JPS6345582B2 - - 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. Photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc. are highly sensitive and have a high signal-to-noise ratio [photocurrent (p)/ It has a high dark current (d)], has the spectral characteristics of the electromagnetic waves to be irradiated, has good photoresponsiveness, has a desired dark resistance value, and is non-polluting to the human body during use. The imaging device is required to have characteristics such as 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 pollution-free nature during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention.
No. 2855718 describes its application as an electrophotographic image forming member, and JP-A-55-39404 describes its application to a photoelectric conversion/reading device. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as weather resistance and moisture resistance. There are points that can be further improved in terms of usage environment characteristics such as performance, and practical solid-state imaging devices, reading devices, electrophotographic image forming members, etc. need to be improved in terms of productivity and mass production. The reality is that it cannot be used effectively by taking this into consideration. For example, when applied to electrophotographic image forming members or solid-state imaging devices, it is often observed that residual potential remains during use, and when such photoconductive members are used repeatedly for a long time, There are many disadvantages such as accumulation of fatigue due to repeated use and so-called ghost phenomenon, which causes afterimages. Furthermore, according to many experiments conducted by the present inventors, for example, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member can be replaced with conventional Se, CdS, ZnO, or OPC such as PVCz or TNF. An electrophotographic image having a single-layer photoconductive layer made of a-Si, which has many advantages compared to (organic photoconductive members), but also has characteristics suitable for use in conventional solar cells. Even if the photoconductive layer of the forming member is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, making it difficult to apply ordinary electrophotographic methods, and in a humid atmosphere. It has been found that the above-mentioned tendency is so remarkable that in some cases, there are cases in which it is not possible to retain any charge at all until the development time, and that there are problems that can be solved. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to obtain desired electrical, optical, and photoconductive properties 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 material used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms An amorphous material containing halogen atoms as a matrix, so-called halogen-containing amorphous silicon (hereinafter referred to as a-
A photoconductive member designed and produced with a layer structure in which a specific intermediate layer is interposed between a photoconductive layer consisting of Si: Not only can it be used, but it is superior in most respects to conventional photoconductive members, and has particularly excellent properties as a photoconductive member for electrophotography. It is based on the discovery of The present invention has stable electrical, optical, and photoconductive properties at all times, and is suitable for all environments with almost no restrictions on usage environments.It has excellent light fatigue resistance and does not deteriorate even after repeated use. The main objective is to provide a photoconductive member in which no or almost no residual potential is observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity, has a spectral sensitivity range that covers substantially the entire visible light range, and has fast photoresponsiveness. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties with sufficient performance and with almost no deterioration of the properties observed even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. The photoconductive member of the present invention is provided between a support, a photoconductive layer made of an amorphous material having silicon atoms as a matrix and containing halogen atoms, and is provided between the support and the photoconductive layer from the support side to the photoconductive layer. an intermediate layer having a function of blocking the inflow of carriers and allowing carriers generated in the photoconductive layer and moving toward the support by electromagnetic wave irradiation to pass from the photoconductive layer side to the support side; In the conductive member, the intermediate layer is (Si _x N _1-x ) _Y H _1-Y (where 0.43≦x≦
0.60, 0.65≦y≦0.98) and is characterized by having a layer thickness of 30 to 1000 Å. A photoconductive member designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent electrical, optical, photoconductive properties, and use environment characteristics. . In particular, when applied as an image forming member for electrophotography or an imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has good electrical properties even in a humid atmosphere. It is stable, has high sensitivity, has a high signal-to-noise ratio, and has excellent resistance to light fatigue and repeated use. Furthermore, in the case of electrophotographic image forming members, it has high density and clear halftones. , and can obtain high-quality visible images with high resolution. Moreover, when applied to an electrophotographic image forming member,
a-Si:X with high dark resistance has low photosensitivity, and conversely, a-Si:X with high photosensitivity has a low dark resistance of around 10 ⁸ Ωcm at most. While the conductive layer could not be used as an image forming member for electrophotography, in the case of the present invention, even an a:SiX layer with a relatively low resistance (5×10 ⁹ Ωcm or more) can be used for electrophotography. a-Si, which has relatively low resistance but high sensitivity, can form a photoconductive layer for
X can also be used sufficiently, and the restrictions from the characteristics of a-Si:X can be alleviated. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain a basic configuration example of a photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has an intermediate layer 102,
It has a layer structure consisting of a photoconductive layer 103 provided in direct contact with the intermediate layer 102,
This is the most basic example of the present invention. The support 101 may be conductive, electrical, or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo,
Examples include metals such as Au, Ir, 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 conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, its surface may be NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
If it is conductive treated by providing a thin film of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr,
The surface is subjected to conductive treatment by treating with a metal such as Mo, Ir, Nb, Ta, V, Ti, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating with the metal. The shape of the support is
It can be of any shape such as cylindrical, belt-like, plate-like, etc.
The shape is determined depending on the need, but for example, if the photoconductive member 100 of FIG. It is desirable to do so. 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. Within this range, it is made as thin as possible. However, in such a case, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The intermediate layer 102 is made of a non-photoconductive amorphous material [abbreviated as a-(SixN ₁ -x)y:H ₁ -y] that has silicon atoms and nitrogen atoms as its base and contains hydrogen atoms. However, 0<x<1, 0<y<1], which effectively prevents carriers from flowing into the photoconductive layer 103 from the support 101 side and prevents carriers from flowing into the photoconductive layer 103 by electromagnetic wave irradiation. occurs in the support 1
This has a function of easily allowing the photo carrier moving toward the photoconductive layer 103 to pass from the photoconductive layer 103 side to the support 101 side. The intermediate layer 102 composed of a-(SixN ₁ -x)y:H ₁ -y can be formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, etc. It is accomplished by doing so. These manufacturing methods are based on manufacturing conditions,
The method is selected and adopted as appropriate depending on factors such as the level of equipment capital investment, production scale, and the desired characteristics of the photoconductive member to be manufactured. The glow discharge method or the sputtering method is preferably adopted because it is relatively easy to control the conditions, and it is easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the intermediate layer to be created. be done. 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 intermediate layer 102 by the glow discharge method, a raw material gas for forming a-(SixN ₁ -x)y:H ₁ -y is mixed with dilution gas at a predetermined mixing ratio as necessary. Then, the introduced gas 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, and a-(SixN ₁ -x )y:
It is sufficient to deposit H ₁ -y. In the present invention, a-(SixN ₁ -x)y:H ₁ -
As the raw material gas for forming y, most of gaseous substances containing at least one of Si, N, and H as a constituent atom or gasified substances that can be gasified 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, starting materials that can be effectively used as raw material gas for forming the intermediate layer 102 include SiH ₄ , Si ₂ H 6 , and SiH ₄ whose constituent atoms are Si and H.
Silicon hydrides such as silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ , nitrogen (N ₂ ), ammonia (NH ₃ ) whose constituent atoms are N or N and H, etc. , hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), and gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides. . In addition to these starting materials for forming the intermediate layer, H ₂ is of course also used as an effective raw material gas for introducing H. To form the intermediate layer 102 by the sputtering method, target a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer containing a mixture of Si and Si ₃ N ₄ ,
These may be performed by sputtering 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 diluting 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 intermediate 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 intermediate layer 102 by a glow discharge method or a sputtering method is a so-called rare gas, such as He,
Preferable examples include Ne, Ar, and the like. The intermediate layer 102 in the present invention is carefully formed to provide the desired properties. In other words, materials whose constituent atoms are Si, N, and H can have structural forms ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. In the present invention, non-photoconductive a-(SixN ₁ -x)y:H The creation conditions are strictly selected so that _1- y is formed. a-(SixN ₁
-x) y: H ₁ -y is the function of the intermediate layer 102 to prevent the injection of carriers from the support 101 side into the photoconductive layer 103 and to prevent the photocarriers generated in the photoconductive layer 103 from moving. The material is formed to exhibit electrically insulating behavior because it allows the material to easily pass through to the support body 101 side. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, it has a mobility value with respect to the carrier that passes through the intermediate layer 102 smoothly.
-(SixN ₁ -x)y: H ₁ -y is created. a-(SixN ₁ -x) with the above characteristics
An important factor in the production conditions for producing y:H ₁ -y is the temperature of the support during production. That is, a-(SixN ₁ -
x) y: When forming the intermediate layer 102 consisting of H ₁ -y, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, is a-
The temperature of the support during layer formation is strictly controlled so that (SixN ₁ -x)y:H ₁ -y can be formed as desired. In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the intermediate layer 102 is appropriately selected in an optimal range in accordance with the method of forming the intermediate layer 102. is executed, but
Normally 100℃~300℃ Preferably 150℃~250℃
It is desirable that the The intermediate layer 102 is formed by forming the intermediate layer 1 in the same system.
Fine control of the composition ratio of atoms constituting each layer and layers can be formed continuously from 02 to the photoconductive layer 103, and further to the third layer formed on the photoconductive layer 103 if necessary. It is advantageous to employ a glow discharge method or a sputtering method because it is relatively easy to control the thickness compared to other methods, but when forming the intermediate layer 102 using these layer forming methods. , the discharge power and gas pressure during layer formation are created as well as the _support temperature described above.
x) y: H ₁ --This is an important factor that influences the characteristics of y. The discharge power conditions for effectively forming a-(SixN ₁ -x)y:H ₁ -y with good productivity, which has the characteristics to achieve the object of the present invention, are usually 1 to 1. 300W, preferably 2-100W.
The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.1 to 5 Torr when layer formation is performed by glow discharge.
When forming a layer by sputtering at about 0.5 Torr, it is usually 10 ^-3 to 5×
10 ^-2 Torr, preferably about 8 x 10 ^-3 to 3 x 10 ^-2 Torr. The amounts of nitrogen atoms and hydrogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are as follows:
Similar to the manufacturing conditions of No. 02, this is an important factor in forming an intermediate layer that provides the desired properties to achieve the object of the present invention. The amount of nitrogen atoms contained in the intermediate layer 102 in the present invention is usually 25 to 55 atomic %, preferably 35 atomic %.
It is desirable that the content be ~55 atomic%.
The content of hydrogen atoms is usually 2~
It is desirable that the hydrogen content be 35 atomic%, preferably 5 to 30 atomic%, and photoconductive members formed when the hydrogen content is in this range are excellent in practice and can be fully applied. It is. That is, if expressed as a-(SixN ₁ -x)y:H ₁ -y, x is usually 0.43 to 0.60, preferably
0.43~0.50, y usually 0.98~0.65, preferably 0.95~
It is 0.70. The numerical range of the layer thickness of the intermediate layer 102 in the present invention is one of the important factors for effectively achieving the object of the present invention. If the layer thickness of the intermediate layer 102 is too thin, it will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the support 101 side, and if it is too thick, , the probability that the photocarriers generated in the photoconductive layer 103 will pass to the side of the support 101 becomes extremely small, and therefore the object of the invention cannot be effectively achieved in either case. Intermediate layer 1 for effectively achieving the object of the present invention
The layer thickness of 02 is usually 30 to 1000 Å, preferably 50 to 600 Å. In the present invention, in order to effectively achieve the purpose, a photoconductive layer 10 laminated on an intermediate layer 102 is used.
3 is a-Si:X having the semiconductor properties shown below.
Consists of. p-type a-Si:X... Contains only acceptor. Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). p ^- type a-Si: Lightly doped with a so-called p-type impurity that has a low acceptor concentration (Na) in the X... type. n-type a-Si:X...Contains only a donor. Or one that contains both donor and acceptor and has a high concentration of donor (Nd). The donor concentration (Nd) is low in the n ^- type a-Si:X type. Lightly doped with so-called n-type impurities. i-type a-Si:X...NaNdO or,
NaNd stuff. In the present invention, by providing the intermediate layer 102, a-Si:X that constitutes the photoconductive layer 103 as described above can be used with a relatively low resistance compared to the conventional one. However, in order to obtain better results, the dark resistance of the photoconductive layer 103 to be formed is preferably 5×10 ⁹ Ωcm or more, most preferably 10 ¹⁰ Ω.
It is preferable that the photoconductive layer 103 is formed to have a thickness of cm or more. In particular, this numerical condition for the dark resistance value is required when the manufactured photoconductive member is used as an image forming member for electrophotography, a highly sensitive reading device or solid-state imaging device used in a low-light region, or a photoelectric conversion device. This is an important element when doing so. The layer thickness of the photoconductive layer of the photoconductive layer member in the present invention is appropriately determined according to the purpose of the application, such as a reading device, a solid-state imaging device, or an electrophotographic image forming member. . In the present invention, the layer thickness of the photoconductive layer is set such that the thickness of the photoconductive layer and the intermediate layer are such that the functions of the photoconductive layer and the function of the intermediate layer are each effectively utilized and the object of the present invention is effectively achieved. The thickness can be determined as desired, and in normal cases, the layer thickness is preferably several hundred to several thousand times the thickness of the intermediate layer. A specific value is usually 1 to 100μ, preferably 2 to 50μ. In the present invention, specific examples of the halogen atom (X) contained in the photoconductive layer include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. Here, "X is contained in the layer"
This means that "X is bonded to Si", "X
It means either a state in which _X2 is ionized and incorporated into the layer, or a state in which X2 is incorporated into the layer, or a combination thereof. In the present invention, the layer composed of a-Si:X is formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. For example, to form an a-Si:X layer by a glow discharge method, a halogen-introducing raw material gas is introduced into a deposition chamber whose interior can be reduced in pressure, along with a Si-generating raw material gas that can generate Si. A glow discharge is generated in the deposition chamber, and a-Si:
What is necessary is to form a layer consisting of. In addition, when forming by 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 halogen may be introduced into the deposition chamber for sputtering. As the Si generation raw material gas used in the present invention, silicon hydride (silanes) in a gaseous state or which can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effectively used. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of handling during layer formation work, good Si generation efficiency, etc. Many halogen compounds are effective as the raw material gas for halogen introduction used in the present invention, such as halogen gas, halides,
Preferred examples include gaseous or gasifiable halogen compounds such as interhalogen compounds. Further, in the present invention, silicon compounds containing halogen, which are in a gaseous state or can be gasified, and which can generate Si and halogen at the same time, can also be mentioned as effective compounds. 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 the silicon compound containing halogen include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ . When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen, silicon hydride gas is used as a raw material gas that can generate Si. At least, a layer made of a-Si:X can be formed on an intermediate layer provided on a predetermined support. When manufacturing the photoconductive member of the present invention according to the glow discharge method, basically silicon halide gas, which is a raw material gas for Si generation, and diluting gas such as Ar, H ₂ , He, etc. are mixed in a predetermined amount. By introducing these gases into a deposition chamber in which a photoconductive layer of a-Si:X is to be formed with the mixing ratio and gas flow rate being adjusted, a glow discharge is generated to form a plasma atmosphere of these gases. a in contact with an intermediate layer formed on a predetermined support;
Although a photoconductive layer consisting of -Si:X can be formed, a layer may also be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen with these gases. Moreover, each gas may be used not only as a single species but also as a mixture of a plurality of them at a predetermined mixing ratio. To form a photoconductive layer made of a-Si:X by a reactive sputtering method or an ion plating method, a target made of Si is used in the case of a sputtering method, and it is exposed to a predetermined gas plasma. Sputtering is performed in an atmosphere, and in the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is used by a resistance heating method, an electron beam method (EB method), etc. This can be carried out by heating and evaporating the flying evaporated material by passing it through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or the above-mentioned halogen-containing silicon compound is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for halogen introduction, but in addition, HF, HCl, HBr, HI
Hydrogen halides such as SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
Halogenated silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and the like, gaseous or gasifiable halides containing hydrogen as one of their constituents can also be cited as effective. These hydrogen-containing halides are suitable for halogen introduction in the present invention because H, which is extremely effective for controlling electrical or photoelectric properties, is introduced at the same time as halogen into the layer during layer formation. used as raw material gas for In order to structurally introduce hydrogen into the photoconductive layer consisting of a-Si:X, in addition to the above, H ₂ or SiH ₄ ,
This can also be done by causing a discharge by causing silicon hydride gas such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ to coexist with silicon or a silicon compound for producing a-Si in a deposition chamber. I can do it. For example, in the case of the reactive sputtering method, Si
Using a target, raw material gas for halogen introduction and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a gas plasma atmosphere, and the Si target is sputtered. As a result, a layer consisting of a-Si:X into which H is introduced is formed on the surface of the support having predetermined properties. Furthermore, B ₂ H ₆ , which also serves as impurity doping,
It is also possible to introduce a gas such as PH ₃ . In the present invention, the amount of X or the amount of (H+X) contained in the photoconductive layer of the photoconductive member to be formed is usually 1 to 40 atomic%, preferably 5 to 40 atomic%.
It is desirable to set it to 30 atomic%. The amount of H contained in the layer can be controlled, for example, by controlling the temperature of the deposition support, the amount of starting material used to incorporate H into the deposition system, the discharge force, etc. Just do it. In order to make the photoconductive layer n-type or p-type, the amount of n-type impurity, p-type impurity, or both impurities is added to the formed layer during layer formation by glow discharge method, reactive sputtering method, etc. This is achieved by controlling and doping. As impurities to be doped into the photoconductive layer, in order to make the photoconductive layer p-type, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferred. and when making it n-type,
Elements of group A of the periodic table, such as N, P, As,
Preferred examples include Sb and Bi. Since the amount of these impurities contained in the layer is on the order of ppm, it is not necessary to pay as much attention to their pollution properties as the main materials constituting the photoconductive layer, but use materials that are as non-polluting as possible. is preferable. From this point of view, B, Ga, P, Sb, etc. are optimal, taking into consideration the electrical and optical characteristics of the layer to be formed. In addition, it is also possible to control the material to be n-type by, for example, interstitial doping with Li or the like by thermal diffusion or implantation. The amount of impurity doped into the photoconductive layer is
It is determined as appropriate depending on the desired electrical and optical properties, but in the case of impurities in Group A of the periodic law,
Usually 10 ^-6 ~ 10 ^-3 atomic%, preferably 10 ^-5 ~
10 ^-4 atomic%, usually 10 ^-8 to 10 ^-3 atomic% in the case of group A of the periodic table, preferably 10 ^-8 to
It is desirable to set it to 10 ^-4 atomic%. FIG. 2 shows a schematic configuration diagram for explaining the configuration of another embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 is similar to the photoconductive member 100 shown in FIG. 1 except that an upper layer 205 having the same function as the intermediate layer 202 is provided on the photoconductive layer 203 It has a layered structure. That is, the photoconductive member 200 is made of a-(Si _x
N _1-x ) _y : An intermediate layer 202 formed using H _1-y to have a similar function, a photoconductive layer 203 composed of a-Si:X, and the photoconductive layer 203 It comprises a top layer 205 having a free surface 204 thereon. When the upper layer 205 is used, for example, when the free surface 204 of the photoconductive member 200 is subjected to charging treatment to form a charge image, the charge that can be retained on the free surface 204 is transferred to the photoconductive layer 203. photocarriers generated in the photoconductive layer 203 when irradiated with electromagnetic waves;
It has a function of easily allowing photo carriers or charged charges to pass through so as to cause recombination with the charged charges in the area irradiated with electromagnetic waves. The upper layer 205 is composed of a-(Si _x N _1-x ) _y :H _1-y having the same characteristics as the middle layer 202, and
a-Si _a C _1-a , a-(Si _a C _1-a ) _b :H _1-b , a-(Si _c
O _1-c ) _d : H _1-d , a-(Si _c O _1-c ) _d : Base atoms forming the photoconductive layer such as H _1-d, and the combination of silicon atom and nitrogen atom or oxygen atom. or amorphous materials containing hydrogen atoms based on these atoms, or these amorphous materials further containing halogen atoms, inorganic insulating materials such as Al ₂ O ₃ , polyester, polypara It can also be composed of an organic insulating material such as xylene or polyurethane. However, the material constituting the upper layer 205 is a-(Si), which has the same characteristics as the intermediate layer 202 from the viewpoint of productivity, mass production, and electrical and environmental safety of the formed layer. _x N _1-x ) _y : Consists of H _1-y , or a-Si _a C _1-a , a-(Si _a C _1-a ) _b :
H _1-b , a-Si _c N _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 ) _i :
It is desirable to configure X _1-i , a-(Si _j N _1-j ) _k :(H+X) _1-k . In addition to the above-mentioned materials, suitable materials for forming the upper layer 205 include silicon atoms and at least two atoms among C, N, and O, and halogen atoms or halogen atoms. Mention may be made of amorphous materials containing atoms and hydrogen atoms. Examples of the halogen atom include F, Cl, Br, etc. Among the above amorphous materials, those containing F are effective from the viewpoint of thermal safety. The selection of the material constituting the upper layer 205 and the determination of its layer thickness are carried out from the upper layer 205 side to the photoconductive layer 203.
When using the photoconductive member 200 in such a manner that the electromagnetic waves that are detected by done carefully. The upper layer 205 can be formed using the same method as the intermediate layer 202, such as a glow discharge method or a reactive sputtering method. As starting materials used in forming the upper layer 205, in addition to the above-mentioned materials used to form the intermediate layer, examples of starting materials for introducing carbon atoms include, for example, materials having 1 to 5 carbon atoms. Saturated hydrocarbon, ethylene hydrocarbon having 1 to 5 carbon atoms, 2 to 4 carbon atoms
Examples include acetylene hydrocarbons and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), and ethylene (C ₂ H ₄ ) as ethylene hydrocarbons.
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of starting materials for incorporating oxygen atoms into the upper layer 205 include oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), and nitric oxide (NO). , nitrogen dioxide (NO ₂ ), dinitrogen monoxide (N ₂ O), and the like. In addition to these, as one of the starting materials for forming the upper layer 205, for example, CCl ₄ , CHF ₃ , CH ₂ F ₂ ,
Halogen-substituted paraffinic hydrocarbons such as CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Alkyl silicides such as Si(C ₂ H ₅ ) ₄ , SiCl(CH ₃ ) ₃ , SiCl ₂ C
Derivatives of silanes such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These starting materials for forming the upper layer 205 include predetermined atoms as constituent atoms of the upper layer 2 to be formed.
05, they are appropriately selected and used during layer formation. For example, if a glow discharge method is used, Si
Single gas such as (CH ₃ ) ₄ , SiCl ₂ (CH ₃ ) ₂ or SiH ₄ ―
O ₂ (-Aγ) system, SiH ₄ -NO ₂ system, SiH ₄ -O ₂ -N ₂
system, SiCl ₄ -CO ₂ -H ₂ system, SiCl ₄ -NO-H ₂ system,
SiH ₄ -NH ₃ system, SiCl ₄ -NH ₄ system, SiH ₄ -N ₂ system,
SiH ₄ -NH ₃ -NO system, Si(CH ₃ ) ₄ -SiH ₄ system, SiCl ₂
A mixed gas such as a (CH ₃ ) ₂ —SiH ₄ system can be used as a starting material for forming the upper layer 105. The layer thickness of the upper layer 205 in the present invention is as follows:
In order to fully exhibit the above-mentioned functions, it is determined as desired depending on the material constituting the layer, the layer formation conditions, etc. The layer thickness of the upper layer 205 in the present invention is as follows:
Usually, the thickness is preferably 30 to 1000 Å, preferably 50 to 600 Å. If a certain type of electrophotographic process is employed when the photoconductive member of the present invention is used as an electrophotographic imaging member, the free surface of the photoconductive member has a layer configuration as shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer on top. In this case, the surface coating layer is, for example,
If an electrophotographic process such as the NP method described in Publications No. 23910 and No. 43-24748 is applied, it must be electrically insulating and have a low ability to retain static charge when subjected to charging treatment. Although it is required to have sufficient thickness and a certain level of thickness, for example, if an electrophotographic process such as the Carlson process is to be applied, it is desirable that the bright and dark potentials after electrostatic image formation be very small. The surface coating layer is required to be extremely thin. In addition to satisfying its desired electrical properties, the surface coating layer should not have any adverse chemical or physical effects on the photoconductive layer or the upper layer, and should have electrical contact with the photoconductive layer or the upper layer. It is formed in consideration of wearability, moisture resistance, abrasion resistance, and cleaning properties. Typical materials effectively used for forming the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Organic insulating materials such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene trifluoride copolymer, polybutene, polyvinyl butyral, polyurethane, polyparaxylylene, silicon nitride Examples include inorganic insulating materials such as silicon oxide and silicon oxide. The synthetic resin or cellulose derivative among these may be formed into a film and laminated onto the photoconductive layer or upper layer, or a coating solution thereof may be formed and applied onto the photoconductive layer or upper layer. It may also be applied to form a layer. The thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.7 to 70 μm.
In particular, when the surface coating layer is required to function as the above-mentioned protective layer, it is usually 10μ or less, and conversely, when it is required to function as an electrical insulating layer, it is usually It is considered to be 10μ or more. However, the layer thickness value that differentiates this protective layer from the electrically insulating layer depends on the materials used, the applied electrophotographic process,
The above value of 10μ is not absolute, as it varies depending on the designed structure of the image forming member. Furthermore, if this surface coating layer also serves as an antireflection layer, its function will be further expanded and it will become more effective. Example 1 Using the apparatus shown in FIG. 3 installed in a completely shielded clean room, an electrophotographic image forming member was produced by the following operations. A 0.5 mm thick, 10 cm square molybdenum plate (substrate) 302 whose surface was cleaned was firmly fixed to a fixing member 303 at a predetermined position in the glow discharge deposition chamber 301. The substrate 302 is heated with an accuracy of ±0.5° C. by a heater 304 inside the fixing member 303.
Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system are closed, the main valve 312 is fully opened, and the chamber 301 is closed.
The inside was evacuated to a vacuum level of approximately 5×10 ^-6 torr.
Thereafter, the input voltage to the heater 304 was increased, and the input voltage was varied while detecting the temperature of the molybdenum substrate until it stabilized at a constant value of 200°C. Thereafter, the auxiliary valve 309, then the outflow valves 313, 319, 331, 337, and the inflow valves 315, 321, 333, 339 were fully opened, and the insides of the flow meters 314, 320, 332, and 338 were also sufficiently degassed to a vacuum state. Auxiliary valve 309,
Valve 313, 319, 331, 337, 31
After closing 5,321,333,339, in _H2
SiH ₄ gas diluted to 10 vol% (hereinafter referred to as SiH ₄ /H ₂
It is abbreviated as Purity 99.999%) Valve 3 of cylinder 336
35. Open the valve 341 of the N ₂ (99.999% purity) gas cylinder 342, and check the outlet pressure gauges 334, 340.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 333, 3.
Gradually open 39 and check the flow meters 332 and 33.
SiH ₄ /H ₂ gas and N ₂ gas were flowed into the chamber. Subsequently, the outflow valves 331 and 337 were gradually opened, and then the auxiliary valve 309 was gradually opened. At this time, the SiH ₄ /H ₂ gas flow rate and N ₂ gas flow rate ratio is 1:
The inflow valves 333 and 339 were adjusted so that the flow rate was 10. Next, while watching the reading on the Pirani gauge 310, adjust the opening of the auxiliary valve 309, and
Auxiliary valve 309 until the inside of 1 becomes 1×10 ^-2 torr.
I opened it. After the internal pressure of the chamber 301 becomes stable, the main valve 312 is gradually closed and the Pirani gauge 31 is closed.
The aperture was closed until the 0 reading was 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, and confirming that the shutter 307 (which also serves as an electrode) is closed, turn on the high frequency power supply 308 and connect the electrode 303 and shutter 307. A high frequency power of 13.56MHz was applied to generate a glow discharge in the chamber 301, resulting in an input voltage of 3W. Under the above conditions, a-(Si _x N _1-x ) is formed on the substrate.
_y : In order to deposit H _1-y , the conditions were maintained for 1 minute to form an intermediate layer. After that, turn on the high frequency power supply 308.
In the off state and with the glow discharge stopped,
Close the outflow valves 331, 337 and fully open the main valve 312 to remove the gas in the chamber 301.
Vacuum was applied to 10 ^-7 torr. After that, auxiliary valve 3
Closed 09. Next, SiF ₄ gas containing 10 vol% H ₂ gas (hereinafter
Abbreviated as SiF ₄ /H ₂ . 99.999%) valve 317 of cylinder 318, diluted to 500 vol ppm with _H2
B ₂ H ₆ gas (hereinafter abbreviated as B ₂ H ₆ /H _2. Purity 99.999
%) Open the valve 323 of the cylinder 324, adjust the pressure of the outlet pressure gauges 316 and 322 to 1Kg/cm ² ,
Gradually open the inflow valves 315 and 321 to introduce SiF ₄ /H ₂ gas into the flow meters 314 and 320.
B ₂ H ₆ /H ₂ gas was introduced. Subsequently, the outflow valves 313 and 319 were gradually opened, and then the auxiliary valve 309 was gradually opened. At this time, SiF ₄ /H ₂
The inflow valves 315 and 321 were adjusted so that the gas flow rate and the B ₂ H ₆ /H ₂ gas flow rate ratio were 70:1. Next, while watching the reading on the Pirani gauge 310, adjust the opening of the auxiliary valve 309 so that the inside of the chamber 301 is at 1.
Auxiliary valve 309 was opened until ×10 ^-2 torr. After the internal pressure of the chamber 301 became stable, the main valve 312 was gradually closed and the opening was throttled until the reading on the Pirani gauge 310 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, and that the shutter 307 is closed, turn on the high frequency power supply 308 and apply 13.56MHz high frequency power between the electrode 303 and the shutter 307. was applied to generate a glow discharge in the chamber 301, resulting in an input power of 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power supply 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valves 313, 319 and Inflow valve 31
5, 321, 333, and 339, and fully open the main valve 312 to reduce the inside of the chamber 301 to 10 ^-5 torr or less, then close the main valve 312 and open the main valve 312.
The inside of the chamber was brought to atmospheric pressure using a leak valve 311, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member obtained in this way was installed in a charging exposure experiment equipment, and the image forming member was placed at 6.0 KV for 0.2 seconds.
Corona charging was performed for a while, and a light image was immediately irradiated. The optical image uses a tungsten lamp light source, 0.8 lux.
A light intensity of sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) onto the surface of the member. 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 5.5 KV using a charging exposure experiment device, and then imagewise exposed at a light intensity of 0.8 lux・sec, and then a charging developer was immediately applied. When cascaded onto the surface of the component and then transferred and fixed onto transfer paper,
An extremely clear image was obtained. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 2 The glow discharge holding time when forming an intermediate layer on a molybdenum substrate was as shown in Table 1 below.
Except for various changes, image forming members indicated by Sample No. ~ were prepared under the same conditions and procedures as in Example 1, and were placed in the same charging exposure experimental apparatus as in Example 1. When images were formed, the results shown in Table 1 below were obtained. As can be seen from the results shown in Table 1, in order to achieve the object of the present invention, the thickness of the intermediate layer must be between 30 Å and 1000 Å.
It is necessary to form within the range of .

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes
×: Not possible
Intermediate layer film deposition rate: 1 Å/sec
Example 3 The process was exactly the same as Example 1, except that the flow rate ratio of SiH ₄ /H ₂ and N ₂ in the intermediate layer was varied as shown in Table 2 when forming the intermediate layer on the molybdenum substrate. Image forming members shown in samples Nos. 9 to 15 were prepared according to the conditions and procedures, and were installed in the charging exposure experimental apparatus exactly as in Example 1 to form images in the same manner, as shown in Table 2. The results shown are obtained. Furthermore, the sample
Table 3 shows the results of analyzing only the intermediate layers of Nos. 11 to 15 by Auger electron spectroscopy. As can be seen from the results shown in Tables 2 and 3, in order to achieve the object of the present invention, it is necessary to form the intermediate layer with x, which is related to the composition ratio of Si and N, in the range of 0.60 to 0.43.

[Table] ◎: Excellent ○: Good △: Can be used for practical purposes ×: Impossible

[Table] Example 4 After forming an intermediate layer according to the same conditions and procedures as in Example 1, the valve 335 of the cylinder 336 and the valve 341 of the cylinder 342 were closed to remove the gas in the chamber 301 ^. Vacuum was applied to ⁷ torr. After that, the auxiliary valve 309, the outflow valves 331, 33
7. After closing the inflow valves 333 and 339,
Open the valve 317 of the SiF ₄ /H ₂ gas cylinder 318, adjust the pressure of the outlet pressure gauge 316 to 1 Kg/cm ² ,
The inflow valve 315 was gradually opened to allow SiF ₄ /H ₂ gas to flow into the flow meter 314. Subsequently, the outflow valve 313 was gradually opened, and then the auxiliary valve 309 was gradually opened. Next, the opening of the auxiliary valve 309 was adjusted while observing the reading on the Pirani gauge 310, and the auxiliary valve 309 was opened until the inside of the chamber 301 reached 1×10 ⁻² torr. After the internal pressure of the chamber 301 became stable, the main valve 312 was gradually closed and the opening was throttled until the reading on the Pirani gauge 310 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, the shutter 307 is closed, and then the high frequency power supply 308 is turned on, and 13.56 MHz high frequency power is applied between the shutter 307 and the electrode 303, and the chamber 3
A glow discharge was generated in 01, and the input power was 60W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power supply 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 313 is turned off.
and close the inflow valve 315, and close the main valve 31.
2 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less, then the main valve 312 was closed, and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. In this case, the total thickness of the formed layer is approximately
It was 9μ. The image forming member thus obtained is
When an image was formed on a transfer paper according to the same procedure as in Example 1, the image quality was superior and extremely clear when the image was formed using corona discharge than when the image was formed using corona discharge. .
From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 5 After forming an intermediate layer on a molybdenum substrate for 1 minute and forming a photoconductive layer for 5 hours under the same conditions and procedures as in Example 1, the high frequency power source 308 was turned on.
In the off state, the glow discharge is stopped.
Close the outflow valves 313, 319 and again.
The outflow valves 331 and 337 were opened to obtain the same conditions as when forming the intermediate layer. Subsequently, the high frequency power supply was turned on again to restart the glow discharge. The input power at that time was also 3W, the same as when forming the intermediate layer. After continuing the glow discharge for 2 minutes to form an upper layer on the photoconductive layer, the heating heater 304 is turned off, and the high frequency power source 30
8 is also turned off, wait until the substrate temperature reaches 100°C, close the outflow valves 331, 337 and inflow valves 333, 339, fully open the main valve 312, and reduce the inside of the chamber 301 to 10 ^-5 torr or less. After that, the main valve 312 was closed, and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. The image forming member thus obtained was placed in the same charging exposure experiment apparatus as in Example 1, and
Corona charging was performed for 0.2 seconds, and a light image was immediately irradiated. The optical image is created using a tungsten lamp light source.
A light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 6 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1,
The deposition chamber was evacuated to 5×10 ⁻⁷ torr, and SiF ₄ /H ₂ gas was introduced into the chamber in the same manner as in Example 1. Thereafter, gas is flowed from the B ₂ H ₆ /H ₂ gas cylinder 324 through the inflow valve 321 to the flow meter 320 at a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 322), and by adjusting the outflow valve 319, the flow meter The opening of the outflow valve 319 is determined so that the reading of 320 is 1/15 of the flow rate of SiF ₄ /H ₂ gas,
Stabilized. Subsequently, the shutter 307 was closed and the high frequency power supply 308 was turned on again to restart the glow discharge. The input power at that time was 60W. After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power supply 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 31
3, 319 and the inflow valves 315, 321 are closed, the main valve 312 is fully opened, and the chamber 301 is closed.
After reducing the internal pressure to 10 ^-5 torr or less, the main valve 312
The chamber 301 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 10μ. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1. The image quality was excellent and extremely clear. From this result, it was found that the image forming member obtained in this example had chargeability dependence. Example 7 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1,
The deposition chamber was evacuated to 5×10 ⁻⁷ torr, and SiF ₄ /H ₂ gas was introduced into the chamber in the same manner as in Example 1. PF ₅ gas ( _hereafter
It is abbreviated as PF ₅ /H ₂ . Gas flows from the cylinder 330 (purity 99.999%) through the inflow valve 327 to the flow meter 326 at a gas pressure of 1 Kg/cm ² (reading of the outlet pressure gauge 328), and by adjusting the outflow valve 325, the reading of the flow meter 326 becomes SiF. ₄ /H ₂
The opening of the outflow valve 325 was set to be 1/60 of the gas flow rate to stabilize it. Subsequently, the shutter 307 was closed and the high frequency power supply 308 was turned on again to restart the glow discharge. The input voltage at that time was 60W.
After continuing the glow discharge for another 4 hours to form a photoconductive layer, the heating heater 304 is turned off, the high frequency power source 308 is also turned off, and after waiting for the substrate temperature to reach 100°C, the outflow valve 304 is turned off.
13, 325 and inflow valves 315, 327, and fully open the main valve 312, the chamber 301
After reducing the internal pressure to 10 ^-5 torr or less, the main valve 312
The chamber 301 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 311, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 11μ. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1. The image quality was excellent and extremely clear. From this result, it was confirmed that the image forming member obtained in this example had charge polarity dependence. Example 8 The surface was cleaned by replacing it with a molybdenum substrate.
Example 1: Corning 7059 glass (1 mm thick, 4 x 4 cm, surface polished) with 1000 Å of ITO deposited on one surface by electron beam evaporation.
on the fixing member 303 of a similar device (Fig. 3).
It was installed with the ITO deposition surface facing downward, and the H ₂ gas cylinder 342 was replaced with an NH ₃ gas cylinder diluted to 10 vol% with H ₂ gas, and the SiH ₄ /H ₂ gas flow rate and NH ₃ /H ₂ during intermediate layer formation were determined. Under the same conditions and procedures as in Example 4, except that the gas flow rate ratio was 1:20,
After forming the intermediate layer and the photoconductive layer on the ITO substrate, it was taken out of the deposition chamber 301 and placed in the charging exposure experimental equipment in the same manner as in Example 1 for an image formation test. In the case of the discharge, charge developer combination, very good quality, high contrast toner images were obtained on the transfer paper. Example 9 Nine image forming members were formed using the same operations and conditions as in Example 1. After that, the upper layer to be formed on the photoconductive layer is formed from A to I under the conditions shown in Table 4,
Nine imaging members were made with each top layer. When forming the upper layer A by the sputtering method, the target 305 is a polycrystalline silicon target with a partially laminated graphite target, and an N ₂ gas cylinder 342 is used.
Changed to Ar gas cylinder. Further, when forming the upper layer E, the target was changed to a Si ₃ N ₄ target, and the N ₂ gas cylinder 342 was changed to an N ₂ gas cylinder diluted 50% with Ar. In addition, when forming the upper layer B by the glow discharge method, when forming the upper layer C, the B ₂ H ₆ gas cylinder 324 is diluted with H ₂ to 10 vol% in a C ₂ H ₄ /H ₂ gas cylinder. For B ₂ H ₆ gun cylinder 324 with H ₂
When forming the upper layer D in a Si(CH ₃ ) ₄ cylinder diluted to 10 vol%, apply the same method as when forming the upper layer B.
The B ₂ H ₆ gas cylinder 324 is replaced with a C ₂ H ₄ /H ₂ gas cylinder, and the PF ₅ gas cylinder 3 is used when forming the upper layer G.
30 is diluted to 10 vol% with H ₂ in a NH ₃ /H ₂ gas cylinder, and when forming the upper layer I, PF ₃ gas cylinder 330 is diluted with H ₂ to 10 vol % in a NH ₃ /H ₂ gas cylinder.
They each changed to gas cylinders. As in Example 1, nine image forming members each having an intermediate layer and a photoconductive layer having upper layers A to I shown in Table 4 were subjected to image formation under the same operations and conditions as in Example 1, and then transferred to transfer paper. When the toner images were transferred to a toner image, extremely clear toner images were obtained that were independent of charging polarity.

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the photoconductive member of the present invention, and FIG. 3 is a diagram of an apparatus for manufacturing the photoconductive member of the present invention. FIG. 2 is a schematic explanatory diagram showing an example. 100,200...Photoconductive member, 101,201
...Support, 102,202...Intermediate layer, 103,2
03...Photoconductive layer, 104,204...Free surface, 2
05... Upper layer.

Claims (1)

[Scope of Claims] 1. A support, a photoconductive layer made of an amorphous material having silicon atoms as a matrix and containing halogen atoms, and a photoconductive layer provided between them, and a photoconductive layer formed from the support side into the photoconductive layer. an intermediate layer having a function of blocking the inflow of carriers and allowing carriers generated in the photoconductive layer and moving toward the support by electromagnetic wave irradiation to pass from the photoconductive layer side to the support side; In the conductive member, the intermediate layer is (Si _x
N _1-x ) _Y H _1-Y (However, 0.43≦x≦0.60, 0.65≦y≦
A photoconductive member comprising a non-photoconductive amorphous material represented by 0.98) and having a layer thickness of 30 to 1000 Å. 2. Claim 1 further comprising, on the upper surface of the photoconductive layer, an upper layer made of a non-photoconductive amorphous material having silicon atoms as a host and containing at least either hydrogen atoms or halogen atoms. photoconductive member. 3. The photoconductive member according to claim 1, further comprising an upper layer made of an inorganic insulating material or an organic insulating material on the upper surface of the photoconductive layer. 4 Has a free surface that serves as a charge image forming surface, and has a diameter of 0.5 to
A photoconductive member according to any one of claims 1 to 3, further comprising a surface coating layer having a layer thickness of 70μ.