JPS628785B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is sensitive to electromagnetic waves such as light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.), and The present invention relates to electrophotographic imaging members used in the forming field. [Prior Art] Photoconductive materials constituting a photoconductive layer in an electrophotographic image forming member include Se, Se-Te, CdS,
OPC materials such as ZnO, PVCz, and TNF are well known, but recently, for example,
As stated in Publications No. 2746967 and No. 2855718, it has properties comparable to other photoconductive materials in terms of photosensitivity, spectral wavelength range, photoresponsivity, dark resistance, etc. , in addition, despite being amorphous, p-n
Amorphous silicon (hereinafter referred to as A-Si) is attracting attention as a promising photoconductive material because it can be easily controlled and is non-polluting to the human body. [Problems to be solved] 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. Although progress is being made, there are still some issues that need to 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-odd microns, the layer may lift or peel from the surface of the support, or it may crack as the time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It is possible to win by causing phenomena such as the occurrence of problems. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there is a need to solve this problem in terms of stability over time. 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, which has properties suitable for use in conventional solar cells. Even if the photoconductive layer of an electrophotographic imaging member having a conductive layer is subjected to charging treatment for forming an electrostatic image, 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 possible 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. [Outline and Purpose] The present invention has been made in view of the above points, and
-As a result of comprehensive research and study on Si from the viewpoint of its suitability and applicability as an electrophotographic image forming member, we found that silicon atoms are the base material, hydrogen atoms (H) and halogen atoms (X). An amorphous material (non-crystalline 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 (H, The image forming member for electrophotography is not only usable for practical purposes, but is also superior in most respects compared to conventional ones, especially in terms of light sensitivity and image quality stability for electrophotography. This is based on the discovery that it has extremely superior properties in The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, has excellent resistance to light fatigue, and does not cause deterioration even after repeated use. The main object of the present invention is to provide an electrophotographic imaging 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 image forming 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. [Means to Solve the Problems] The electrophotographic image forming member of the present invention comprises an electrophotographic support having a surface made of aluminum oxide containing water in its chemical structure, and a hydrogen atom (H) and a halogen atom ( X)
Amorphous material based on silicon atoms [A-Si
(H, It has a layer region containing carbon atoms, which is uniform in the layer thickness direction, non-uniform in the layer thickness direction, and is distributed more heavily on the surface side opposite to the support, and the carbon atom content is 0.005. ~90 atomic %, and the maximum value of the distribution concentration in the layer thickness direction is 0.03 to 90 atomic %. [Function] 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, and photoconductive properties. Indicates usage environment characteristics. 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, is extremely resistant to light fatigue, has excellent repeatability, and can always stably obtain high-quality visible images with high density, clear halftones, and high resolution. Furthermore, floating from the support,
It has advantages such as no peeling or layer cracking, excellent mechanical and electrical contact and adhesion, and no deterioration of initial properties even after repeated use over a long period of time. [Embodiment Examples] 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 that is provided in direct contact with the barrier layer 102 and exhibits photoconductivity, and the amorphous layer 103 has a layer region containing carbon atoms in at least a portion thereof. The distribution of carbon atoms in the layer region is substantially uniform in a plane substantially parallel to the surface of the support 101, and is non-uniform in the thickness direction of the layer. The carbon atoms contained in the region are more distributed on the surface side opposite to the support 101, and the carbon atom content is
Ct is 0.005 to 30 atomic %, and the maximum value Cmax of the distribution concentration in the layer thickness direction exists on the surface opposite to the support 101 or very close to the surface,
Cmax is said to be 0.03 to 90 atomic%. Support 1
01 has an aluminum oxide film containing water in its chemical structure at least on its surface, but such a film is most simply a pure aluminum oxide film that has been processed and formed for use in electrophotography and then subjected to appropriate pretreatment. Al ₂ O ₃ H ₂ O or Al ₂ O ₃・3H ₂ O
It is obtained with the following composition. 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% oxalate solution,
3% solution of malonic acid or its salts, oxalic acid 35
Examples include those dissolved in water at a ratio of 1 g and 1 g of KMnO ₄ . 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 3.
The power is 20 Amp/dm 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 concentration of the electrolyte 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 it at 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 15 volts.
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
It takes about 2KWh to obtain a hard film, and about 0.5 to 1KWh to obtain a soft film. 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 is 20 to 30°C, the voltage is approximately 12 volts, and the current density is 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. administered. The boiling water treatment can 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 , etc. to completely remove the components of the electrolyte adhering to the film. The anodized medium may be kept in superheated steam of about 4 to 5.6 kg/cm ² for a suitable 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 properties 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, Anticodal, Pantal, SilalV, RS, 52S,
56S, Hydroalium, BS-Seewasser, 4S, KS-
Seewasser, 3S, 14S, 17S, 24S, Y alloy,
Examples include those commercially available under product standard names such as 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, and prevents free carriers from flowing into the amorphous layer 103 due to electromagnetic wave irradiation. , 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 function, but the same function as the above-mentioned barrier layer 102 is performed at 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 effect is sufficiently exhibited. The barrier layer 102 is an amorphous material that has silicon atoms as its base material and contains at least one type of atom selected from carbon atoms and nitrogen atoms, and at least one of hydrogen atoms and halogen atoms as necessary. These are collectively called A- [Six (C, N) _1-x ] _y
(H, X) Written as _1-y (0<x<1, 0
<y<1)> Or, it is composed of an electrically insulating metal oxide or an electrically insulating organic compound. In the present invention, preferred halogen atoms (X) contained in the barrier layer 102 are F,
Cl, Br, and I, with F and Cl being particularly desirable. Specifically, carbon-based amorphous materials such as A-Si _a C _1-a and 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 as a nitrogen-based amorphous material −
(Si _k N _1-k ) _l X _1-l , A-(Si _n N _1-n ) _o (H+X) _1-o
Furthermore, among the above-mentioned amorphous materials, examples include amorphous materials containing two types of atoms, C and N, as constituent atoms (provided that 0<a, b, c,
d, e, f, g, h, i, j, k, l, m, n<
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. Especially from the viewpoint of properties, it is more preferable to select a carbon-based amorphous material. When the barrier layer 102 is made of the above-mentioned amorphous material, the layer can be formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. 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 containing Si and H are effectively used as the raw material gas for forming the barrier layer 102 made of a carbon-based amorphous material. Silicon hydride gas such as silanes such as ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., saturated hydrocarbons containing C and H as constituent atoms, e.g. 1 to 5 carbon atoms, carbon atoms Examples include ethylene hydrocarbons having 1 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
As propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), inbutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons teeth,
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,
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 halogen. Examples include intermediate compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, and HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , and ClF ₅ ,
BrF 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 silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₆ , Si ₄ H ₁₀ , etc. I can do it. In addition to these, CCl ₄ , CHF ₃ , CH ₂ F ₂ ,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Alkyl silicides such as Si(C ₂ H ₅ ) ₄ , SiCl(CH ₃ ) ₃ , SiCl
Derivatives of silanes such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These barrier layer forming raw materials are used to form the barrier layer so that the barrier layer to be formed contains silicon atoms, carbon atoms, and optionally halogen atoms and hydrogen atoms in a predetermined composition ratio. It is selected and used as desired. For example, SiHCl _{3 and} SiCl contain Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form a barrier layer with desired characteristics. _{A- ( Si f C 1- 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, the barrier layer 10
Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms to form 2 are nitrogen (N ₂ ), ammonia, etc., which have N as a constituent atom, or N and H as constituent atoms. (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides; 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. 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 , SiCl( _CH3 ) _2, or _SiH4 - _NH3 system, _SiCl4 - _NH4 system, _{SiH4- N2}
Examples include mixed gases such as Si( _CH3 ) ₄ - _SiH4 -based, _SiCl2 ( _CH3 ) ₂ - _SiH4- based, and the like. To form the barrier layer 102 made of a carbon-based amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is used. This can be done by sputtering these as targets in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing carbon atoms and water atoms (H) or halogen atoms (X) may be diluted with a diluent gas as necessary for sputtering. The Si wafer may be sputtered by introducing these gases into a deposition chamber to form a gas plasma of these gases. Alternatively, a gas containing at least a hydrogen atom (H) or a halogen atom (X) can be produced by using separate targets for Si and C or by using a single target containing a mixture of Si and C. This is done by sputtering in an atmosphere. As the raw material gas for introducing carbon atoms, hydrogen atoms, or halogen atoms, the raw material gases shown in the glow discharge example described above can also be used as effective gases 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, a Si ₃ N ₄ wafer, or a mixture of Si and Si ₃ N ₄ is used. This can be done by sputtering the contained wafers in various gas atmospheres, using them as targets. 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 H ₂ or NH ₃ , diluted with a diluting gas as necessary and introduced into a sputtering deposition chamber,
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 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, e.g.
Suitable examples include He, Ne, Ar, and the like. When the barrier layer 102 is made of the amorphous material described above, it is carefully formed to provide the desired properties. In other words, a substance containing Si, at least one of C, N, and optionally H or/and , in terms of electrical properties, the properties range from conductivity to semiconductivity to insulation.
In addition, since each exhibits properties ranging from photoconductive properties to non-photoconductive properties, in the present invention, the production conditions are adjusted so that a non-photoconductive amorphous material is formed. Choices are made rigorously. The amorphous material constituting the barrier layer 102 has the function of the barrier layer 102 from the support 101 side to the amorphous layer 103 side or from the amorphous layer 103 side to the support 1
The purpose of this is to prevent free carriers from being injected into the 01 side and easily allow photocarriers generated in the amorphous layer 103 to move and pass through to the support 101 side. It is formed to exhibit insulating behavior. 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. The support temperature when forming the barrier layer 102 is appropriately selected in accordance with the method of forming the barrier layer 102, and the barrier layer 102 is formed. , preferably 50℃~
A temperature of 250°C is desirable. To form the barrier layer 102, the barrier layer 102 to the amorphous layer 103, and further the amorphous layer 1 as necessary, are formed in the same system.
It is possible to continuously form up to the third layer formed on 03, and delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. For this reason, it is advantageous to adopt a glow discharge method or a sputtering method. However, when forming the barrier layer 102 using these layer forming methods, the discharge temperature during layer formation as well as the support temperature described above must be Power and gas pressure can be cited as important factors that influence the characteristics of the barrier layer 102 that is created. The discharge power condition for effectively creating the barrier layer 102 with the characteristics necessary to achieve the purpose with good productivity is usually 1 to 300 W, preferably 2 to 150 W. Also, the gas pressure inside the deposition chamber is usually 3×10 ^-3 ~
5 Torr, preferably about 8×10 ⁻³ to 0.5 Torr. The amount of carbon atoms, nitrogen atoms, hydrogen atoms, and halogen atoms contained in the barrier layer 102 is
Similar to the production conditions in No. 2, this is an important factor in forming a barrier layer with desired characteristics. When the barrier layer 102 is composed of A-Si _a C _1-a , the carbon atom content is 0.1 to 0.4 expressed as a, preferably 0.2 to 0.35, optimally 0.25 to 0.3, and A
- (Si _b C _1-b ) _c H _-c , the content of carbon atoms is expressed as b, c, where b is usually
0.1~0.5, 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 _ _}
d and f are usually 0.1 to 0.47, preferably 0.1 to 0.35,
Optimal is 0.15 to 0.3, e and g are usually 0.8 to 0.99,
It is preferably 0.85 to 0.99, most preferably 0.85 to 0.98. 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, preferably 0.43 to 0.60, expressed as h.
It is estimated to be 0.43 to 0.50. When composed of A-(Si _i N _1-i ) _j H _1-j , the nitrogen atom content is expressed as i and 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 ₊ is usually 0.8 to 0.99, preferably 0.85 to 0.98. Examples of the electrically insulating metal oxide constituting the barrier layer 102 include TiO ₂ , Ce ₂ O ₃ , ZrO ₂ , HfO ₂ ,
_GeO2 , CaO _, BeO, _P2O5 , _{Y2O3 , Cr2O3 ,}
Preferred examples include Al ₂ O ₃ , MgO, MgO.Al ₂ O ₃ , and SiO _2.MgO . Two or more of these may be used in combination to form the barrier layer 102. 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 electron beam method, or the like. For example, the barrier layer 10 can be formed by sputtering.
2 can be formed by sputtering in a sputtering gas atmosphere such as He, Ne, Ar, etc. using a wafer as a starting material for forming the barrier layer as a target. When using the electron beam 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. It is formed as a material exhibiting electrically insulating behavior since it serves to prevent photocarriers generated in the amorphous layer 103 from moving and easily pass through to the support body 101 side. be done. The numerical range of the layer thickness of the barrier layer 102 is one of the important factors for effectively achieving its purpose. If the layer thickness of the barrier layer 102 is sufficiently thin,
If the thickness is too thick, the function of preventing free carriers from flowing into the amorphous layer 103 from the side of the support 101 will not be sufficiently achieved;
The probability that photocarriers generated in the amorphous layer 103 will pass to the side of the support 101 becomes extremely small, and therefore the object of the invention cannot be effectively achieved in any case. 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, an amorphous layer 10 provided on a support 101 is used to effectively achieve the purpose.
3 is A-Si(H,
X), and carbon atoms are doped in the layer thickness direction with a distribution as described below. p-type A-Si(H,X)...Contains only acceptor. Alternatively, it may contain both donor and acceptor, and the acceptor concentration (Na)
Something with a high price. The so-called p type has a low acceptor concentration (Na) in the p -type A ^- Si (H,
Lightly doped with type impurities. n-type A-Si(H,X)...Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd). An n ^- type A-Si (H, i-type A-Si(H,X)...NaNd0 or NaNd. In the present invention, specific examples of the halogen atoms (X) contained in the amorphous layer 103 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 is uneven in the thickness direction of the layer. The surface side opposite to the support 101 (in FIG. 1, the free surface 104
side), and its maximum distribution concentration Cmax
A layer region containing carbon atoms is formed such that the carbon atoms are located at or very close to the surface. 2 to 5 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 5, the vertical axis indicates the layer thickness t of the amorphous layer 103, and _t0 is the interface of the amorphous layer 103 with other things such as the support 101 or the barrier layer 102. Position (bottom surface)
, t _s represents the interface position (upper surface) of the amorphous layer 103 on the free surface 104 side (same position as the free surface 104 in FIG. 1), and from t ₀ to t _s Therefore, the layer thickness t increases, and the horizontal axis shows the distribution concentration C of carbon atoms at any position in the layer thickness direction of the amorphous layer 103, and the distribution concentration increases in the direction of the arrow. is shown, and Cmax indicates the maximum distribution concentration of carbon atoms in the amorphous layer 103. In the example shown in FIG. 2, the distribution state of carbon atoms contained in the amorphous layer 103 in the layer 103 is as follows from the lower surface position _t0 to the upper surface position _ts . The distribution concentration C increases monotonically and continuously, reaching the maximum distribution concentration Cmax at position _t1 , and thereafter there is no fluctuation in the distribution concentration C up to the surface position _ts , and Cmax
The value of is maintained. In Figure 3, near t ₀ , it appears as if no carbon atoms are contained at all, but below the detection limit of carbon atoms, no carbon atoms are contained. This is because they are treated in the same way. Therefore, in the present invention, the amount of carbon atoms is 0.
(e.g. t ₀ and t ₂ in Fig. 3)
The layer region between the two layers is treated as containing no carbon atoms or less than the detection limit. At present, at our technological level, the detection limit for carbon atoms is 10 atomic ppm relative to silicon atoms. In the photoconductive member of the present invention, in order to obtain high photosensitivity and stable image quality characteristics, the distribution state of carbon atoms is such that the distribution amount increases as the position approaches the upper surface position _ts . Carbon atoms are contained in the crystalline layer 103. When the amorphous layer 103 of the photoconductive member 100 prepared _as shown in FIG. The free surface 104 can be provided with a significant increase in its ability to retain the charge applied to the free surface 104. In this case, such a layer region serves as a so-called barrier layer. In this way, the content of carbon atoms in the vicinity of the free surface 104 of the amorphous layer 103 is extremely increased compared to other layer regions, and the upper barrier layer is
Alternatively, the upper barrier layer can be formed on the surface of the amorphous layer 103 using the same material as the barrier layer 102. In this case, the thickness of the upper barrier layer is usually 30 Å to 5 μm, preferably 50 Å to 2 μm. In the example shown in FIG. 3, the layer region between t ₀ and t ₂ on the lower side of the amorphous layer 103 does not contain any carbon atoms or contains less than the detection limit amount. From position _t2 to _t3 , the distribution concentration of carbon atoms increases monotonically in a linear function or a function close to a linear function, and at position _t3 ,
The increasing distribution concentration Cmax is reached. In the layer region between t ₃ and t _s , carbon atoms have a maximum distribution concentration
It is uniformly contained at Cmax. In the example shown in FIG. 4, carbon atoms are uniformly contained in the lower layer region (between t ₀ and t ₄ ) of the amorphous layer 103 at a constant concentration C _{1 .} In the upper layer region (t ₄ and t ₃ ), carbon atoms are contained in a uniformly distributed state with a maximum distribution concentration Cmax, and in the lower layer region and the upper layer region, carbon atoms are contained. The distribution amount is discontinuous. In the example shown in FIG.
From position t ₀ to position t ₅ on the lower surface of 3, carbon atoms are contained with a constant distribution amount C ₂ , and the distribution concentration of carbon atoms gradually decreases from position t ₅ to position t ₆ . from position t ₆ to upper surface position t _s
The distribution amount of carbon atoms increases rapidly until the upper surface position t _s is reached, and the maximum distribution concentration Cmax is reached.
Carbon atoms are distributed as follows. In the present invention, the maximum distribution concentration of carbon atoms
Cmax can normally take the values mentioned above, but is preferably 0.05 to 90 atomic%, most preferably
It is desirable to select from the range of 0.1 to 90 atomic %. 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 thickness direction of the amorphous layer 103, and have a maximum distribution concentration at or near the upper surface position _{ts .} , and a desired distribution state function such that a distribution state in which the distribution concentration decreases from the upper surface position t _s to the lower surface position t ₀ is formed in the layer thickness direction in the amorphous layer 103. Accordingly, by being added to the amorphous layer 103, the intended purpose of the present invention is effectively achieved, but furthermore, it is added to the amorphous layer 103 as a whole. The content of carbon atoms present is also important in achieving the intended purpose of the invention. In the present invention, the value of the total amount of carbon atoms contained in the amorphous layer 103 can normally take the above-mentioned value, more preferably 0.005 to 20 at%, most preferably It is desirable to select from the range of 0.005 to 10 atomic %. In the present invention, in order to form the amorphous layer 103 mainly composed of A-Si (H, done by. For example, to form an amorphous layer by glow discharge method, Si can be generated.
Along with Si generation raw material gas, for hydrogen atom introduction or/
Then, a raw material gas for introducing halogen 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 ( What is necessary is to form a layer consisting of H, X). 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 a 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, hydrogen atoms or / Then, a gas for introducing halogen atoms may be introduced into a deposition chamber for sputtering. In this case, the method of 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 formation, in conjunction with the growth of the layer, or to Sometimes, sputtering is carried out using a target for introducing carbon atoms that has been provided in advance in the deposition chamber. In the present invention, the Si generation raw material gas used when forming the amorphous layer 103 includes 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 forming operations. SiH ₄ is easy to handle and has 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. Furthermore, silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or can be gasified, are also 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 consisting of A-Si;X can be formed on a predetermined support. When creating the amorphous layer 103 containing halogen atoms according to the glow discharge method, basically, a silicon halide gas, which is a raw material gas for Si generation, and a silicon halide gas are used.
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber to form an amorphous layer 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 amorphous layer 103 on a predetermined support, a silicon compound gas containing hydrogen atoms may be added to these gases in order to introduce hydrogen atoms. A layer may be formed by mixing a predetermined amount. 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 the amorphous layer 103 mainly 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 silanes, etc., may be 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 reactive 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. When forming an amorphous layer by sputtering, in addition to the above, a target for introducing carbon atoms may be provided in the deposition chamber, and the target may be sputtered as the layer grows. . In the present invention, a gaseous or easily gaseous starting material is effectively used as a raw material gas for introducing carbon atoms into the amorphous layer 103. A large number of carbon compounds can be mentioned. Such starting materials include, for example, saturated hydrocarbons having 1 to 5 carbon atoms, consisting of C and H, and saturated hydrocarbons having 2 to 5 carbon atoms.
5, an acetylene hydrocarbon 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 ), and butylene (C ₄ H ₆ ). In addition to these, Si(CH ₃ ) ₄ , Si
Alkyl silicides such as (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 ₃ CH ₃ , CCl ₄ , CHF ₃ ,
Halogen-substituted paraffinic hydrocarbons such as CH ₂ F ₂ , CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl can also be mentioned as effective. In order to form the amorphous layer 103 into which carbon atoms are introduced by the sputtering method, the amorphous layer 10
3, a single-crystal or polycrystalline Si wafer is sputtered in an atmosphere of a raw material gas for introducing carbon atoms, or a single-crystal or polycrystalline Si wafer is
Sputtering may be performed using a Si wafer and a C wafer or a wafer containing a mixture of Si and C as a target. For example, if a Si wafer is used as a target, the same raw material gases listed for glow discharge as raw material gases for introducing carbon atoms and hydrogen atoms (H) or halogen atoms (X) are used.
The Si wafer may be sputtered by diluting it with a diluting gas if necessary and introducing it into a deposition chamber for sputtering to form a gas plasma of these gases. Alternatively, a gas atmosphere containing at least hydrogen atoms (H) or halogen atoms (X) can be created by using Si and C as separate targets or by using a single target containing Si and C. This is done by sputtering inside. 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, examples of starting materials that serve as raw material gas for introducing oxygen atoms include oxygen (O ₂ ), ozone (O ₃ ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ) or
For example disiloxane H ₃ SiOSiH ₃ , trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ . In addition, the amorphous layer 1 can be formed using a sputtering method.
In the present invention, SiO ₂ , SiO, and the like are effectively used as materials capable of forming a target for introducing oxygen atoms when forming 03. In the present invention, effective starting materials for the raw material gas for introducing halogen atoms used when forming the amorphous layer 103 include the above-mentioned halogen compounds or silicon compounds containing halogen, but there are others. , HF, HCl, HBr,
Hydrogen halides such as HI, SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents, such as halogen-substituted silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , and SiHBr ₃ , are also effective starting materials for forming an amorphous 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 at the same time as halogen atoms are introduced into the layer when forming an amorphous layer. is used as a suitable raw material for halogen introduction. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride gas such as Si ₃ H ₈ and Si ₄ H ₁₀ is converted into A-Si
This can also be done by coexisting with a silicon compound in the deposition chamber to generate a discharge. 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, it also serves as doping with impurities.
Gases such as B ₂ H ₆ , PH ₃ and PF ₃ can also be introduced. In the present invention, H or X contained in the amorphous layer of the photoconductive member to be formed is also determined by the amount or (H+X)
The amount of is usually 1 to 40 atomic %, preferably 5 to 30 atomic %.
Preferably, it is expressed as atomic percent. The amount of H and/or All you have to do is control the force. The amorphous layer has n-type tendency or p-type tendency or i
To form a mold, n-type impurities or p-type impurities are added during layer formation by glow discharge method, reactive sputtering method, etc.
This is accomplished by doping a type impurity or both impurities into the layer to be formed while controlling the amount thereof. 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 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, the amount of impurity introduced into the amorphous layer in order to have a desired conductivity type is in the range of 3×10 ^-2 atomic % or less in the case of impurities in group A of the periodic table. In the case of impurities belonging to group A of the periodic table, doping may be performed in an amount of 5×10 ^-3 atomic % or less. The thickness of the amorphous layer is determined as desired so that the photocarriers generated in the amorphous layer are efficiently transported in a predetermined direction, and is usually 1 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 to which 5 g of aluminum sulfate was added at a temperature of 18°C. After anodizing for about 5 minutes, the substrate was lifted from the sulfuric acid solution and immediately immersed in a boiling pure water tank. After about 10 minutes, the substrate was lifted 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, the sixth unit was placed in a completely shielded clean room.
Using the apparatus shown in the figure, an electrophotographic image forming member was prepared by the following operations. The aluminum alloy substrate 609 treated by the above method was firmly fixed to a fixing member 603 at a predetermined position in the glow discharge deposition chamber 601. Substrate 60
9 is heated with an accuracy of ±0.5° C. by a heater 608 within the fixed member 603. Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system were closed, the main valve 610 was fully opened to evacuate the chamber 601 to a degree of vacuum of approximately 5×10 ^-6 Torr. Thereafter, the input voltage to the heater 608 was increased, and the input voltage was varied while detecting the temperature of the aluminum alloy substrate until it stabilized at a constant value of 250°C. After that, the auxiliary valve 641, then the outflow valves 626, 627, 629 and the inflow valve 621,
622 and 624 were fully opened, and the mass flow controllers 616, 617, and 619 were also sufficiently degassed to a vacuum state. Auxiliary valve 641, valves 626, 62
After closing 7,629,621,622,624, _SiH4 gas diluted to 10 vol% with _H2 (purity
99.999%, hereinafter abbreviated as SiH ₄ (10)/H ₂ ) cylinder 61
1 bulb 631, diluted to 0.1 vol% with _H2
C ₂ H ₄ gas (purity 99.999%, below C ₂ H ₄ (0.1)/H ₂
It is abbreviated as ) Open the valve 632 of the cylinder 612,
Adjust the pressure of the outlet pressure gauges 636, 637 to 1 Kg/cm ² and gradually open the inflow valves 621, 622 to introduce SiH ₄ into the mass flow controllers 616, 617.
(10)/H ₂ gas and C ₂ H ₄ (0.1)/H ₂ gas were introduced. Subsequently, the outflow valves 626 and 627 were gradually opened, and then the auxiliary valve 641 was gradually opened. At this time, SiH ₄ (10)/H ₂ gas flow rate and C ₂ H ₄ (0.1)
Mass flow controllers 616 and 617 were adjusted so that the gas flow ratio was 10:0.1. Next, while watching the reading on the Pirani gauge 642, adjust the opening of the auxiliary valve 641 so that the inside of the chamber 601 is 1×.
Auxiliary valve 641 was opened until 10 ^-2 Torr. After the internal pressure of the chamber 601 became stable, the main valve 610 was gradually closed, and the opening was throttled until the Villany gauge 642 indicated 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 643, close the shutter (also serves as an electrode) 605, and connect the electrode 603 and shutter 605.
High frequency power of 13.56MHz was applied to generate glow discharge in the chamber 301, resulting in an input power of 10W. The above conditions were maintained for 3 hours to form a lower region layer constituting the amorphous layer. After that, turn on the high frequency power supply 643.
With the OFF state and the glow discharge stopped, the outflow valve 627 is closed, and then the C ₂ H ₄ gas (99.999% purity) cylinder 614 is connected to the valve 634.
Gas pressure of 1Kg/ ^cm2 through (outlet pressure gauge 639
reading), the inflow valve 624 and the outflow valve 62
9 gradually open to the mass flow controller 619.
C ₂ H ₄ gas was supplied and the mass flow controller 619 was adjusted so that the C ₂ H ₄ gas was stabilized at 1/10 of the SiH ₄ (10)/H ₂ gas flow rate. Subsequently, the high frequency power supply 643 was turned on again to restart the glow discharge. The input power at that time was set to 3W. In this way, the glow discharge is further increased by 10
The upper region layer constituting the amorphous layer is
After forming to a thickness of 600 Å, heating heater 608
is turned OFF, the high frequency power supply 648 is also turned OFF, and after waiting for the substrate temperature to reach 100°C, the outflow valves 626, 629 and the inflow valves 621,
622 and 624 are closed, the main valve 610 is fully opened, and the inside of the chamber 601 is brought down to 10 ^-5 Torr or less. Then, the main valve 610 is closed, and the inside of the chamber 601 is brought to atmospheric pressure by the leak valve 606, and the substrate is taken out. did. In this case, the total thickness of the layer formed is approximately 9
It was μ. 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 irradiated with a light image. The optical image was created using a dungsten lamp light source at 1.0 lux.
A light intensity of sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. In addition, when the above-described image forming process was repeated and the electrophotographic image forming member was tested for durability, the image obtained on the 10,000th sheet of transfer paper was also of extremely good quality. There was no difference in comparison with the image on the transfer paper, demonstrating that this electrophotographic image forming member has excellent corona ion resistance, abrasion resistance, cleanability, etc., and is extremely durable. Note that blade cleaning was adopted as the cleaning method, 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. Example 2 Mirror-finished aluminum alloy 61S (contains Cu, Si, and Cr) measuring 10 cm x 10 cm with a thickness of 1 mm
The substrate was subjected to the same anodic oxidation treatment as in Example 1, thoroughly dried, and then left in a heated 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] 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 601 was heated 5× by the same operation as in Example 1.
After creating a vacuum of 10 ^-6 Torr and maintaining the substrate temperature at 250°C, the auxiliary valve 641 and then the outflow valves 626, 627, 62 were opened in the same manner as in Example 1.
9 and inflow valves 621, 622, 624, and mast controllers 616, 617, 61.
9 was also sufficiently degassed and vacuumed. Auxiliary valve 6
41, valve 626, 627, 629, 621,
After closing 622 and 624, valve 631 of SiH ₄ (10)/H ₂ gas (99.999% purity) cylinder 611;
C ₂ H ₄ (0.1) / Valve 63 of H ₂ gas cylinder 612
2, and the pressure on the outlet pressure gauges 636 and 637 is set to 1.
Kg/cm ² and gradually open the inflow valves 621 and 622 to control the mass flow controllers 616 and 6.
SiH ₄ (10)/H ₂ gas and C ₂ H ₄ (0.1)/H ₂ were each introduced into the chamber 17. Subsequently, the outflow valve 626,
627 was gradually opened, and then the auxiliary valve 641 was gradually opened. At this time, SiH ₄ (10)/H ₂ gas flow rate and
Mass flow controllers 616 and 617 were adjusted so that the C ₂ H ₄ (0.1)/H ₂ gas flow rate ratio was 10:0.1. Next, while watching the reading on the Pirani gauge 642, adjust the opening of the auxiliary valve 641, and
Auxiliary valve 64 until the inside of 1 becomes 1×10 ^-2 Torr.
I opened 1. After the internal pressure of the chamber 601 stabilizes, the main valve 610 is gradually closed and the Pirani gauge 6 is closed.
The aperture was narrowed down until the instruction number 41 was 0.1 Torr.
After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter (which also serves as an electrode) 605 and turn on the high frequency power source 643.
13.56MHz high frequency power is applied between the electrodes 603 and 605 to generate a glow discharge in the chamber 601,
The input power was 10W. At the same time as starting to deposit the lower region layer constituting the amorphous layer on the substrate under the above conditions, the mass flow controller 617
Continuously increase the flow rate setting value, and after 5 hours
The ratio of SiH ₄ (10)/H ₂ gas flow rate to C ₂ H ₄ (0.1)/H ₂ gas flow rate was adjusted to 1:1. After 5 hours have elapsed, the high frequency power source 643
is turned OFF, the outflow valve 627 is closed with the glow discharge centered, and then the inflow valve is closed with a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 639) from the C ₂ H ₄ gas cylinder 614 through the valve 634. 624, the outflow valve 629 is gradually opened to flow C ₂ H ₄ gas to the mass flow controller 619, and by adjusting the mass flow controller 619, C ₂ H ₄
The gas was stabilized at 1/10 of the SiH ₄ (10)/H ₂ gas flow rate. Subsequently, the high frequency power supply 643 was turned on again to restart the glow discharge. The input power at that time was set to 3W. In this way, the glow discharge is further increased by 15
After forming the upper region layer constituting the amorphous layer for a minute, the heating heater 608 is turned off, the high frequency power supply 643 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 62 is turned off.
6,629 and inflow valves 621, 622, 62
4 and fully open the main valve 610 to reduce the inside of the chamber 601 to 10 ^-5 Torr or less, close the main valve 610 and open the inside of the chamber 601 with the leak valve 60.
6 to bring the pressure to atmospheric pressure and take out the substrate. 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 quality was obtained. Example 5 An aluminum substrate obtained by processing in the same manner as in Example 1 was installed, and then the inside of the glow discharge deposition chamber 601 was made into a vacuum of 5 × 10 ^-6 Torr by the same operation as in Example 1, and the substrate was removed. After the temperature was maintained at 250°C, the auxiliary valve 641, then the outflow valves 626, 627 and the inflow valve 6 were opened in the same manner as in Example 1.
21 and 622 were fully opened, and the mass flow controllers 616 and 617 were also sufficiently degassed and brought into a vacuum state.
Auxiliary valve 641, valves 626, 627, 62
After closing 1,622, SiH ₄ (10)/H ₂ gas (purity
99.999%) Valve 631 of cylinder 611, C ₂ H ₄
(0.1)/H ₂ Open the valve 632 of the gas cylinder 612, and the pressure on the outlet pressure gauges 636, 637 is 1Kg/cm ²
and gradually open the inflow valves 621 and 622 to enter the mass flow controllers 616 and 617.
SiH ₄ (10)/H ₂ gas and C ₂ H ₄ (0.1)/H ₂ were respectively introduced. Subsequently, the outflow valves 626 and 627 were gradually opened, and then the auxiliary valve 641 was gradually opened. At this time, SiH ₄ (10)/H ₂ gas flow rate and C ₂ H ₄
The inflow valves 621 and 622 were adjusted so that the (0.1)/H ₂ gas flow rate ratio was 10:0.1. Next, the opening of the auxiliary valve 641 was adjusted while observing the reading on the Pirani gauge 642, and the auxiliary valve 641 was opened until the inside of the chamber 601 became 1×10 ⁻² Torr. After the internal pressure of the chamber 601 became stable, the main valve 610 was gradually closed and the opening was throttled until the reading on the Pirani gauge 641 reached 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter 605 (which also serves as an electrode), turn on the high frequency power source 643, and turn on the electrode 6.
Between 03 and 605, high frequency power of 13.56MHz was applied to generate glow discharge in the chamber 601, resulting in an input power of 10W. Under the above conditions, the flow rate setting value of the mass flow controller 617 was continuously increased for 5 hours at the same time as the photoconductive layer was started to be deposited on the substrate, and the SiH ₄ (10)/H ₂ gas flow rate after 5 hours was and C ₂ H ₄
(0.1)/H ₂ gas flow rate ratio was adjusted to 1:10. After forming the photoconductive amorphous layer in this way, the heating heater 608 is turned off, the high frequency power supply 643 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 626, 627 and the inflow valves are turned off. 621 and 622 are closed, and main valve 6 is closed.
10 is fully opened to reduce the temperature inside the chamber 601 to 10 ^-5 Torr or less, then the main valve 610 is closed and the chamber 601 is
The inside of the chamber was brought to atmospheric pressure using a leak valve 606, 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 6 The SiH ₄ (10)/H ₂ gas cylinder 611 was replaced with a SiF ₄ gas (purity 99.999%) cylinder, and the C ₂ H ₄ (0.1)/H ₂ gas cylinder 612 was replaced with argon containing 0.2 vol% ethylene (hereinafter referred to as "C ₂ H ₄ (0.2)/Ar". Purity 99.999
%) Instead of using a gas cylinder, the SiF ₄ gas flow rate at the initial stage of amorphous layer deposition and the C ₂ H ₄ (0.2)/Ar gas flow rate ratio of 1:0.5 were set to start layer formation and form an amorphous layer. SiF ₄ gas flow rate and C ₂ H ₄ (0.2)/Ar at the end of layer deposition
C ₂ H ₄ (0.2)/ so that the gas flow ratio is 1:15.
A photoconductive layer was formed on the pretreated aluminum substrate under the same operating conditions as in Example 5, except that the Ar gas flow rate was continuously increased and the input power for glow discharge was 100 W. The thickness of the layer formed in this case 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 5, an extremely clear image was obtained. Example 7 An aluminum substrate pretreated and prepared in the same manner as in Example 1 was installed, and then, by the same operation as in Example 1, the inside of the glow discharge deposition chamber 601 was heated 5×.
After applying a vacuum of 10 ^-6 Torr and maintaining the substrate temperature at 250°C, the auxiliary valve 641 and then the outflow valve 6
26, 627, 628, 629 and inflow valve 6
21, 622, 623, 624 fully open, mass flow controller 616, 617, 618, 619
The interior was also sufficiently degassed and vacuumed. Auxiliary valve 641, valve 626, 627, 6
28,629,621,622,623,624
After closing SiH ₄ (10)/H ₂ gas cylinder 611 valve 631, C ₂ H ₄ (0.1)/H ₂ gas cylinder 612 valve 632, B ₂ H ₆ diluted to 50 volppm with H ₂
Gas (purity 99.999%, hereinafter referred to as "B ₂ H ₆ (50)/H ₂ ")
It is abbreviated as )Open the valve 633 of the cylinder 613,
The pressure of outlet pressure gauges 636, 637, 638 is 1
Adjust to Kg/cm ² , inflow valve 621, 622, 6
23 gradually open the mass flow controller 61.
SiH ₄ (10)/H ₂ gas, C ₂ H ₄ into 6,617,618
(0.1)/H ₂ gas and B ₂ H ₆ (50)/H ₂ gas were introduced. Subsequently, the outflow valves 626, 627, 6
28 was gradually opened, and then the auxiliary valve 641 was gradually opened. At this time, SiH ₄ (10)/H ₂ gas flow rate and
C ₂ H ₄ (0.1)/H ₂ gas flow ratio is 10:0.1, SiH ₄
(10)/H ₂ gas flow rate and B ₂ H ₆ (50)/H ₂ gas flow rate
Mass flow controller 61 so that the ratio is 50:1.
6,617,618 was adjusted. Next, while paying close attention to the reading on the Pirani gauge 642, the auxiliary valve 64
The auxiliary valve 641 was opened until the pressure inside the chamber 601 was 1×10 ⁻² Torr. After the internal pressure of the chamber 601 became stable, the main valve 610 was gradually closed and the opening was throttled until the reading on the Pirani gauge 642 reached 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, turn on the high frequency power supply 643, close the shutter (also serves as an electrode) 605, and apply 13.56MHz high frequency power between the power supply 603 and shutter 605. Insert
A glow discharge was generated in the chamber 601, and the input power was 10W. The above conditions were maintained for 3 hours to form a lower region layer constituting a photoconductive amorphous layer. After that, the high frequency power supply 643 is turned off, and the outflow valves 627, 6 are turned off, and the glow discharge is stopped.
The mass flow controller 61 is closed by gradually opening the inflow valve 624 and the outflow valve 629 at a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 639) from the C ₂ H ₄ gas cylinder 614 through the valve 634.
Flow C ₂ H ₄ gas through mass flow controller 6.
16,619, C ₂ H ₄ gas is converted into SiH ₄
The flow rate was stabilized to 1/10 of the (10)/H ₂ gas flow rate. Subsequently, the high frequency power supply 643 was turned on again to restart the glow discharge. The input power at that time was set to 3W. In this way, the glow discharge is further increased by 10
The upper region layer constituting the amorphous layer is
After forming to a thickness of 600 Å, heating heater 608
is turned OFF, the high frequency power supply 643 is also turned OFF, and after waiting for the substrate temperature to reach 100°C, the outflow valves 626, 629 and the inflow valves 621,
622, 623, 624 are closed, and main valve 6 is closed.
10 is fully opened to reduce the temperature inside the chamber 601 to 10 ^-5 Torr or less, then the main valve 610 is closed and the chamber 601 is
The inside was brought to atmospheric pressure using a leak valve 606, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member obtained in this way was placed in a charging exposure experimental device and exposed to 5.5KV.
Corona charging was performed for 0.2 seconds, and a light image was immediately irradiated. The optical image is 1.0 using a Dangs lamp light source.
A light amount of 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 image forming member was corona charged for 0.2 seconds at 6.0 KV using a charging exposure experiment device.
Immediately perform image exposure with a light intensity of 0.8 lux・sec,
Immediately thereafter, a charged developer was cascaded onto the surface of the member, and then transferred and fixed onto transfer paper, resulting in an extremely clear image. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 8 Using the apparatus shown in FIG. 6, an electrophotographic image forming member was prepared by the following operations. An aluminum substrate 609 prepared by pretreatment in the same manner as in Example 1 was firmly fixed to a fixing member 603 at a predetermined position in the deposition chamber 601. The target 604 is made of high purity graphite (99.999%) placed on polycrystalline purity silicon (99.999%). The substrate 609 is heated with an accuracy of ±0.5° C. by a heater 608 within the fixing member 603. Temperature was measured directly on the backside of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 610 is fully opened and the
The vacuum is evacuated to about 10 ^-6 Torr (at this time, the system valves are closed), and the auxiliary valve 641 and the outflow valves 626, 627, 629, 630 are
is opened and the mass flow controllers 616, 61
After the inside of No. 7,619,620 was sufficiently degassed, outflow valves 626, 627, 629, 630 and auxiliary valve 641 were closed. Argon (purity
99.999%) After opening the valve 635 of the gas cylinder 615 and adjusting the reading of the outlet pressure gauge 640 to be 1 Kg/cm ² , the inflow valve 625 is opened.
The outflow valve 630 was then gradually opened to allow argon gas to flow into the chamber 601. Until the Villaney Gauge 611 indicates 5×10 ^-4 Torr,
The outflow valve 630 was gradually opened, and after the flow rate became stable in this state, the main valve 610 was gradually closed, and the opening was narrowed until the indoor pressure reached 1×10 ⁻² Torr. When the shutter 605 is opened,
After confirming that the mass flow controller 620 is stable, turn on the high frequency power supply 643 and connect the target 604 and the fixing member 603.
13.56MHz, 100W 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 100 Å intermediate layer. Thereafter, the high frequency power supply 643 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 630 was closed, and the main valve 610 was fully opened to remove gas from the chamber 601, creating a vacuum of 5×10 ⁻⁶ Torr. Thereafter, the input voltage of the heater 608 was increased, and the input voltage was varied while detecting the substrate temperature until it stabilized at a constant value of 200°C. Thereafter, a photoconductive layer was formed using the same operations and conditions as in Example 1. 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 9 The same operation as in Example 6 except that the Alcon gas cylinder 612 containing 0.2 vol% ethylene in Example 6 was replaced with a hydrogen gas cylinder containing 0.2 vol% ethylene.
A photoconductive amorphous layer was formed on an aluminum substrate pretreated under the following conditions. 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 6, an extremely clear image was obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram for explaining the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG.
5 to 5 are schematic illustrations for explaining the distribution state of carbon atoms contained in the amorphous layer of the photoconductive member of the present invention, and FIG. 6 is a photoconductive member prepared according to the present invention. FIG. 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 one of a hydrogen atom and a halogen atom and having a silicon atom as its matrix, an amorphous layer exhibiting photoconductivity, and the amorphous layer is substantially uniform in at least a portion thereof in a plane substantially parallel to the surface of the support, and is substantially uniform in the layer thickness direction. It has a layer region containing carbon atoms in a non-uniform manner and more distributed toward the surface opposite to the support, and the content of carbon atoms is 0.005.
30 atom %, and the maximum value of the distribution concentration in the layer thickness direction is 0.03 to 90 atom %.