JPH0368379B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. In terms of stability, stability over time, and durability, each individual property has been improved, but the reality is that there is still room for further improvement in terms of overall property improvement. be. For example, when applied to an electrophotographic image forming member, there may be insufficient prevention of charge injection from the support side in dark areas, there may be problems with pressure resistance or durability against repeated and continuous use, or For example, there may be image defects commonly called "white spots" on images transferred to transfer paper, which are thought to be caused by localized discharge breakdown phenomena, or defects that may be caused by rubbing when a blade is used for cleaning, for example. A so-called image defect called "white stripe" may occur. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X),
A photoconductive material composed of so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter "a-Si(H,X)" is used as a generic term for these). A photoconductive member designed and produced by specifying the layer structure of the photoconductive member as explained below not only exhibits extremely superior properties in practical use, but also has superior properties compared to conventional photoconductive members. This is based on the discovery that it is superior in all respects when compared, and that it has particularly excellent properties as a photoconductive member for electrophotography. The main object of the present invention is to provide a photoconductive member that is extremely resistant to light fatigue, does not deteriorate even after repeated use, and has excellent durability. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. The photoconductive member of the present invention includes a support for the photoconductive member, a silicon atom as a matrix, hydrogen atoms as constituent atoms, and 1×10 ^-3 atomic% or more, 25 atomic%.
An auxiliary layer made of an amorphous material containing up to nitrogen atoms, and a charge injection made of an amorphous material whose constituent atoms are silicon atoms and which belong to group 3 of the periodic table. It is characterized by having a prevention layer and an amorphous layer made of an amorphous material having silicon atoms as a matrix and containing at least either a hydrogen atom or a halogen atom as a constituent atom and exhibiting photoconductivity. do. The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and exhibits extremely excellent durability, pressure resistance, and use environment characteristics. In particular, when applied as an electrophotographic image forming member, its electrical properties are stable, it has excellent light fatigue resistance and repeated use characteristics, and high-quality images can be stably and repeatedly produced. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic diagram schematically showing the layer structure of a photoconductive member according to a first embodiment of the present invention. A photoconductive member 100 shown in FIG. 1 has a silicon atom (Si) as a base material and a hydrogen atom (H) as a constituent atom on a support 101 for a photoconductive member.
The amorphous layer 104 includes an auxiliary layer 102 made of an amorphous material containing less than 25 atomic% of nitrogen atoms (N), a charge injection prevention layer 103, and an amorphous layer 104 having photoconductivity. It has a free surface 106. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103.
It is made of materials that will be described later so that it has an affinity with both of 3. The charge injection prevention layer 103 mainly has a function of effectively preventing charge from being injected into the amorphous layer 104 from the support 101 side. Amorphous layer 104
has the function of generating photocarriers in the layer 104 upon irradiation with sensitive light and transporting the photocarriers in a predetermined direction. The auxiliary layer in the present invention is made of silicon atoms (Si).
contains nitrogen atoms and hydrogen atoms as constituent atoms, and the nitrogen atom content C(N) is
Amorphous materials (hereinafter referred to as a-
It is written as (Si _a N _1-a ) _b H _1-b . However, 0.6<a, 0.65≦
b). The auxiliary layer composed of a-(Si _a N _1-a ) _b H _1-b can be formed by glow discharge method, sputtering method, ion implantation method, ion plating method, electron beam method, etc. done by. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Although it is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member with
The glow discharge method or the sputtering method is preferably employed because of the advantage that it is easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the auxiliary layer to be formed. Furthermore, in the present invention, the intermediate layer 102 may be formed by using a glow discharge method and a sputtering method in the same apparatus. To form the auxiliary layer by glow discharge method,
a-(Si _a N _1-a ) _b H _{1-b The raw material gas for forming b H 1-b} is mixed at a mixing ratio of diluent gas and a predetermined material as needed, and the mixture is poured into a vacuum deposition chamber equipped with a support. The gas is introduced into a deposition chamber, and the introduced gas is turned into gas plasma by causing a glow discharge, and a-(Si _a
N _1-a ) _b H _1-b may be deposited. In the present invention, the raw material gas for forming a-(Si _a N _1-a ) _b H _1-b is at least one of Si, N, and H.
Most gaseous substances or gasified substances having two constituent atoms can be used. When using a raw material gas containing Si as one of Si, N, and H, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing N as a constituent atom, and a raw material gas containing H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing N and H as constituent atoms may be mixed at a desired mixing ratio. Can be used by mixing. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, the starting materials that can be effectively used as raw material gas for forming the auxiliary layer are:
SiH ₄ , Si ₂ H ₆ , Si ₃ H ₃ whose constituent atoms are Si and H,
Silicon hydrides such as silanes such as Si ₄ H ₁₀ ,
Examples of nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ Mention may be made of gaseous or gasifiable nitrogen such as N ₃ ), nitrogen compounds such as nitrides and azides. In addition to these starting materials for forming the auxiliary layer, H ₂ is of course also effective as a raw material gas for introducing H. To form the auxiliary layer by the sputtering method, a monocrystalline or polycrystalline Si wafer or
This can be carried out by sputtering a Si ₃ N ₄ wafer or a wafer containing a mixture of Si and Si ₃ N ₄ in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing N and H, e.g.
H ₂ and N ₂ or NH ₃ are diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer. Just do it. Alternatively, by using Si and Si ₃ N ₄ as separate targets or by using a single target formed by mixing Si and Si ₃ N ₄ , a gas containing at least H atoms can be produced. This is done by sputtering in an atmosphere. As a raw material gas for introducing N or H, the starting material gas for forming the auxiliary layer shown in the glow discharge example described above can also be used as an effective gas for sputtering. In the present invention, the diluent gas used when forming the auxiliary layer by the glow discharge method or sputtering method includes so-called rare gases such as He, Ne,
Ar and the like can be cited as suitable examples. a-(Si _x N _1-x ) _y H _1-y constituting the auxiliary layer of the present invention
is required for the auxiliary layer because the function of the auxiliary layer is to strengthen the adhesion between the support and the charge injection prevention layer, and also to make the electrical contact between them uniform. The manufacturing conditions are strictly selected and carefully formed so that the desired characteristics are provided. a-(Si _a
An important factor in the preparation conditions for N _1-a ) _b H _1-b is the temperature of the support during preparation. That is, when forming an auxiliary layer consisting of a-(Si _a N _1-a ) _b H _1-b on the surface of a support, the temperature of the support during layer formation influences the structure and properties of the formed layer. In the present invention, the support during layer formation is an important factor to ensure that a-(Si _a N _1-a ) _b H _1-b having the desired properties can be created as desired. Body temperature is strictly controlled. In order to effectively achieve the purpose of the present invention, the optimum range of the support temperature when forming the auxiliary layer is selected as appropriate in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is carried out. However, in normal cases, the temperature is 50℃~
A temperature of 350°C, preferably 100°C to 250°C is desirable. The auxiliary layer can be formed continuously in the same system, from the auxiliary layer to the charge injection prevention layer, the amorphous layer, and even other layers formed on the amorphous layer if necessary. However, the glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of the layer thickness are relatively easy compared to other methods. , When forming an auxiliary layer using these layer forming methods, the discharge power and gas pressure during layer formation are created in the same way as the support temperature described above. a-(Si _a N _1-a ) _b H It is cited as an important factor that influences the characteristics of _1-b . The discharge power condition for effectively forming a-(Si _a N _1-a ) _b H _1-b with good productivity, which has the characteristics to achieve the purpose of the present invention, is usually 1. ~
300W, preferably 2-100W. The gas pressure in the deposition chamber is usually about 0.01 to 5 Torr, preferably about 0.1 to 0.5 Torr when layer formation is performed by glow discharge.
When forming a layer by sputtering, the temperature is usually 10 ^-3 to 5 x 10 ^-2 Torr, preferably 8 x
It is desirable that it be about 10 ^-3 to 3×10 ^-2 Torr. The amounts of nitrogen atoms (N) and hydrogen atoms (H) contained in the auxiliary layer in the photoconductive member of the present invention are determined to provide the desired characteristics to achieve the object of the present invention, as well as the conditions for producing the auxiliary layer. This is an important factor in the formation of an auxiliary layer. The amount C(N) of nitrogen atoms (N) contained in the auxiliary layer in the present invention is usually within the above-mentioned value range, but if expressed in atomic%, it is preferably as follows:
1×10 ^-3 ≦C(N)<25, more preferably 1≦C
(N)<25, optimally 10≦C(N)<25. The amount of hydrogen atoms (H) is preferably 2 to 35 atomic %, most preferably 5 to 30 atomic %. When expressed as a and b in a-(Si _a N _1-a ) _b H _1-b , the value of a is preferably 0.6<a≦
0.99999, more preferably 0.6<a≦0.99, optimally 0.6<a≦0.9, and the value of b is preferably
It is desirable that 0.65≦b≦0.98, more preferably 0.7≦b≦0.95. The numerical range of the layer thickness of the auxiliary layer in the present invention is appropriately determined as desired so as to effectively achieve the object of the present invention. In order to effectively achieve the purpose of the present invention, the thickness of the auxiliary layer is usually 30 Å to 2 μ, preferably
It is desirable that the thickness be 40 Å to 1.5 μ, most preferably 50 Å to 1.5 μ. The charge injection prevention layer that achieves the photoconductive member of the present invention has a silicon atom (Si) as its base material, and preferably contains atoms belonging to Group 3 of the periodic table (Group atoms) and hydrogen atoms (H) or halogen atoms. (X), or both of these as constituent atoms (hereinafter referred to as "a-Si(,H,X)"), and the layer thickness t and the number of group atoms in the layer are Content C()
is determined as appropriate in order to effectively achieve the object of the present invention. The layer thickness t of the charge injection prevention layer in the present invention is preferably 0.3 to 5μ, more preferably 0.5 to 2μ.
It is desirable that the content of group atoms C() is preferably 1×10 ² to 1×
¹⁰⁵ atomic ppm, more preferably 5× ¹⁰² to 1
It is desirable to set it to ×10 ⁵ atomic ppm. In the present invention, the atoms belonging to group of the periodic table contained in the charge injection prevention layer are B (boron), Al (aluminum), Ga (gallium), In (indium), Tl ( thallium) etc.
Particularly preferably used are B and Ga. In the present invention, specific examples of the halogen atom (X) contained in the charge injection prevention layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something. To form the charge injection prevention layer composed of a-Si(,H,X), as in the case of forming the auxiliary layer,
For example, a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is employed. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having silicon atoms, and group atoms, hydrogen atoms (H) and halogen atoms (X) as necessary, are created in the charge injection prevention layer. The glow discharge method or the sputtering method is preferably employed because of the advantages such as ease of introduction. Furthermore, in the present invention, the charge injection prevention layer may be formed by using both the glow discharge method and the sputtering method in the same apparatus system. For example, a-Si (, H,
To form the charge injection prevention layer composed of X), basically silicon atoms (Si) can be supplied.
Along with the raw material gas for Si supply, the raw material gas for introducing group atoms that can supply group atoms, and the raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. , is introduced into a deposition chamber whose interior can be made to have a reduced pressure, a glow discharge is generated in the deposition chamber, and a-
A layer consisting of Si (, H, X) may be formed.
In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce group atoms. The source gas for sputtering may be introduced into the deposition chamber for sputtering together with a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as required. In the present invention, the following starting materials are effective as raw material gases used to form the charge injection prevention layer. First, silicon hydrides (silanes) in a gaseous state or that can be gasified, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₃ , and Si ₄ H ₁₀ , are effective as starting materials that serve as raw material gas for supplying Si. It is said to be used for many reasons, especially in terms of ease of layer creation work and good Si supply efficiency.
Preferred examples include SiH ₄ and Si ₂ H ₆ . If these starting materials are used, the auxiliary layer formed by appropriately selecting the layer forming conditions will contain
H may also be introduced together with Si. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Preferred examples include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ . Furthermore, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be cited as starting materials for supplying Si for forming an effective charge injection prevention layer. Even when these silicon compounds containing halogen atoms (X) are used, the charge injection prevention layer formed by appropriately selecting the layer formation conditions as described above can be used.
X can be introduced together with Si. The silicon halide compound containing a hydrogen atom in the above-mentioned starting material is an extremely effective hydrogen atom (H ) is also introduced, so it is used as a suitable starting material for introducing a halogen atom (X) in the present invention. In addition to the above-mentioned materials, examples of effective starting materials as raw material gases for introducing halogen atoms (X) used in forming the auxiliary layer in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine. , BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ ,
Interhalogen compounds such as ICl, IBr, HF, HCl,
Examples include hydrogen halides such as HBr and HI. In order to structurally introduce group atoms into the charge injection prevention layer, during layer formation, the starting material for introducing the group atoms is placed in a gaseous state in a deposition chamber to form the charge injection prevention layer. It would be better to introduce it together.
As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing a group group atom include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such _{as B6H12} , _{B6H14 , BF3} , _BCl3 ,
Examples include boron halides such as BBr ₃ and the like. In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃
etc. can also be mentioned. In the present invention, the group atoms contained in the charge injection prevention layer to provide charge injection prevention properties are
It is preferable that the charge injection prevention layer be distributed substantially uniformly in a plane substantially parallel to the layer thickness direction (a plane parallel to the surface of the support) and in the layer thickness direction. In addition, when forming a charge injection prevention layer by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, The raw material gas for introducing group atoms may be introduced into the vacuum deposition chamber where sputtering is performed together with the raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. In the present invention, the content of group atoms introduced into the charge injection prevention layer is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, and the support. It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. In the present invention, the halogen atoms (X) that may be contained in the charge injection prevention layer if necessary include the same ones as described in the description of the auxiliary layer. In the present invention, the diluent gas used when forming the charge injection prevention layer by a glow discharge method or a sputtering method is a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H, X),
Basically, in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited so that the internal pressure can be reduced. A glow discharge is generated in the deposition chamber to form a layer made of a-Si(H, Just let it happen. In addition, when forming by sputtering, Si is formed in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases.
When sputtering a target composed of the following, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, as the halogen atom (X) contained in the amorphous layer if necessary, the same halogen atoms (X) as mentioned in the case of the auxiliary layer can be mentioned. In the present invention, the raw material gas for supplying Si used to form the amorphous layer includes SiH ₄ , which was mentioned when explaining the auxiliary layer and the charge injection prevention layer.
Gaseous or gasifiable silicon hydrides (silanes) such as Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ can be used effectively, especially because they are easy to handle in layer-forming operations. SiH ₄ , Si ₂ H ₆ in terms of good Si supply efficiency, etc.
are listed as preferred. As in the case of the auxiliary layer, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer in the present invention, such as halogen gas, halides, and halogen atoms. Preferred examples include gaseous or gasifiable halogen compounds such as compounds and halogen-substituted silane derivatives. Furthermore, silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified and are composed of silicon atoms (Si) and halogen atoms (X), can also be cited as effective in the present invention. In the present invention, hydrogen atoms contained in the charge injection prevention layer and the amorphous layer of the photoconductive member to be formed
Amount of (H) or amount of halogen atom (X) or hydrogen atom
The sum of the amounts of (H) and halogen atoms (X) (H+X) is usually 1 to 40 atomic%, preferably 5 to 40 atomic%.
It is desirable to set it to 30 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain the atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, a so-called rare gas, such as He,
Preferable examples include Ne, Ar, and the like. In the present invention, the thickness of the amorphous layer is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 100 μm.
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity is imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 differs from the photoconductive member 100 shown in FIG.
An upper auxiliary layer 204 is provided between the charge injection prevention layer 203 and the amorphous layer 205 exhibiting photoconductivity. That is, the photoconductive member 200 includes a support 201 and a lower auxiliary layer 2 laminated in this order on the support 201.
02, charge injection prevention layer 203, upper auxiliary layer 204
and an amorphous layer 205, the amorphous layer 205
has a free surface 206. Upper auxiliary layer 204
This strengthens the adhesion between the charge injection prevention layer 203 and the amorphous layer 205 and makes the electrical contact uniform at the contact interface between both layers. By providing the charge injection prevention layer 203, the layer quality of the charge injection prevention layer 203 is made strong. The lower auxiliary layer 202 and the upper auxiliary layer 204 constituting the photoconductive member 200 shown in FIG.
Auxiliary layer 1 constituting the photoconductive member 100 shown in the figure
Using the same amorphous material as in the case of 02, it is formed by the same layer forming procedure and conditions so as to provide similar properties. The charge injection prevention layer 203 and the amorphous layer 205 have the same characteristics and functions as the charge injection prevention layer 103 and the amorphous layer 104 shown in FIG. 1, respectively, and are formed in the same manner as in the case of FIG. Formed by procedures and conditions. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 3 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. Gas cylinders 302, 303, 304, and 305 in the figure are sealed with raw material gases for forming the respective layers of the present invention. For example, 302 is SiH ₄ gas diluted with He. (Purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 3
03 is B ₂ H ₆ gas diluted with He (purity 99.999
%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 304 is
_NH3 gas (99.9% purity) (99.99% purity) cylinder,
305 is SiF ₄ gas diluted with He (purity 99.999
%, hereinafter abbreviated as SiF ₄ /He. ) It is a cylinder. The valves 322 to 32 of the gas cylinders 302 to 305 are used to flow these gases into the reactant 301.
5. Confirm that the leak valve 335 is closed, and confirm that the inflow valves 312 to 315, the outflow valves 317 to 320, and the auxiliary valve 332 are open, and first open the main valve 334 to drain the reaction chamber. 301, exhaust the inside of the gas pipe. Next, when the reading on the vacuum gauge 336 reaches approximately 5×10 ^-6 torr, the auxiliary valve 332 and the outflow valves 317 to 3
Close 20. To give an example of forming a layer on the base cylinder 337, SiH ₄ /
He gas and B ₂ H ₆ /He gas from gas cylinder 303, respectively, by opening valves 322 and 323 and adjusting the pressure of outlet pressure gauges 327 and 328 to 1 Kg/cm ² ,
The inflow valves 312 and 313 are gradually opened to allow the flow into the mass flow controllers 307 and 308. Subsequently, the outflow valves 317 and 318 and the reinforcing valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 301. At this time, the outflow valves 317 and 318 are adjusted so that the ratio of the SiH ₄ /He gas flow rate and the B ₂ H ₆ /He gas flow rate becomes a desired value, and
Check the vacuum gauge 3 so that the pressure inside the reaction chamber reaches the desired value.
Adjust the opening of the main valve 334 while checking the reading of 36. After confirming that the temperature of the base cylinder 337 is set within the range of 50 to 400°C by the heating heater 338, the power source 340 is set to the desired power to generate glow discharge in the reaction chamber 301. to form the desired layer on the base cylinder. When containing halogen atoms in the layer to be formed, for example,
SiF ₄ /He is further added and sent into the reaction chamber. It goes without saying that all outflow valves for gases other than those required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 301 and the outflow valves 317 to 317 are closed. 320
In order to avoid residual water remaining in the piping leading from to the reaction chamber 301, the outflow valves 317 to 320 are closed, the auxiliary valve 332 is opened, and the main valve 334 is closed.
If necessary, fully open the system and evacuate the system to high vacuum. Further, during layer formation, the base cylinder 337 is operated by a motor 339 in order to ensure uniform layer formation.
rotates at a constant speed. Examples will be described below. Example 1 A layer was formed on a drum-shaped aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG.

[Table] The electrophotographic image forming member thus obtained was placed in a copying machine, corona charged at 5 kV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux·sec. The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper, and the transfer development was very good. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process. Even after repeating this process more than 100,000 times, no layer peeling occurred and the image remained good. Example 2 An electrophotographic imaging member was produced in the same manner as in Example 1 except that the content of nitrogen atoms relative to silicon atoms in the auxiliary layer was changed. The results of evaluation in the same manner as in Example 1 are shown below.

[Table] Example 3 An electrophotographic image forming member was produced in exactly the same manner as in Example 1 except that the thickness of the auxiliary layer was changed. The results of evaluation in the same manner as in Example 1 are shown below.

[Table] Example 4 An electrophotographic image forming member was produced in exactly the same manner as in Example 1, except that the layer thickness and boron content of the charge injection prevention layer were changed as follows. All results were good.

[Table] Example 5 A layer was formed on a drum-shaped aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG.

[Table] The obtained drum was of high quality and had no layer peeling or image defects. Example 5 A layer was formed on a drum-shaped aluminum substrate using the manufacturing apparatus shown in FIG. 3 under the following conditions.

[Table] The electrophotographic image forming member thus obtained was evaluated in the same manner as in Example 1, and very good results were obtained.

[Brief explanation of drawings]

FIGS. 1 and 2 are schematic layer configuration diagrams schematically showing the layer structure of preferred embodiments of the photoconductive member of the present invention, and FIG. 3 is a diagram showing the method for manufacturing the photoconductive member of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of a device for 100,200...Photoconductive member, 101,20
1...Support, 102,202,204...Auxiliary layer, 104,205...Amorphous layer, 105,10
6...Free surface.

Claims (1)

[Claims] 1 A support for a photoconductive member, a silicon atom as a matrix, a hydrogen atom as a constituent atom, and 1×
an auxiliary layer made of an amorphous material containing at least 10 ^-3 atomic% and up to 25 atomic% nitrogen atoms;
A charge injection prevention layer made of an amorphous material that has silicon atoms as its base and contains atoms belonging to Group Group of the Periodic Table as its constituent atoms, and a charge injection prevention layer that has silicon atoms as its base and contains either hydrogen atoms or halogen atoms as its constituent atoms. 1. A photoconductive member comprising an amorphous material containing at least one of the above and an amorphous layer exhibiting photoconductivity.