiOSiH ₃ and trisiloxane H ₃ SiOSiH ₂ OSiH ₃ . Further, in the present invention, materials such as SiO ₂ and SiO are effectively used as materials capable of forming a target for introducing oxygen atoms when forming the amorphous layer 103 by sputtering. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effective as starting materials for the raw material gas for introducing halogen atoms used when forming the amorphous layer 103. However, in addition,
Hydrogen halides such as HF, HCl, HBr, HI,
Halogen-substituted silicon hydrides such as SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc., and halides that have a hydrogen atom as one of their constituents in a gaseous state or can be gasified are also used. It can be mentioned as an effective starting material for forming an amorphous layer. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer, so the present invention It is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the amorphous 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. has certain characteristics, mainly a-Si
An amorphous layer consisting of (H,X) is formed. 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 amorphous 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 amorphous layer have an n-type tendency, a p-type tendency, or an i-type, an n-type impurity, a p-type impurity, or both impurities are formed during layer formation by a glow discharge method, a reactive sputtering method, etc. This is done by doping the layer in a controlled amount. In order to make the amorphous layer i-type or p-type, impurities doped into the amorphous layer include elements of group A of the periodic table, such as B, Al, Ga,
Preferred examples include In and Tl. In the case of having an n-type tendency, elements of group A of the periodic table, such as N, P, As, Sb, Bi, etc., are suitable. In the present invention, in order to have a desired conductivity type,
The amount of impurities introduced into the amorphous layer is 3× in the case of impurities in group A of the periodic table.
Doping can be done in an amount range of 10 ^-2 atomic% or less, and in the case of impurities in group A of the periodic table,
Doping may be carried out in an amount of 5×10 ^-3 atomic % or less. The layer thickness of the amorphous layer 103 is appropriately determined as desired so that photocarriers generated in the amorphous layer 103 are efficiently transported, and is usually 3 to 100 mm thick.
μ, preferably 5 to 50 μ. Example 1 A mirror-finished aluminum alloy 52S (containing Si, Mg, and Cr) substrate with a thickness of 1 mm and a size of 10 cm x 10 cm was washed with alkali and acid, and then washed with pure water. This substrate was anodized in a 7% sulfuric acid solution containing 5 g/l of aluminum sulfate at a temperature of 18°C. After anodizing for about 5 minutes, the substrate was pulled out of the sulfuric acid solution and immersed in a rapidly boiling pure water tank. After about 10 minutes, the substrate was pulled out of the pure water bath. The thickness of the coating layer on the aluminum alloy substrate treated in this way was about 0.8μ. Using this aluminum alloy substrate, No. 9 was installed in a completely shielded clean room.
An electrophotographic image forming member was produced using the apparatus shown in the figure and by the following operations. The aluminum 909 described above was firmly fixed to a fixing member 903 at a predetermined position within the glow discharge deposition chamber 901. The substrate 909 is heated with an accuracy of ±0.5° C. by a heater 908 within the fixing member 903. Temperature was measured directly on the backside of the substrate by a thermoelectric (alumel-chromel). Next, after confirming that all valves in the system were closed, the main valve 910 was fully opened to evacuate the chamber 901 to a degree of vacuum of approximately 5×10 ^-6 Torr. Thereafter, the input voltage to the heater 908 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 250°C. Then the auxiliary valve 941 and then the outflow valve 9
26,927,929 and inflow valve 921,9
22,924 were fully opened, and the mass flow controllers 916, 917, and 919 were also sufficiently degassed to a vacuum state. Auxiliary valve 941, valve 926, 9
After closing 27,929,921,922,924, _SiH4 gas diluted to 10 vol% with _H2 (purity
99.999%, hereinafter abbreviated as SiH ₄ /H ₂ . )Cylinder 911
Open the valve 931 of the C ₂ H ₄ gas (99.999% purity) cylinder 914 and check the outlet pressure gauge 9.
36,939 to 1 Kg/cm ² and gradually open the inflow valves 921, 924 to flow SiH ₄ /H ₂ gas into the mass flow controllers 916, 919.
C ₂ H ₄ gas was injected into each. Subsequently, the outflow valves 926 and 929 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time, SiH ₄ /H ₂
Mass flow controllers 916 and 919 were adjusted so that the ratio of gas flow rate to C ₂ H ₄ gas flow rate was 10:1. Next, adjust the opening of the auxiliary valve 941 while watching the reading on the Pirani gauge 942, and
Auxiliary valve 9 until the inside of 01 becomes 1×10 ^-2 Torr.
I opened 41. After the internal pressure in the chamber 901 is stabilized, the main valve 9
10 was gradually closed, and the aperture was narrowed down until the reading on the Pirani gauge 941 became 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 905 (which also serves as an electrode) is closed, the high frequency power source 943 is turned on, and the electrode 90 is turned on.
A high frequency power of 13.56 MHz was applied between 3,905 and 3,905 to generate a glow discharge in the chamber 901, resulting in an input power of 3 W. After forming a lower layer with a thickness of 600 Å on the molybdenum substrate by maintaining the above conditions for 10 minutes, the high frequency power source 943 is turned off, and the outflow valve 929 is closed while the glow discharge is stopped.
Then _{C 2 H 4} gas diluted to 0.1 vol% with H 2 (purity
99.999%, hereinafter abbreviated as C ₂ H ₄ /H ₂ . )Cylinder 912
With a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 937) through the valve 932 of the inlet valve 922,
The outflow valve 927 is gradually opened to allow C ₂ H ₄ /H ₂ gas to flow through the mass flow controller 917, and by adjusting the mass flow controllers 916 and 917.
The flow ratio of C ₂ H ₄ /H ₂ gas and SiH ₄ /H ₂ gas was adjusted to 1:1. Continue to turn on the high frequency power supply 9 again.
43 was turned on to restart glow discharge.
The input power at that time was set to 10W. Under the above conditions, the flow rate set value of the mass flow controller 917 was continuously decreased for 3 hours at the same time as the photoconductive layer was started to be deposited on the lower layer, and SiH ₄ /H ₂ was deposited after 3 hours.
The gas flow rate and C ₂ H ₄ /H ₂ gas flow rate ratio were adjusted to be 10:0.1. After forming the layer in this way for 5 hours, the heating heater 908 is turned off, the high frequency power source 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 92 is turned off.
1,922,924 is closed, main valve 910
After fully opening the chamber 901 to bring the pressure within the chamber 901 to 10 ^-5 Torr or less, the main valve 910 was closed, the chamber 901 was brought to atmospheric pressure by the leak valve 906, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9 microns. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.5 KV for 0.2 seconds, and immediately exposed to a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developed material (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. In addition, when the above-described image forming process was repeated and tested for durability by applying it to the electrophotographic image forming member, there was no difference at all when compared with the image obtained on the 10,000th sheet of transfer paper. It has been demonstrated that the electrophotographic image forming member has excellent corona ion resistance, abrasion resistance, cleaning properties, etc., and is extremely durable. As for cleaning properties, blade cleaning was used, and the blade was molded from urethane rubber. In addition, the surface potential of the electrophotographic image forming member during the repeated process of image formation is always constant, with the dark area potential being approximately 240 V and the bright area potential being approximately 50 V. No increase occurred at all. Example 2 A mirror-finished aluminum alloy 61S (containing Cu, Si, and Cr) substrate with a thickness of 1 mm and a size of 10 cm x 10 cm was subjected to the same anodizing treatment as in Example 1, and then After sufficiently drying, it was left in a superheated steam tank at 3 atm for 20 minutes. An image forming member was formed using this substrate in exactly the same manner as in Example 1, and the image quality and durability were evaluated, and good results were obtained in both cases. Example 3 A photoconductive layer was formed in the same manner as in Example 1, except that the thickness of the coating layer on the substrate surface was changed by changing the anodic oxidation time, and the image quality and repeatability were further improved. Upon evaluation, the results shown in Table 1 were obtained. Here, magnetic brush development was used for development, and a development bias value that gave the best image for each photoreceptor was selected.

【table】

[Table] Example 4 An aluminum substrate prepared in the same manner as in Example 1 was placed in a predetermined position, and then the inside of the glow discharge deposition chamber 901 was heated 5× by the same operation as in Example 1.
After creating a vacuum of 10 ^-5 Torr and maintaining the substrate temperature at 250°C, the auxiliary valve 941, then the outflow valves 926, 927, and the inflow valves 921, 922 were fully opened by the same operation as in Example 1. The insides of the mass flow controllers 916 and 917 were also sufficiently degassed and vacuumed. Auxiliary valve 941, valve 92
After closing 6,927,921,922, in H ₂
SiH ₄ /H ₂ gas cylinder 911 diluted to 10 vol%
Bulb 931, diluted to 0.1 vol% with _H2
Open the valve 932 of the C ₂ H ₄ /H ₂ gas cylinder 912 and adjust the pressure on the outlet pressure gauges 936 and 937 to 1 kg/
cm ² and gradually opened the inflow valves 921 and 922 to allow SiH ₄ /H ₂ gas and C ₂ H ₄ /H ₂ to flow into the mass flow controllers 916 and 917, respectively.
Subsequently, the outflow valves 926 and 927 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time, the inflow valves 921 and 922 are adjusted so that the SiH ₄ /H ₂ gas flow rate and C ₂ H ₄ /H ₂ gas flow rate ratio is 1:10.
adjusted. Next, the opening of the auxiliary valve 941 was adjusted while observing the reading on the Pirani gauge 942, and the auxiliary valve 941 was opened until the inside of the chamber 901 reached 1×10 ⁻² Torr. After the internal pressure of the chamber 901 stabilizes, the main valve 910 is gradually closed, and the Pirani gauge 941 is closed.
The aperture was narrowed down until the reading was 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 905 (which also serves as an electrode) is closed, the high frequency power source 943 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 903 and 905. and generate a glow discharge in the chamber 901,
The input power was 10W. At the same time as the photoconductive layer was started to be deposited on the substrate under the above conditions, the flow rate setting of the mass flow controller 917 was continuously decreased for 5 hours, and the SiH ₄ /H ₂ gas flow rate after 5 hours was
The C ₂ H ₄ /H ₂ gas flow rate ratio was adjusted to 10:0.1. After forming the photoconductive layer in this manner, the heating heater 908 is turned off, the high frequency power source 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927 and the inflow valve 92 are turned off.
1,922 was closed and the main valve 910 was fully opened to bring the inside of the chamber 901 to 10 ^-5 Torr or less, then the main valve 910 was closed and the inside of the chamber 901 was brought to atmospheric pressure by the leak valve 906 and the substrate was taken out. . In this case, the total thickness of the layer formed was approximately 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 5 After forming a lower layer and a photoconductive layer on an aluminum substrate prepared by performing the same pretreatment under the same operations and conditions as in Example 1, the high frequency power source 934 was turned off to stop glow discharge. In this state, the outflow valve 927 is closed, and then the outflow valve 929 is opened again. By adjusting the mass flow controllers 919 and 916, the C ₂ H ₄ gas flow rate becomes equal to the SiH ₄ /H ₂ gas flow rate.
It was stabilized to 1/10. Subsequently, the high frequency power supply 943 was turned on again to restart the glow discharge. The input power at that time is the same as before.
I set it to 3W. After continuing the glow discharge for another 15 minutes to form an upper layer with a thickness of 900 Å, the heating heater 908 is turned off, the high frequency power supply 943 is also turned off, and the substrate temperature is waited for to reach 100°C. Outflow valves 926, 929 and inflow valve 92
1,922,924 is closed, main valve 910
After fully opening the chamber 901 and reducing the pressure within the chamber 901 to 10 ⁻⁵ Torr or less, the main valve 910 was closed, and the chamber 901 was brought to atmospheric pressure by the leak valve 906 and the substrate was taken out. The total thickness of the layer formed in this case is approximately 9
It was μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 6 After forming a photoconductive layer on a pretreated aluminum substrate under the same operations and conditions as in Example 4,
With the high frequency power supply 943 turned off and glow discharge stopped, the outflow valve 927 is closed, then the outflow valve 929 is opened again, and the C ₂ H ₄ gas flow rate is adjusted to SiH 4 /SiH ₄ by adjusting the mass flow controllers 919 and 916. The flow rate was stabilized at 1/10 of the _H2 gas flow rate. Then turn on the high frequency power supply 943 again.
The glow discharge was restarted. The input power at that time was also 3W as before. After continuing the glow discharge for another 10 minutes to form an upper layer with a thickness of 900 Å, the heating heater 9
08 is turned off, the high frequency power supply 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 929 and the inflow valves 921,
922, 924, and fully open the main valve 910 to bring the inside of the chamber 901 to 10 ^-5 Torr or less, then close the main valve 910 and bring the inside of the chamber 901 to atmospheric pressure using the leak valve 906, and take out the substrate. did. In this case, the total thickness of the layer formed was 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 7 In the same manner as in Example 1, a pretreated aluminum substrate was installed, and then the inside of the glow discharge deposition chamber 901 was made into a vacuum of 5 × 10 ^-6 Torr by the same operation as in Example 1, and the substrate temperature was was maintained at 250°C, and then the auxiliary valve 941, the outflow valves 926, 927, and the inflow valve 9 were opened by the same operation as in Example 1.
21 and 922 were fully opened, and the mass flow controllers 916 and 917 were also sufficiently degassed and brought into a vacuum state.
Auxiliary valve 941, valves 926, 927, 92
Valve 931 of SiH ₄ /H ₂ gas cylinder 911 diluted to 10 vol% with H ₂ after closing 1,922;
Open the valve 932 of the C ₂ H ₄ /H ₂ gas cylinder 912 diluted with H ₂ to 0.1 vol%, and check the outlet pressure gauge 93.
6,937 to 1 Kg/cm ² and gradually open the inflow valves 921, 922 to flow SiH ₄ /H ₂ gas into the mass flow controllers 916, 917.
C ₂ H ₄ /H ₂ were each injected. Subsequently, the outflow valves 926 and 927 were gradually opened, and then the auxiliary valve 941 was gradually opened. At this time, SiH ₄ /H ₂
The inflow valves 921 and 922 were adjusted so that the gas flow rate and the C ₂ H ₄ /H ₂ gas flow ratio were 1:10. Next, the opening of the auxiliary valve 941 was adjusted while observing the reading on the Pirani gauge 942, and the auxiliary valve 941 was opened until the inside of the chamber 901 reached 1×10 ⁻² Torr. After the internal pressure of the chamber 901 stabilizes, the main valve 910 is gradually closed, and the Pirani gauge 941 is closed.
The aperture was narrowed down until the reading was 0.3Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 905 (which also serves as an electrode) is closed, the high frequency power source 943 is turned on, and 13.56 MHz high frequency power is applied between the electrodes 903 and 905. and generate a glow discharge in the chamber 901,
The input power was 10W. At the same time as the photoconductive layer was started to be deposited on the substrate under the above conditions, the flow rate setting value of the mass flow controller 917 was continuously decreased for 2.5 hours, and the SiH ₄ /H ₂ gas flow rate and C ₂ H after 2.5 hours were _{The 4} / _H2 gas flow ratio was adjusted to 10:0.1. After maintaining the same conditions for 30 minutes, the flow rate setting value of the mass flow controller 917 was continuously increased in the opposite direction to the previous one, and the SiH ₄ /H ₂ gas flow rate and C ₂ H ₄ /H ₂ gas flow rate after 2.5 hours were changed. The ratio was adjusted to 1:10. After forming the photoconductive layer in this manner, the heating heater 908 is turned off, the high frequency power source 943 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927 and the inflow valve 92 are turned off.
1,922 was closed and the main valve 910 was fully opened to bring the inside of the chamber 901 to 10 ^-5 Torr or less, then the main valve 910 was closed and the inside of the chamber 901 was brought to atmospheric pressure by the leak valve 906 and the substrate was taken out. . In this case, the total thickness of the layer formed was approximately 17μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 8 After forming a lower layer on a pretreated aluminum substrate using the same operations and conditions as in Example 1, the outflow valve 929 was closed with the high frequency power source 943 turned off and glow discharge stopped. After
C ₂ H ₄ /H ₂ gas cylinder 912 valve 932, H ₂
B ₂ H ₆ gas (purity 99.999) diluted to 50 vol ppm with
%, hereinafter abbreviated as B ₂ H ₆ /H ₂ ) Open the valve 933 of the cylinder 913, adjust the pressure of the outlet pressure gauges 937, 938 to 1 Kg/cm ² , and open the inlet valves 922, 92.
3 gradually open the mass flow controller 91.
C ₂ H ₄ /H ₂ gas and B ₂ H ₆ /H ₂ gas were flowed into No. 7,918. Subsequently, the outflow valves 927, 928
was gradually opened, and the SiH ₄ /H ₂ gas flow rate and C ₂ H ₄ /H ₂ gas flow rate ratio was 1:10, and the SiH ₄ /H ₂ gas flow rate and B ₂ H ₆ /
Mass flow controllers 916, 917, and 918 were adjusted so that the H ₂ gas flow rate ratio was 50:1. Next, readjust the opening of the auxiliary valve 941 while watching the reading on the Pirani gauge 942, and
The internal pressure inside 1 was set to 1×10 ^-2 Torr. Furthermore, after the internal pressure in the chamber 901 became stable, the main valve 910 was also readjusted so that the indication on the Pirani gauge 942 was set to 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 943 again.
A high frequency power of 13.56 MHz was applied to restart glow discharge in the chamber 901, resulting in an input power of 10 W. Under the above conditions, the flow rate setting value of the mass flow controller 917 was continuously decreased for 5 hours at the same time as the photoconductive layer started to be deposited.
SiH ₄ /H ₂ gas flow rate and C ₂ H ₄ /H ₂ gas flow rate ratio is 10:
Adjusted to 0.1. After forming the layer in this way for 5 hours, the heating heater 908 is turned on.
off state, and the high frequency power supply 943 is also off state,
After waiting for the substrate temperature to reach 100°C, the outflow valves 926, 927, 928 and the inflow valve 92
1,922, 923, and 924, and fully open the main valve 910 to reduce the inside of the chamber 901 to 10 ^-5 Torr.
After the main valve 910 is closed, the chamber 90
1 was brought to atmospheric pressure using a leak valve 906, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.5 KV for 0.2 seconds, and immediately exposed to a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component.
When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the above-mentioned image forming member was corona charged at 6.0KV for 0.2 seconds using a charging exposure experiment device, and immediately subjected to image exposure at a light intensity of 1.0 lux・sec. Immediately thereafter, a charged developer was applied to the surface of the member. When the image was cascaded and then transferred and fixed onto transfer paper, an extremely clear image was obtained. From this result and the previous results, it was found that the electrophotographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of an amphipolar image forming member. Example 9 SiH ₄ /H ₂ gas cylinder 911 is replaced with SiF ₄ gas (purity 99.999%) cylinder, C ₂ H ₄ /H ₂ gas cylinder 9
12 with argon containing 0.2 vol% ethylene (hereinafter
It is abbreviated as C ₂ H ₄ /Ar. (purity 99.999%) gas cylinder, and SiF ₄ gas flow rate at the initial stage of photoconductive layer deposition.
Layer formation was started by setting the C ₂ H ₄ /Ar gas flow rate ratio to 1:15, and the SiF ₄ gas flow rate and C ₂ H ₄ /Ar gas flow rate ratio at the end of photoconductive layer deposition was 1:0.5. so that it becomes
A photoconductive layer was formed on the pretreated aluminum substrate under the same operating conditions as in Example 2, except that the C ₂ H ₄ /Ar gas flow rate was continuously decreased and the input power of the glow discharge was 100 W. Formed. In this case, the thickness of the layer formed was approximately 18μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained. Example 10 Using the apparatus shown in FIG. 9, an electrophotographic image forming member was prepared by the following operations. An aluminum substrate pretreated in the same manner as in Example 1 is fixed to a fixing member 90 at a predetermined position in a deposition chamber 901.
It was firmly fixed at 3. The target 904 is made of high purity graphite (99.999%) placed on polycrystalline high purity silicon (99.999%). Board 9
09 is a heater 908 inside the fixed member 903
heated with an accuracy of ±0.5℃. The temperature is
The backside of the substrate was directly measured by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, fully open the main valve 910 and temporarily reduce the temperature to 5×10 ^-6 Torr.
(all valves in the system are closed at this time), auxiliary valve 941 and outflow valves 926, 927, 929, 930 are opened, and mass flow controllers 916, 917, 9
After the inside of 19,920 was sufficiently degassed, outflow valves 926, 927, 929, 930 and auxiliary valve 941 were closed. Argon (99.999% purity)
After opening the valve 935 of the gas cylinder 915 and adjusting the reading of the outlet pressure gauge 940 to 1 Kg/cm ² , the inflow valve 925 is opened, and then the outflow valve 930 is gradually opened to supply argon gas to the chamber. 901. Pirani gauge 911
The outflow valve 930 is gradually opened until the indication becomes 5×10 ^-4 Torr, and after the flow rate stabilizes in this state, the main valve 910 is gradually closed.
The aperture was constricted until the room pressure was 1×10 ^-2 Torr. After opening the shutter 905 and confirming that the mass flow controller 920 is stable,
Turn on the high frequency power supply 943 and turn on the target 9.
13.56MHz, 100W between 04 and fixed member 903
AC power was input. Matching was performed under these conditions so that stable discharge could continue, and a layer was formed. Discharge was continued in this manner for 1 minute to form a lower layer with a thickness of 100 Å. After that, turn on the high frequency power supply 943.
The battery was turned off and the discharge was temporarily stopped. Subsequently, the outflow valve 930 is closed, and the main valve 910 is closed.
Fully open to remove the gas in chamber 901, and
Vacuum was applied to 10 ^-6 Torr. Then heater 90
The input voltage of 8 was increased, and the input voltage was varied while detecting the substrate temperature, until it stabilized at a constant value of 200℃. Thereafter, a photoconductive layer was formed using the same operations and conditions as in Example 2. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 11 An aluminum substrate was pretreated under the same operations and conditions as in Example 9, except that the argon gas cylinder 912 containing 0.2 vol% ethylene in Example 9 was replaced with a hydrogen gas cylinder containing 0.2 vol% ethylene. A photoconductive layer was formed thereon. The thickness of the layer formed in this case was approximately 15μ. When an image was formed on a transfer paper using this image forming member under the same conditions and procedures as in Example 1, an extremely clear image was obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIGS. FIG. 9 is a schematic explanatory diagram showing an example of an apparatus for producing the photoconductive member of the present invention. 100...Photoconductive member, 101...Support, 1
02... Barrier layer, 103... Amorphous layer.

Claims (1)

[Claims] 1 An electrophotographic support having a surface made of aluminum oxide containing water in its chemical structure, and an amorphous material containing at least either a hydrogen atom or a halogen atom and having a silicon atom as its matrix, an amorphous layer exhibiting photoconductivity, the amorphous layer has a layer region containing carbon atoms in at least a portion thereof, and the distribution of carbon atoms in the layer region is similar to that of the support. is substantially uniform in a plane substantially parallel to the surface of the layer, and is non-uniform in the thickness direction of the layer, such that carbon atoms contained in the layer region are closer to the support than in the center of the layer region. The carbon atoms are distributed more toward the surface side where the support is provided, and the content of carbon atoms in the entire layer region is 0.005 to 30 atomic%, and the surface of the layer region on the side where the support is provided, or the surface An electrophotographic image forming member characterized by having a distribution peak in the vicinity thereof having a value in the range of 0.03 to 90 atomic%.