JPS6242266B2 - - 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 members constituting the photoconductive layer in electrophotographic image forming 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 will accumulate and a ghost phenomenon will occur. This causes problems such as white spots in the transferred image. Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or cracks may develop over time after it is taken out of the vacuum deposition chamber for layer formation and left in the air. 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 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. 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 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 have sufficient charge retention ability 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 in which almost no is observed. 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. and an amorphous layer that exhibits photoconductivity, the amorphous layer contains nitrogen atoms, and the amorphous layer has a distribution amount C ₁ of nitrogen atoms. A lower layer region is distributed substantially uniformly in the layer thickness direction with a distribution amount C ₂ , an upper layer region is distributed substantially uniformly in the layer thickness direction with a distribution amount C 2, and these two layer regions are and an intermediate layer region in which oxygen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₃ (however, C ₃ <C ₁ , C ₂ ). shall be. 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 use in 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 contains nitrogen atoms, and the distribution of the nitrogen atoms is adjusted to the surface of the support 101. It is substantially uniform in a plane substantially parallel to , and is different in each layer region 104 , 105 , 106 in the thickness direction of the layer. That is, the amorphous layer 103 has a lower layer region 104 in which nitrogen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₁ and a lower layer region 104 in which nitrogen atoms are substantially uniformly distributed in the layer thickness direction with a distribution amount C ₂ . an upper layer region 106 in which nitrogen atoms are distributed as shown in _FIG . It is made up of. In the present invention, the distribution amount C ₁ , C ₂ , C ₃ of nitrogen atoms in each layer region has a magnitude relationship such that C ₃ <C ₁ ,
Although it is possible to take a desired value such that C ₂ , the upper limit of the values of distribution amounts C ₁ and C ₂ is 60 atomic % or less, preferably 57 atomic % or less,
The optimum value is preferably 50 atomic % or less, and the lower limit is usually 11 atomic % or more, preferably 15 atomic % or more. As for the value of the distribution amount _C3 , its upper limit is usually
It is 10 atomic% or less, preferably 5 atomic% or less, optimally 2 atomic% or less, and the lower limit is usually 0.01 atomic% or more, preferably 0.02 atomic% or more, and optimally 0.03 atomic% or more. is desirable. 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. The surface of the pure aluminum or aluminum alloy substrate is anodized, and then, after an appropriate treatment if necessary, a boiling water treatment or a steam treatment is performed to produce Al ₂ O ₃ H _{2 .} 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 voltage is about 40 to 120 Volt. 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
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. administered. The boiling water treatment can be carried out by immersing the anodized substrate in water that has been desalinated 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-Seewaser, 4S,
Examples of commercially available products include KS-Seewasser, 3S, 14S, 17S, 24S, Y alloy, NS, RS, Silumin, American alloy, German alloy, Kupfer-Silumin, Silumin-Gamma, etc. . 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 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 sufficiently exhibited. Furthermore, by containing a sufficient amount of nitrogen 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 a part of the layer region of the amorphous layer 103.
It is possible to provide the same function as 02, and in this case, the content of nitrogen atoms in the layer region that exhibits such function is usually preferably 25 to 60 atomic%. . 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- [Six (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 the amorphous material constituting the barrier layer 102, which can be effectively used in the present invention, for example, carbon-based amorphous material such as a-
Si _a C _1-a , a-(Si _b C _1-b ) _c H _1-c , a-(Si _d C _1-d ) _e X
_1-e , a-(Si _f C _1-f ) _g (H+X) _1-g , a-Si _h N _1-h , a-(Si _i N _1-i ) _j as a nitrogen-based amorphous material H _1-j ,
a-(Si _k N _1-k ) _l X _1-l , a-(Si _n N _1-n ) _o (H+X) _1
-
o , a-Si _p O _1-p , a- as an oxygen-based amorphous material
(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 seed atoms as constituent atoms. (However, 0<a, b, c, d,
e, f, g, h, i, j, k, l, m, n, o,
p, q, r, s, t, u<1). These amorphous materials 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 laminated on 02 and the like. Particularly from the viewpoint of properties, it is preferable to select carbon-based or nitrogen-based amorphous materials. 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 ₄ 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 ₁₀ , saturated hydrocarbons containing C and H as constituent atoms, e.g. having 1 to 5 carbon atoms, ethylene hydrocarbons having 1 to 5 carbon atoms, carbon atoms Examples include 2 to 4 acetylene hydrocarbons. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. As a raw material gas containing Si and H as constituent atoms,
Alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ can be mentioned. In addition to these raw material gases, H ₂ is of course also used as an effective 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 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 , as silicon hydride, SiH ₄ , Si ₂ H ₆ ,
Examples include silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ . 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, C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si( _C2H5 ) _{4 ,}
Alkyl silicides such as SiCl(CH ₃ ) ₃ , SiCl ₂
Silane derivatives such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These barrier layer forming substances are used to form a barrier layer so that the formed barrier layer contains silicon atoms, carbon atoms, and optionally halogen atoms and hydrogen atoms in a predetermined composition ratio. They are selected and used as desired. For example, SiHCl _{3 and} SiCl contain Si(CH ₃ ) ₄ and halogen atoms, which can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and form a barrier layer with desired characteristics. ₄ , SiH ₂ Cl ₂ , or SiH ₃ Cl in a gaseous state at a predetermined mixing ratio to generate a glow discharge, a-(Si _f C _{1 -f} ) _g (X+H) _1-
A barrier layer consisting of _g can be formed. 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 ), hytrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ H ₂ ), 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. The starting material for introducing an oxygen atom is added to a starting material selected from among the starting materials for the formation as desired.The starting material for introducing an oxygen atom is a gaseous material having at least an oxygen atom as a constituent atom. Most substances or gasified versions of gasifiable substances 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), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), Si, O, and H as constituent atoms, such as disiloxane H ₃ SiOSiH ₃ , trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ SiH 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−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 system and SiCl ₂ (CH ₃ ) ₂ -SiH ₄ system. 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 using the wafer as a target in these 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 separate targets for 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, 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 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 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 into the raw material gas shown in the glow discharge example described above can also be 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, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, The preparation conditions are carefully selected so that a non-photoconductive amorphous material is formed. The amorphous material constituting the barrier layer 102 of the present invention has the function of blocking the injection of free carriers from the support 101 side to the amorphous layer 103 side, and preventing the injection of free carriers in the amorphous layer 103. It is formed to exhibit electrically insulating behavior because it easily allows the generated photo carriers to move and pass through to the support 101 side. 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 properties of the formed layer. In the present invention, the temperature of the support during layer formation is strictly controlled so that the amorphous material having the desired properties can be formed as desired. In order to effectively achieve the purpose of the present invention, the optimum 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. is executed, but
In the case of systems containing hydrogen atoms or halogen atoms, the temperature is usually 100°C to 300°C, preferably 150°C to 250°C.
°C, and in the case of systems that do not contain hydrogen atoms or halogen atoms, it is usually 20 to 200 °C, preferably 20 to 150 °C.
It is preferable to set the temperature to ℃. barrier layer 10
2, the barrier layer 102 to the amorphous layer 103 are formed in the same system, and further the amorphous layer 103 is formed as necessary.
It can be formed continuously up to the third layer formed on top. 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, discharge power and gas pressure during layer formation are important factors that influence the characteristics of the barrier layer 102 created, as well as the support temperature described above. This can be mentioned as a factor. 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.
~300W, preferably 2-150W. Furthermore, the gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8×
It is desirable that it be about 10 ^-3 to 0.5 Torr. 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 manufacturing conditions of 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 formed of a-SiaC _1-a , the representation of a is 0.1 to 0.4, preferably 0.2 to 0.35, optimally 0.25 to 0.3, and a-(Si _b C _1-b ) When composed of _c H _1-c , b is usually 0.1 to 0.5, preferably 0.1 to 0.35, optimally
0.15-0.3, c is usually 0.60-0.99, preferably 0.65
~0.98, optimally 0.7~0.95, a-
(Si _d C _1-d ) _e X _1-e or a-(Si _f C _1-f ) _g (H+X) _1-g
In the case of displaying d, e, f, g, d and f are usually 0.1 to 0.47, preferably 0.1 to 0.
0.35, optimally 0.15~0.3, e, g usually 0.8~
0.99, preferably 0.85-0.99, optimally 0.85-0.98
It is said that When the barrier layer 102 is made of a nitrogen-based amorphous material, first, in the case of a-Si _h N _1-h , h is usually 0.43 to 0.60, preferably 0.43 to 0.50. a-(Si _i N _1-i ) _j H _1-j , i,
If expressed as j, i is usually 0.43 to 0.6, preferably 0.43 to 0.5, j is usually 0.65 to 0.98, preferably 0.7 to 0.95, and a-(Si _k N _1-k ) _l X When composed of _1-l or a-(Si _n N _1-n ) _o (H+X) _1-o , k, l are usually expressed as k, l, m, n.
0.43 to 0.60, preferably 0.43 to 0.49, and m and n are usually 0.8 to 0.99, preferably 0.85 to 0.98. When the barrier layer 102 is made of an oxygen-based amorphous material, first, in a-Si _p O _1-p , the value of o is usually 0.33 to 0.40, preferably 0.33 to 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 0.37, and t and u are usually 0.80 to 0.99, preferably 0.85 to 0.98. 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 manufactured. 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 electron beam method, a starting material for forming a barrier layer may be put into a vapor deposition port 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 toward the amorphous layer 103 from the side of the support 101 cannot be sufficiently achieved, and if it is too thick, free carriers may be generated in the amorphous layer 103. The probability of the photo carrier passing to the support 101 side becomes extremely small, and therefore, in any case, the object of the present invention cannot be effectively 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 nitrogen atoms are doped in the layer thickness direction in the distribution state described above. p-type a-Si(H,X)... Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). The so-called p ^- type a-Si(H,X)... has a low acceptor concentration (Na).
Lightly doped with type impurities. n-type a-Si(H,X): Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd). An n ^- type a-Si (H, i-type a-Si(H,X)...NaNdO or NaNd. In the present invention, specific examples of the halogen 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 present invention, in order to form the amorphous layer 103 mainly composed of a-Si (H, done by. For example, in order to form the amorphous layer 103 by the glow discharge method, the internal pressure is reduced between the Si-generating source gas that can generate Si and the source gas for introducing hydrogen atoms and/or halogen atoms. a-Si(H,
What is necessary is to form a layer consisting of. To introduce nitrogen atoms into the layer being formed, along with the growth of the layer,
A raw material gas for introducing nitrogen atoms may be introduced into the deposition chamber during formation 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 nitrogen atoms into the amorphous layer 103 is to introduce a raw material gas for introducing nitrogen atoms into the deposition chamber at the time of layer growth, or to At the time of layer formation, a target for introducing nitrogen atoms, which has been provided in advance in the deposition chamber, may be sputtered. 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. Furthermore, silicon compounds containing silicon atoms and halogen atoms, which are in a gaseous state or contain gasifiable halogens, can also be cited as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, and IBr. Preferred examples of silicon compounds containing halogens, so-called halogen-substituted silane derivatives include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ . When employing such a halogen-containing silicon compound to form the characteristic photoconductive member of the present invention by a glow discharge method, silicon hydride gas is used as a raw material gas that can generate Si. Even if it is not necessary, an amorphous layer made of a-Si:X can be formed on a predetermined support. When manufacturing the amorphous layer 103 containing halogen atoms by 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 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 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. Nitrogen 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 nitrogen 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. In the present invention, a gaseous or easily gaseous starting material is effectively used as a raw material gas for introducing nitrogen atoms into the amorphous layer 103. A large number of nitrogen compounds can be mentioned. Such starting materials include, for example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), gaseous or gasifiable nitrogen such as ammonium azide (NH ₄ N ₃ ), and nitrogen compounds such as nitrides and azides. In addition to the above, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be used, as they can also introduce halogen atoms in addition to nitrogen atoms. I can list them. To form the amorphous layer 103 into which nitrogen atoms are introduced by the sputtering method, a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a Si wafer is used.
Targeting wafers containing a mixture of Si 3 N 4 and Si ₃ N ₄ , these can be sputtered in various gas atmospheres, or single-crystal or polycrystalline Si wafers can be used as a raw material for introducing nitrogen atoms. All you have to do is sputtering in a gas atmosphere. 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 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. In the present invention, in addition to nitrogen atoms, carbon atoms and/or oxygen atoms can be introduced into the amorphous layer 103 in order to obtain the same effect as that obtained by introducing nitrogen atoms. . As a starting material that can be used as a raw material gas for introducing carbon atoms or oxygen atoms, those mentioned above as starting materials for forming a barrier layer are employed as effective starting materials, as well as, for example, oxygen (O ₂ ), ozone ( _O3 ),
Carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO), carbon dioxide (CO ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitric oxide (N ₂ O) , nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), whose constituent atoms are Si, O, and H. , e.g. disiloxane H ₃ SiOSiH ₃ , trisiloxane
Lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like can also be mentioned. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms used in forming the amorphous layer, but other gases may be used. In addition, hydrogen halides such as HF, HCl, HBr, HI, SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements, such as halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ , can also be cited as effective starting materials for forming an amorphous layer. I can do it. 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, Tl, and the like. 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.
It is sufficient to dope in an amount of 10 ^-2 atomic% or less, and in the case of impurities in group A of the periodic table, 5.
Doping may be done in an amount of ×10 ^-3 atomic% or less. The layer thickness of the amorphous layer 103 is appropriately determined as desired so that the photocarriers generated in the amorphous layer 103 are efficiently transported, and is usually 1 to 10%.
The thickness is 100μ, preferably 5 to 50μ. 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 pulled out of the sulfuric acid solution and immersed in a rapidly 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 the apparatus shown in FIG. 2 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations. The aluminum plate 209 treated as described above was firmly fixed to a fixing member 203 at a predetermined position within the glow discharge deposition chamber 201. The substrate 209 is heated by the heater 208 inside the fixing member 203.
Heated with an accuracy of 0.5℃. Temperature was measured directly on the back side of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 210 is fully opened, and the inside of the chamber 201 is evacuated.
The vacuum level was set to ×10 ^-6 Torr. Then heater 2
The input voltage of 08 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 241 and then the outflow valve 2
26, 227, 229 and inflow valves 221, 2
22 and 224 were fully opened, and the mass flow controllers 216, 217, and 219 were also sufficiently degassed and brought into a vacuum state. Auxiliary valve 226, 227, 229, 2
After closing 21 and 224, the valve 231 of SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ /H ₂ ) diluted with H ₂ to 10 vol% and NH ₃ gas (purity 99.999%) cylinder Open the valve 234 of 214 and set the pressure of the outlet pressure gauges 236 and 239 to 1 kg/
cm ² , and the inflow valves 221 and 224 were gradually opened to allow SiH ₄ /H ₂ gas and NH ₃ gas to flow into the mass flow controllers 216 and 219, respectively.
Subsequently, the outflow valves 226, 229 were gradually opened, and then the auxiliary valve 241 was gradually opened.
At this time, mass flow controllers 216 and 219 were adjusted so that the ratio of SiH ₄ /H ₂ gas flow rate to NH ₃ gas flow rate was 50:1. Next, while watching the reading on the Pirani gauge 242, check the auxiliary valve 241.
The auxiliary valve 241 was opened until the pressure inside the chamber 201 became 1×10 ⁻² Torr. After the internal pressure of the chamber 201 became stable, the main valve 210 was gradually closed and the opening was throttled until the reading on the Pirani gauge 241 reached 0.1 Torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 305 (which also serves as an electrode) is closed, the high frequency power source 243 is turned on, and the electrode 2 is turned on.
Between 03.03 and 205, 13.56MHz high frequency power was applied to generate glow discharge in the room 201, and the input power was 3W. After maintaining the above conditions for 10 minutes to form a lower layer region with a thickness of 600 Å on the molybdenum substrate, the high frequency power supply 243 is turned off, the glow discharge is stopped, the outflow valve 229 is closed, and then the H NH ₃ gas (purity 99.999%, hereinafter abbreviated as NH ₃ /H ₂ ) diluted to 0.1 vol% with ₂
At a gas pressure of 1 Kg/cm ² (reading of outlet pressure gauge 237) through valve 222 of No. 2, inlet valve 22
2. Gradually open the outflow valve 227 to flow NH ₃ /H ₂ gas to the mass flow controller 317, and adjust the gas flow ratio of SiH ₄ /H ₂ and NH ₃ /H ₂ by adjusting the mass flow controllers 216 and 217. ,
Adjusted to 10:1. Subsequently, the high frequency power supply 243 was turned on again to restart glow discharge. At that time, the input power was set to 10W. After forming the intermediate layer region for 5 hours under the above conditions, the high frequency power source 343 is turned off to stop the glow discharge and the outflow valve 227 is closed.Then, the outflow valve 229 is opened again and the mass flow controllers 219, 216 are closed. Through adjustment, the flow rate of NH ₃ gas was stabilized to 1/50 of the flow rate of SiH ₄ /H ₂ gas. Continue to turn on the high frequency power supply 243 again.
I turned it on and restarted the glow discharge. The input power at that time was also 3W as before. Continue the glow discharge for 15 minutes to remove the upper layer area.
After forming the film to a thickness of 900 Å, a heating heater 208 is installed.
off state, and the high frequency power supply 243 is also off state,
After waiting for the substrate temperature to reach 100°C, the outflow valves 226, 229 and the inflow valves 221, 22
2, 224 was closed and the main valve 210 was fully opened to bring the inside of the chamber 201 to 10 ^-5 Torr or less, and then the main valve 210 was closed and the inside of the chamber 201 was brought to atmospheric pressure by the leak valve 206 and the substrate was taken out. . In this case, the total thickness of the amorphous layer formed is approximately 15
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 tungsten lamp light source, and a light intensity of 1.1 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. 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. After thoroughly 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] Example 4 An aluminum substrate treated in the same manner as in Example 1 was installed, and then the inside of the deposition chamber 201 was made into a vacuum of 5×10 ^-5 Torr by the same operation as in Example 1. By the same operation as 1, the auxiliary valve 241,
Then the outflow valves 226, 227, 229, 23
0 and inflow valves 221, 222, 224, 22
5 fully open, mass flow controller 216,
217, 219, and 220 were also sufficiently degassed and vacuumed. Auxiliary valve 241, valves 226, 22
7,229,230,219,220,221,
After closing 222, the valve 235 of the argon (99.999% purity) gas cylinder 215 was opened, and the reading of the outlet pressure gauge 240 was adjusted to 1 Kg/cm ² . Thereafter, the inlet valve 225 was opened, and then the outlet valve 230 was gradually opened to allow the argon gas to flow into the chamber 201. Pirani gauge 21
The outflow valve 230 is gradually opened until the indication in step 1 becomes 5×10 ^-4 Torr, and after the flow rate stabilizes in this state, the main valve 210 is gradually closed and the indoor pressure is reduced to 1×10 ^-2 Torr. The aperture was narrowed until . After opening the shutter 205 and confirming that the mass flow controller 220 is stable, turn on the high frequency power supply 243 and place high purity graphite (99.999% purity) on polycrystalline high purity silicon (99.999% purity). (Target 204). Target 204 and fixing member 20
13.56MHz, 100W AC power was input during the 3-hour period. 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 barrier layer with a thickness of 100 Å.
Thereafter, the high frequency power supply 243 was turned off to temporarily stop the discharge. Subsequently, the outflow valve 230,
Close the shutter 205, fully open the main valve 210 to remove the gas from the chamber 201, and release the gas to 5×10 ^-6 Torr.
It was vacuumed up to. Thereafter, the input voltage to the heater 208 was increased, and the input voltage was varied while detecting the substrate temperature until it stabilized at a constant value of 200°C. Thereafter, an amorphous layer consisting of a lower layer region, an intermediate layer region, and an upper layer region was formed using the same operations and conditions as in Example 1. The image forming member thus obtained was subjected to the same conditions and procedures as in Example 1.
When the image is formed on the transfer paper, it is extremely clear.
Image quality was achieved. Example 5 After installing an aluminum substrate treated in the same manner as in Example 1, the NH ₃ /H ₂ gas cylinder 212
Bulb 232, diluted to 50 volppm with _H2
B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /H ₂ ) Open the valve 233 of the cylinder 213, adjust the pressure of the outlet pressure gauges 237, 238 to 1 Kg/cm ² , and open the inflow valve 222. , 223 gradually into the mass flow controllers 217 and 218.
NH ₃ /H ₂ and B ₂ H ₆ /H ₂ gases were introduced. Subsequently, the outflow valves 227 and 228 are gradually opened,
SiH ₄ /H ₂ gas flow rate and NH ₃ /H ₂ gas flow rate ratio are
The mass flow controllers 216, 217, and 218 were adjusted so that the SiH ₄ /H ₂ gas flow rate and the B ₂ H ₆ /H ₂ gas flow rate ratio were 10:0.2. Next, the opening of the auxiliary valve 241 was readjusted while observing the reading on the Pirani gauge 242, and the internal pressure in the chamber 201 was set to 1×10 ⁻² Torr. Furthermore, since the internal pressure of the chamber 201 became stable, the main valve 210 was also readjusted so that the indication on the Pirani gauge 242 was set to 0.1 Torr. After confirming that the gas inflow was stable and the internal pressure was stable, the high-frequency power supply 243 was turned on again, and 13.56MHz high-frequency power was applied to restart the glow discharge in the chamber 201, resulting in an input power of 10W.
After forming the lower layer region for 30 minutes under the above conditions, the high frequency power source 243 was turned off to stop the glow discharge. After that, SiH ₄ /H ₂ gas flow rate and NH ₃ /H ₂
The gas flow rate ratio was 10:0.3, and the discharge time was 4 hours.
The intermediate layer region was formed under exactly the same conditions as the lower layer region formation, except that the time was 30 minutes. Close the outflow valves 227 and 228, then close the outflow valve 22
9, open the mass flow controller 219,2
By adjusting step 16, the NH ₃ gas flow rate can be changed to SiH ₄ /H ₂
The flow rate was stabilized at 1/5 of the gas flow rate. Subsequently, the high frequency power supply 243 was turned on again to restart glow discharge. The input power at that time was 10 W, which is the same as when forming the lower layer and intermediate layer regions. After continuing the glow discharge for 15 minutes to form the upper layer region to a thickness of 900 Å, heating heater 20
8 is turned off, the high frequency power supply 243 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 226, 227, 228 and the inflow valve 2 are turned off.
21, 222, 223, and 224, and fully open the main valve 210, the inside of the chamber 201 is
After reducing the pressure to 10 ^-5 Torr or less, the main valve 210 was closed, and the inside of the chamber 201 was brought to atmospheric pressure by the leak valve 206, and the substrate was taken out. In this case, the total thickness of the amorphous layer formed was about 15μ. The image forming section thus obtained was installed in a charging exposure experimental device, corona charging was performed at 5.5 KV for 0.2 seconds, and a light image was immediately irradiated. 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 chargeable 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 6.0KV using a charging exposure experiment device, and immediately
Immediately after image exposure was performed with a light intensity of 1.0 lux·sec, 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 photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of an amphipolar image forming member. Example 6 In advance, SiH ₄ /H ₂ gas cylinder 211 was heated to 10 vol% with Ar.
A lower barrier layer was formed on the aluminum substrate using the same operations and conditions as in Example 4, except that the SiF ₄ gas (purity 99.999%) diluted in a cylinder was used instead. After that, the high frequency power supply 243 is turned off to stop the glow discharge, and the outflow valve 230 and the shutter 205 are turned off.
was closed, and then the main valve 210 was fully opened to remove gas from the chamber 201, creating a vacuum of 5×10 ⁻⁶ Torr. Thereafter, the input voltage to the heater 208 was increased, and the input voltage was varied while detecting the substrate temperature until it stabilized at a constant value of 200°C. After that, close the shutter 205 and adjust the SiF ₄ gas flow rate using SiF ₄ gas and NH ₃ /H ₂ gas.
The lower layer region was formed under the same operations and conditions as in Example 1, except that the NH ₃ /H ₂ gas flow rate ratio was set to 1:20 and the input power for glow discharge was 100 W. Subsequently, the discharge was temporarily stopped, and the SiF ₄ gas flow rate and NH ₃ /
The intermediate layer region was formed under the same operations and conditions as in Example 1, except that the H ₂ gas flow rate ratio was changed to 1:1.2. Furthermore, after discontinuing the single discharge, an upper layer region was formed under the same conditions as when forming the lower layer region. After forming the upper layer region, the heater 208 is turned on.
OFF state, the outflow valves 226 and 228 were closed, and the shutter 205 was opened again. Substrate temperature is 80℃
At the point when the surface barrier layer was formed, a surface barrier layer was formed using the same operations and conditions as those used for forming the lower barrier layer. As described above, after forming the lower barrier layer, the lower layer region, the intermediate layer region, the upper layer region, and the surface barrier layer on the pre-treated aluminum substrate, the high frequency power source 243 is turned off, and the outflow valve 230
and close the inflow valves 221, 222, 225,
The main valve 210 is fully opened and the inside of the chamber 201 is
After reducing the pressure to 10 ^-5 Torr or less, the main valve 210 was closed, and the inside of the chamber 201 was brought to atmospheric pressure by the leak valve 206, 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 7 In Examples 1 to 6, N ₂ , N ₂ O was used instead of NH ₃
Electrophotographic images in each of the corresponding examples were obtained for photoconductive members prepared under substantially the same conditions and procedures in each example, except that (N ₂ + O ₂ ) was used. When the forming process was applied, transfer images of extremely high quality could be obtained. Further, no deterioration in transferred image quality was observed even after repeated use over a long period of time.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram for explaining the layer structure of a preferred embodiment of the photoconductive member of the present invention, and FIG.
The figure is a schematic explanatory view for explaining 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, 104...
...Lower layer region, 105... Upper layer region, 106...
...Middle layer region, 107...Free surface.

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, and an amorphous layer exhibiting photoconductivity, the amorphous layer contains nitrogen atoms, and the amorphous layer has a distribution amount C ₁ of nitrogen atoms substantially uniform in the layer thickness direction. The lower layer area is distributed as follows, and the distribution amount C ₂
The upper layer region is distributed substantially uniformly in the layer thickness direction, and the nitrogen atoms are sandwiched between these two layer regions, and the nitrogen atoms are distributed substantially uniformly in the layer thickness direction with a distribution amount C ₃ . (However,
An electrophotographic image forming member characterized in that C ₃ <C ₁ , C ₂ ).