JPS6341059B2 - - 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 photoconductive materials constituting photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, document reading devices, etc., highly sensitive,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], has the spectral characteristics of the electromagnetic waves to be irradiated, has good photoresponsiveness, and has a desired dark resistance value.
Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily remove 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 Si) is a photoconductive material that has recently attracted attention.
For example, German Publication No. 2746967 and German Publication No. 2855718 describe its application as an image forming member for electrophotography, 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 resistivity, photosensitivity, and photoresponsiveness, as well as moisture resistance. There are points that can be further improved in terms of the usage environment characteristics of The reality is that it cannot be used effectively. 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, Accumulation of fatigue occurs due to repeated use. There have been many disadvantages such as so-called ghost development, which causes afterimages. Furthermore, for example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional Se, CdS, ZnO, PVCz, TNF, etc. Although it has many advantages compared to OPC (organic photoconductive material), a-Si has been given characteristics for use in conventional solar cells.
Even when the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for electrostatic image formation, dark decay is extremely fast, compared to ordinary electrophotography. The above-mentioned tendency is remarkable in a humid atmosphere, and in some cases, it may not be possible to retain the electrostatic charge at all until the development time.There are some points that can be solved. is known to exist. 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 A specific intermediate layer is formed between a photoconductive layer made of an amorphous material containing hydrogen atoms, so-called hydrogenated amorphous silicon (hereinafter referred to as a-Si; H), and a support that supports the photoconductive layer. A photoconductive member designed and produced with a layer structure with intervening layers is not only usable for practical use, but also superior in most respects when compared with conventional photoconductive members. This is based on the discovery that it has particularly excellent properties as a photoconductive member for electrophotography. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent resistance to light fatigue and does not cause deterioration even after repeated use. The main object of the present invention is to provide 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 have charge retention properties 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 which has excellent electrophotographic properties with sufficient electrophotographic properties and whose properties hardly deteriorate 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 hydrogen atoms, and is provided between the support and the photoconductive layer from the support side. an intermediate layer having a function of preventing carriers from being injected into the photoconductive layer 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; The photoconductive member is characterized in that the intermediate layer is made of an amorphous material whose constituent elements are silicon atoms, nitrogen atoms, and halogen atoms, and has 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 a solid-state imaging device, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, and has excellent 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 it is possible to obtain high-quality visible images with high resolution. Moreover, when applied to an electrophotographic image forming member,
a-Si:H, which has high dark resistance and low resistance, has low photosensitivity, and conversely, a-Si:H, which has high photosensitivity, has a low dark resistance of around 10 ⁸ Ωcm, and in both cases, the conventional layer structure Whereas the photoconductive layer could not be used as an electrophotographic image forming member, in the case of the present invention, an a-Si:H layer with relatively low resistance (5×10 ⁹ Ωcm or more) was used. However, a-Si:H, which has relatively low resistance but high sensitivity, can form a photoconductive layer for electrophotography.
can also be used satisfactorily, and restrictions from the characteristics of a-Si:H 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,
This layer structure includes a photoconductive layer 103 provided in direct contact with the intermediate layer 102, and 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, Ae, Cr, Mo,
Examples include metals such as Au, Nb, Ta, V, Ti, Pt, and 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,
Ae, 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, Ae, Ag, Pb, Zn, Ni, Au, Cr,
The surface is treated with a metal such as Mo, Ir, Nb, Ta, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired, but for example,
If the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for 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. The intermediate layer 102 is made of a non-photoconductive amorphous material [a-(Si _x N _1-x ) containing silicon atoms and nitrogen atoms as a matrix and halogen atoms (denoted as X).
_y : Abbreviated as X1 _-y . However, 0<x<1, 0<y<
1], which effectively prevents carriers from flowing into the photoconductive layer 103 from the support 101 side, and which is generated in the photoconductive layer 103 by electromagnetic wave irradiation and directed toward the support 101 side. It has a function of easily allowing the photo carrier moving along the substrate to pass from the side of the photoconductive layer 103 to the side of the support 101. a-(Si _x N _1-x ) _y : Intermediate layer 1 composed of X _1-y
02 is formed by a glow discharge method, a sputtering method, an ion implantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and characteristics desired for the photoconductive member to be manufactured. Glow discharge has advantages such as it is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having a A sputtering method or a sputtering method is preferably employed. 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 system. To form the intermediate layer 102 by the glow discharge method, the raw material gas for forming a-(Si _x N _1-x ) _y :X _{1-y is}
If necessary, the gas is mixed with a dilution gas at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition in which the support 101 is installed, and the introduced gas is caused to generate a gas plasma by causing a glow discharge. It is sufficient to deposit a-(Si _x N _1-x ) _y :X _1-y on the support 101 by converting it into In the present invention, the raw material gas for forming a-(Si _x N _1-x ) _y :X _1-y is a gaseous substance containing at least one of Si, N, and X as a constituent atom. Alternatively, most gasified substances can be used. When using a raw material gas containing Si as one of Si, N, and X, 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 Alternatively, a raw material gas containing Si and a raw material gas containing N and X may be mixed at a desired mixing ratio. Can be used by mixing. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, preferred halogen atoms X are F, Cl, Br, and I, with F and Cl being particularly preferred. In the present invention, the intermediate layer 102 is a-(Si _x
N _1-x ) _y :Although it is composed of X _1-y , the intermediate layer 102 can further contain hydrogen atoms. The inclusion of hydrogen atoms in the intermediate layer 102 is advantageous in terms of production costs since it is possible to share some of the raw material gas types when forming a continuous layer with the photoconductive layer 103. In the present invention, starting materials that can be used as raw material gases that can be effectively used to form the intermediate layer 102 include those in a gaseous state or substances that can be easily gasified at normal temperature and normal pressure. I can do it. Examples of starting materials for forming such an intermediate layer include nitrogen, nitrides, nitrogen compounds such as fluorinated nitrogen and azides, simple halogens, hydrogen halides,
Examples include interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, nitrogen (N ₂ ) nitrogen compounds include ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ )
etc., halogen gases include fluorine, chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, HBr, and interhalogen compounds include BrF, ClF, ClF ₃ , ClF ₅ , BrF. _Five ,
BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br, SiCl ₂ Br ₂ ,
SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , silicon hydride includes silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. I can do it. These starting materials for forming the intermediate layer are selected such that the intermediate layer to be formed contains silicon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. They are selected and used as desired during formation. For example, SiH ₄ or Si ₂ H ₆ can easily contain silicon atoms and hydrogen atoms and form an intermediate layer with desired characteristics, and N ₂ or NH ₃ can contain nitrogen atoms. SiF ₄ , SiH ₂ F ₂ , SiHCl ₃ , SiCl ₄ as substances containing halogen atoms,
By introducing SiH ₂ Cl ₂ or SiH ₃ Cl, etc. in a gaseous state at a predetermined mixing ratio into the intermediate layer forming equipment system and causing a glow discharge, a-Si _x N _1-x :
An intermediate layer consisting of X:H can be formed. Alternatively, SiF ₄ , etc., which can contain silicon atoms and halogen atoms, and N ₂ , etc., which can contain nitrogen atoms, at a predetermined mixing ratio, and if necessary, He, Ne, It is also possible to form an intermediate layer made of a-Si _x N _1-x :F by introducing it together with a rare gas such as Ar into an apparatus system for forming an intermediate layer to generate a glow discharge. To form the intermediate layer 102 by the sputtering method, a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer formed by mixing Si and Si ₃ N ₄ is used as a target. etc., by sputtering in various gas atmospheres containing halogen and optionally hydrogen as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing N and The Si wafer may be sputtered by forming plasma. 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 halogen atoms can be produced. This is done by sputtering in an atmosphere. As the raw material gas for introducing N, X, and H if necessary, the starting material for forming the intermediate layer shown in the glow discharge example mentioned above is also used as an effective material in the sputtering method. can be done. In the present invention, a so-called rare gas, such as He,
Preferable examples include Ne and Ar. The intermediate layer 102 in the present invention is carefully formed to provide the desired properties. In other words, substances whose constituent atoms are Si, N, X, and optionally H have a structure ranging from crystalline to amorphous depending on the conditions for their creation, and electrical properties ranging from conductivity to amorphous. In the present invention, non-photoconductive a-(Si _x N _1-x ) _y : The conditions for creating it are strictly selected so that X _1-y is formed. a-(Si _x
N _1-x ) _y :X _1-y indicates that the function of the intermediate layer 102 is to prevent carriers from flowing into the photoconductive layer 103 from the support 101 side, and to prevent photocarriers generated in the photoconductive layer 103. It is formed to exhibit electrically insulating behavior because it allows the material to easily move and pass through to the support body 101 side. Further, when the photocarrier generated in the photoconductive layer 103 passes through the intermediate layer 102, a has a mobility value for the passing carrier to such an extent that the photocarrier passes through the intermediate layer 102 smoothly. -(Si _x N _1-x ) _y :X _1-y is an important factor in the production conditions, including the temperature of the support during production. That is, a-(Si _x N _1-x ) is formed on the surface of the support 101.
When forming the intermediate layer 102 consisting of y:X1 _-y , the temperature of the support during layer formation is an important factor that influences the structure and _properties of the formed layer. a-(Si _x N _1-x ) having the desired properties
The temperature of the support during layer formation is strictly controlled so that _y : X _1-y can be formed as desired. In the present invention, in order to effectively achieve the desired purpose, 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. Formation of the intermediate layer 102 is carried out, typically at 100-300°C, preferably
The temperature is preferably 150 to 250°C. For forming the intermediate layer 102, the intermediate layer 102 is formed in the same system.
The photoconductive layer 103 can be formed continuously from the photoconductive layer 103 to the third layer formed on the photoconductive layer 103 if necessary. Glow discharge method and sputtering method are advantageous because delicate control of the composition ratio of atoms constituting each layer and control of layer thickness are relatively easy compared to other methods. , when forming the intermediate layer 102 using these layer forming methods, the discharge power during layer formation is created in the same manner as _the support _temperature described above _. It is one of the important factors that influences the characteristics of _1-y . The discharge power conditions for effectively producing a-(Si _x N 1 _{- x} ) _y :
It is 10-300W, preferably 20-100W. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.01 to 5 Torr when layer formation is performed using the glow discharge method.
When layer formation is performed by sputtering method to about 0.1 to 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 halogen atoms contained in the intermediate layer 102 in the photoconductive member of the present invention are the same as the manufacturing conditions of the intermediate layer 102, so that an intermediate layer can be obtained that achieves the desired characteristics to achieve the object of the present invention. This is an important factor. The amount of nitrogen atoms contained in the intermediate layer 102 in the present invention is usually 30 to 60 atomic%, preferably
A desirable value is 40 to 60 atomic%. The content of halogen atoms is usually 1 to 20 atomic%, preferably 2 to 15 atomic%, and photoconductive members produced when the halogen content is in this range are actually used. It can be applied to many surfaces. The content of hydrogen atoms that are included as necessary is usually
It is desirable that the content be 19 atomic % or less, preferably 13 atomic % or less. That is, the previous a-
(Si _x N _1-x ) _y : If expressed as X _1-y , x is usually 0.43
~0.60, preferably 0.49~0.43, y usually 0.99~
0.80, preferably 0.98 to 0.85. If both halogen atoms and hydrogen atoms are included, the numerical range of x and y in this case can also be calculated by using the same expression a-(Si _x N _1-x ) _y : (H+X) _1- y as before. a
-(Si _x N _1-x ) _y : Almost the same as the case of X _1-y . 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,
If the thickness is too thick, the photoconductive layer 1 will not be able to sufficiently prevent carriers from flowing into the photoconductive layer 103 from the side of the support 101.
Photocarrier support 1 produced in 03
The probability of passing to the 01 side becomes extremely small,
Therefore, in either case, the object of the present invention cannot be effectively achieved. 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 composed of a-Si:H having the semiconductor properties shown below. p-type a-Si:H... Contains only acceptor. Or one that contains both donor and acceptor and has a high concentration of acceptor (Na). p ^- type a-Si: H...type with a write-read bleed of the so-called p-type impurity, which has a low acceptor concentration (Na). n-type a-Si:H...Contains only a donor. Or one that contains both donor and acceptor and has a high donor concentration (Nd). n ^- type a-Si:H...type with low donor concentration (Nd), lightly doped with so-called n-type impurities. i-type a-Si:H...NaNdO or,
NaNd stuff. In the present invention, by providing the intermediate layer 102, a-Si:H 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 Ωcm.
It is desirable that the photoconductive layer 103 be formed as described above. 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 as follows:
The thickness relationship between the photoconductive layer and the intermediate layer can be appropriately determined as desired so that the functions of the photoconductive layer and the intermediate layer can be effectively utilized and the objects of the present invention can be effectively achieved. In normal cases, the layer thickness is preferably several hundred to several thousand times or more than the thickness of the intermediate layer. A specific value is usually 1 to 100μ, preferably 2 to 50μ. In the present invention, in order to make the photoconductive layer a layer composed of a-Si:H, when forming these layers, H is contained in the layer by the following method. . Here, "H is contained in the layer"
This means that "a state in which H is combined with Si", "a state in which H is ionized and incorporated into the layer", or "a state in which H is incorporated into the layer as H ₂ " or the like. It means a state of being a combination of. As a method for incorporating H into the photoconductive layer, for example, when forming the layer, SiH ₄ , Si ₂ H ₆ ,
It is introduced in the form of silicon compounds such as silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ , and these compounds are decomposed by a glow discharge decomposition method to remove the contained substances as the layer grows. Ru. When forming a photoconductive layer by this glow discharge method, the starting materials for forming a-Si are SiH ₄ ,
When a layer is formed by decomposing silicon hydride gas such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _10, etc., H is automatically contained in the layer. When using the reaction sputtering method, He or
H ₂ gas is introduced when sputtering is performed using Si as a target in an inert gas such as Ar or a mixed gas atmosphere based on these gases, or SiH ₄ , Si ₂ H ₆ , Si ₃ H Silicon hydride gas such as ₈ , Si ₄ H ₁₀ , or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping may be introduced. According to the findings of the present inventors, the H content of the photoconductive layer composed of a-Si:H influences whether the formed photoconductive member can be sufficiently applied in practice. It has been found that this is one of the major factors and is extremely important. In the present invention, in order for the photoconductive member to be formed to be sufficiently applicable to practical applications, the amount of H contained in the photoconductive layer is usually 1 to 40 atomic%, preferably 5 to 30 atomic%. It is preferable to set it as %. 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, an n-type impurity, a p-type impurity, or both impurities are added to the formed layer during layer formation using a glow discharge method, a reactive sputtering method, etc. This is achieved by doping while controlling the amount. As impurities to be doped into the photoconductive layer, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferably used to make the photoconductive layer p-type. and when making it n-type,
Elements of group A of the periodic table, such as N, P, As,
Preferable 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 table, it is usually 10 ^-6 to 10 ^-3 atomic%, preferably 10 ^-5 to 10 -3 atomic%.
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 light guide member 200 shown in FIG. 2 has the same layers as the photoconductive member 100 shown in FIG. It has a structure. That is, the photoconductive member 200 includes an intermediate layer 202 formed on a support 201 using the same material as the intermediate layer 102 and having the same function, and a photoconductive layer 203 composed of a-Si:H. and the photoconductive layer 203
a top layer 20 provided thereon and having a free surface 204;
It is equipped with 5. 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 held on the free surface 204 is transferred to the photoconductive layer 203. When the photoconductive layer 203 is irradiated with electromagnetic waves, the photocarriers generated in the photoconductive layer 203 and the electrostatic charges in the portions irradiated with the electromagnetic waves are recombined. In addition, it has the function of easily allowing the passage of photo carriers or charged charges. The upper layer 205 has the same characteristics as the intermediate layer 202, and optionally contains a-(Si _x
N _1-x ) _y : Composed of X _{1-y and} a-Si _a C _1-a , a-
(Si _a C _1-a )b:H _1-b ,a-(Si _a C _1-a )b:(H+
X) _1-b , a-Si _c O _1-c , a-(Si _c O _1-c ) d: H _1-d ,
a-(Si _c O _1-c ) d: (H+X) _1-d , a-Si _e N _1-e , etc. Composed of a silicon atom, which is the host atom, and a nitrogen atom or an oxygen atom or hydrogen atoms (H) or / using these atoms as parent atoms.
and an amorphous material containing a rogen atom (X),
It can also be composed of an inorganic insulating material such as Al ₃ O ₃ or an organic insulating material such as polyester, polyparaxylylene, or polyurethane. However, the material constituting the upper layer 205 is selected from the middle layer 202 in terms of productivity, mass production, and electrical and usage environmental stability of the formed layer.
or a-(Si _a C _{1-a ) b} : X _{1 - b} , a with the same characteristics as
―(Si _c N _1-c ) d: H _1-d , a―(Si _e N _1-e ) f:
X _1-f , a-(Si _g C _1-g )h: H _1-h or a-Si _x C _1-x , a that does not contain a halogen atom or a hydrogen atom
- It is desirable to consist of Si _z N _1-z . Upper layer 20
In addition to the substances listed above, suitable materials for forming 5 include silicon atoms, C,
At least two atoms among N and O are used as a parent body,
Examples include amorphous materials containing halogen atoms or halogen 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 stability. 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 the photoconductive member 200 is used in such a way as to irradiate electromagnetic waves that are sensitive to 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 for forming the intermediate layer, starting materials for introducing carbon atoms include, for example, carbon atoms having 1 to 4 carbon atoms. Saturated hydrocarbon, ethylene hydrocarbon having 1 to 4 carbon atoms, 2 to 3 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 ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ) , putene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₄ H ₄ ). , butyne (C ₄ H ₆ ), and the like. Examples of starting materials for containing oxygen atoms in the upper layer 205 include oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ),
Examples include nitric oxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen monoxide (N ₂ O). 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 l, C ₂ H ₃ Cl, fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si(CH ₃ ) ₄ , Si Alkyl silicides such as (C ₂ H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Derivatives of silanes such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ may also be mentioned as useful. These starting materials for forming the upper layer 205 are used to form the upper layer 205 in which predetermined atoms are formed as constituent atoms.
5, they are appropriately selected and used during layer formation. For example, if you use the glow discharge method,
Single gas such as Si(CH ₃ ) ₄ , SiCl ₂ (CH ₃ ) ₂ or SiH ₄
-N ₂ O system, SiH ₄ -O ₂ (-Ar) 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 ―
Mixed gases such as SiH ₄ series, SiCl ₂ (CH ₃ ) ₂ -SiH ₄ series, etc. can be used as a starting material for forming the upper layer 205 . 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:
In normal cases, 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 in the layer configuration shown in FIG. 1 or FIG. It is necessary to further provide a surface coating layer. In this case, the surface coating layer is, for example, disclosed in Japanese Patent Publication No. 42-23910, No. 43-24748.
If an electrophotographic process such as the NP method described in the publication is to be applied, it must be electrically insulating, have sufficient ability to retain static charge when subjected to charging treatment, and be thicker than a certain level. However, if an electrophotographic process such as the Carlson process is applied, it is desirable that the potential in the bright area after electrostatic image formation is very small, so the thickness of the surface coating layer should be is required to be very thin. In addition to satisfying its desired electrical properties, the surface coating layer must not have any adverse chemical or physical effects on the photoconductive layer or the upper layer, and must not have electrical contact with the photoconductive layer or the upper layer. It is formed in consideration of adhesion, moisture resistance, abrasion resistance, cleanability, etc. 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 insulators such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer, ethylene trifluoride-vinylidene fluoride copolymer, polybutene, polyvinyl butyral, polyurethane, polyparaxylylene, silicon nitride and inorganic insulators such as silicon oxide. These synthetic resins or cellulose derivatives may be made into a film and laminated onto the photoconductive layer or the upper layer, or a coating solution may be formed,
It may be coated on the photoconductive layer or the upper layer 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 0.5 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,
On the other hand, when a function as an electrically insulating layer is required, the thickness is usually set to 10μ or more. However, the layer thickness differentiating between the protective layer and the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the designed structure of the imaging member.
The above value of 10μ is not an absolute value. 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) 309 whose surface was cleaned was firmly fixed to a fixing member 303 at a predetermined position in a glow discharge deposition chamber 301 placed on a support stand 302 . The substrate 309 is
It is heated with an accuracy of ±0.5° C. by a heater 308 inside the fixed member 303. Temperature was measured directly on the backside of the substrate by a thermocouple (alumel-chromel). Next, after confirming that all valves in the system are closed, the main valve 310 is fully opened to exhaust the inside of the chamber 301.
The degree of vacuum was set at approximately 5×10 ^-6 torr. Thereafter, the input voltage to the heater 308 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. After that, fully open the auxiliary valve 340, then the outflow valves 325, 326, 327, 329 and the inflow valves 320-2, 321, 322, 324,
Flow meter 316, 317, 318, 320
-1 was also sufficiently degassed and vacuumed. Auxiliary valve 340, valves 325, 326, 327, 32
After closing 9,320-2,321,322,324, SiF ₄ gas containing 10 vol% H ₂ (hereinafter referred to as SiF ₄ /H ₂
It is abbreviated as Purity 99.99%) Valve 3 of cylinder 311
30. Open the valve 331 of the _N2 gas (99.999% purity) cylinder 312, and check the outlet pressure gauges 335, 33.
Adjust the pressure of 6 to 1Kg/cm ³ and open the inflow valve 320-
Gradually open 2,321 and check the flow meter 31.
SiF ₄ /H ₂ gas and N ₂ gas were flowed into 6,317. Subsequently, the outflow valves 325 and 326 were gradually opened, and then the auxiliary valve 340 was gradually opened. At _this time, _the inflow valve _320-2 ,
321 was adjusted. Next, the opening of the auxiliary valve 340 was adjusted while observing the reading on the Pirani gauge 341, and the auxiliary valve 340 was opened until the inside of the chamber 301 became 1×10 ⁻² torr. After the internal pressure of the chamber 301 became stable, the main valve 310 was gradually closed and the opening was throttled until the Pirani gauge 341 indicated 0.5 torr. It was confirmed that the gas inflow was stable and the internal pressure was stable. Next, turn on the high frequency power supply 342.
Turn it ON and connect the induction coil 343 to 13.56MHz.
high-frequency power is applied to chamber 3 of the coil section (upper chamber).
A glow discharge was generated in 01, and the input power was 60W. In order to deposit a layer on the substrate under the above conditions, the conditions were maintained for 1 minute to form an intermediate layer. after that,
With the high frequency power supply 342 turned off and glow discharge stopped, the outflow valves 325 and 326 are closed, and then B ₂ H ₆ gas diluted to 50 volppm with H ₂ (hereinafter referred to as B ₂ H ₆ /H ₂ ) It is abbreviated as ) Open the valve 332 of the cylinder 313 and the valve 334 of the SiH ₄ gas (hereinafter abbreviated as SiH ₄ /H ₂ ) diluted with 10 vol% H ₂ cylinder 315, and set the pressure of the outlet pressure gauges 337 and 339 to 1 Kg/cm. ³ , inlet valve 322, 32
4 gradually open the flow meters 318 and 320.
-B ₂ H ₆ /H ₂ gas and SiH ₄ /H ₂ gas were flowed into the chamber. Subsequently, the outflow valves 327, 329 were gradually opened. At this time, B ₂ H ₆ /H ₂ gas flow rate and
The inflow valves 322 and 324 were adjusted so that the SiH ₄ /H ₂ gas flow rate ratio was 1:50. Next, the instructions on the Pirani gauge 341 are as same as when forming the intermediate layer.
The openings of the auxiliary valve 340 and main valve 310 were adjusted to stabilize the pressure to 0.5 Torr. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was reduced to 10W compared to before. After continuing the glow discharge for another 3 hours to form a photoconductive layer, the heating heater 308 is turned off, the high frequency power supply 342 is also turned off, and the substrate temperature reaches 100°C.
Wait until the outflow valves 327, 329
and inflow valve 320-2, 321, 322, 3
24 and fully open the main valve 310.
After reducing the inside of the chamber 301 to 10 ^-3 torr or less, the main valve 310 is closed, and the inside of the chamber 301 is closed by the leak valve 34.
4 to bring the pressure to atmospheric pressure and take out the substrate. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 6.0 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 0.8 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a charged developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the image forming member was corona charged at 5.5 KV for 0.2 seconds using a charging exposure experiment device, and image exposure was immediately performed at a light intensity of 0.8 lux・sec, and then a charging developer was immediately applied to the surface of the member. When the image was 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 charge polarity and had the characteristics of a bipolar image forming member. Example 2 Sample No. An image forming member shown in . . . . was prepared, and when it was installed in the same electrostatic exposure experimental apparatus as in Example 1 and the same image formation was performed, 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 purpose of the present invention, the thickness of the intermediate layer is 30 Å to 1000 Å.
It is necessary to form within the range of .

[Table] ◎: Excellent, ○: Good, △: Practically usable, ×: Not possible, intermediate layer film deposition rate
Degree: 1Å/sec
Example 3 When forming an intermediate layer on a molybdenum substrate
The SiF ₄ /H ₂ gas flow rate and N ₂ gas flow rate ratio are
Image forming members indicated by sample numbers ~ were prepared under the same conditions and procedures as in Example 1, except for making various changes as shown in the table, and were placed in the same electrostatic exposure experimental apparatus as in Example 1. When the same image formation was carried out using the same apparatus, the results shown in Table 2 below were obtained. Samples ~ were analyzed by Auger electron spectroscopy, and the results shown in Table 3 were obtained. From the results in Tables 2 and 3, in order to achieve the purpose of the present invention, the composition ratio X of Si and N in the intermediate layer is
It must be formed within the range of 0.43 to 0.60.

【table】

[Table] Example 4 A molybdenum substrate was installed in the same manner as in Example 1, and then a vacuum of 5×10 ^-6 Torr was created in the glow discharge deposition chamber 301 by the same operation as in Example 1, and the substrate temperature was was maintained at 200°C, and then the SiF ₄ , N ₂ , and SiH ₄ gas inflow system was heated 5× in the same manner as in Example 1.
10 ^-6 torr vacuum and then auxiliary valve 340
and after closing each outflow valve 325, 326, 329 and each inflow valve 320-2, 321, 324,
Valve 330 of SiF ₄ /H ₂ gas cylinder 311 containing 10 vol% H ₂ , valve 33 of N ₂ gas cylinder 312
1, and the pressure of the outlet pressure gauges 335 and 336 is set to 1.
Adjust to Kg/cm ² , inflow valve 320-2,321
were gradually opened to allow SiF ₄ /H ₂ gas and N ₂ gas to flow into the flow meters 316 and 317. Subsequently, the outflow valves 325 and 326 were gradually opened, and then the auxiliary valve 340 was gradually opened. At this time
The inflow valves 320-2 and 321 were adjusted so that the ratio of SiF ₄ /H ₂ gas flow rate to N ₂ gas flow rate was 1:90. Next, while watching the reading on the Pirani gauge 341, adjust the opening of the auxiliary valve 340, and
Auxiliary valve 340 until the inside becomes 1×10 ^-2 Torr.
I opened it. After the internal pressure of the chamber 301 becomes stable, the main valve 310 is gradually closed and the Pirani gauge 34 is closed.
The aperture was narrowed down until the instruction in step 1 was 0.5 Torr. The gas inflow is stable, the indoor pressure is constant, and the substrate temperature is
After the temperature stabilized at 200°C, the high frequency power supply 342 was turned on as in Example 1, glow discharge was started with an input power of 60W, and the same conditions were maintained for 1 minute to form an intermediate layer on the substrate. High frequency power supply 342
off state, close the outflow valves 325, 326, 322 while stopping the glow discharge, and then
Open the valve 334 of the SiH ₄ /H ₂ gas cylinder 315 diluted to 10 vol% with H ₂ and check the outlet pressure gauge 33.
Adjust the pressure at 9 to 1Kg/cm ² and gradually open the inflow valve 324 to enter the flow meter 320-1.
SiH ₄ /H ₂ gas was introduced. Subsequently, the outflow valve 329 was gradually opened. Next, the indication of the Pirani gauge 341 is 0.5 Torr as in the case of forming the intermediate layer.
Auxiliary valve 340, main valve 31 so that
0 openings were aligned and stabilized. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was set to 10W, which was lower than before. After continuing the glow discharge for another 5 hours to form a photoconductive layer, the heater 308 is turned off.
After turning off the high frequency power supply 342 and waiting for the substrate temperature to reach 100°C, the outflow valve 329 and the inflow valve 320-2, 321, 32 are turned off.
4 was closed and the main valve 310 was fully opened to bring the inside of the chamber 301 to 10 ^-5 torr or less.The main valve 310 was then closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 344, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 15μ. Regarding this image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the image quality was better when the image was formed using corona discharge than when the image was formed using corona discharge. The image quality was excellent and extremely clear. From this result, it was confirmed that the photoreceptor obtained in this example had a dependence on charging function. Example 5 After forming an intermediate layer on a molybdenum substrate for 1 minute under the same conditions and procedures as in Example 1, the high frequency power source 342 was turned off and the outflow valve was opened with the glow discharge stopped. 325,326
Close and then _PH3 diluted to 25vol ppm with _H2
Gas (hereinafter abbreviated as PH ₃ /H ₂ ) valve 333 of cylinder 314, SiH ₄ /H ₂ diluted to 10 vol% with H 2
Open the valve 334 of the H ₂ cylinder 315, adjust the pressure of the outlet pressure gauges 338, 339 to 1 Kg/cm ² , and gradually open the inflow valves 323, 324 to allow PH ₃ /H ₂ gas into the flow meters 319, 320-1. ,
SiH ₄ /H ₂ gas was introduced. Subsequently, the outflow valves 328, 329 were gradually opened. At this time
PH ₃ /H ₂ gas flow rate and SiH ₄ /H ₂ gas flow rate ratio is 1:
The inflow valves 323 and 324 were adjusted so that the value was 50. Next, in the same way as when forming the intermediate layer, Pirani gauge 3
Auxiliary valve 34 so that the instruction of 41 becomes 0.5torr
0. The opening of the main valve 310 was adjusted and stabilized. Subsequently, the high frequency power supply 342 was turned on again to restart the glow discharge. The input power at that time was 10W. In this way, the glow discharge is further increased by 4
After forming the photoconductive layer for a certain period of time, the heating heater 308 is turned off, and the high frequency power source 342 is also turned off.
After setting the off state and waiting for the substrate temperature to reach 100°C, open the outflow valves 328, 329 and the inflow valve 3.
20-2, 321, 323, 324 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is
After reducing the pressure to below 10 ^-5 torr, the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 344, 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 found that the photoreceptor obtained in this example had charge polarity dependence. Example 6 After forming an intermediate layer on a molybdenum substrate, when subsequently forming a photoconductive layer, the B ₂ H ₆ /H ₂ gas flow rate was set to 1/10 of the SiH ₄ /H ₂ gas flow rate. An intermediate layer and a photoconductive layer were formed on a molybdenum substrate under the same conditions and procedures as in Example 1. 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 superior to images formed by corona discharge, and they were extremely clear. From this result, it was found that the photoreceptor obtained in this example had charge polarity dependence. However, its charge polarity dependence was opposite to that of the image forming members obtained in Examples 4 and 5. Example 7 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, a high frequency power source 342 was applied.
The outflow valves 327 and 329 were closed while the was turned off to stop glow discharge, and the outflow valves 325 and 326 were opened again 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 is the same as when forming the intermediate layer.
It was set to 60W. After continuing the glow discharge for 2 minutes to form an upper layer on the photoconductive layer, the heating heater 308 is turned to the ORR state, and the high frequency power source 342 is also turned off.
After waiting for the substrate temperature to reach 100°C, open the outflow valves 325, 326 and the inflow valve 32.
0-2, 321, 322, 324 are closed, the main valve 310 is fully opened, and the inside of the chamber 301 is
After reducing the pressure to below 10 ^-5 torr, the main valve 310 was closed and the inside of the chamber 301 was brought to atmospheric pressure by the leak valve 344, and the substrate was taken out. The image forming member thus obtained was placed in a charging exposure experimental apparatus similar to that in Example 1, corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a 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 8 Prior to forming the imaging member, the N ₂ gas cylinder 312 of the apparatus shown in FIG. 3 was replaced with a NH ₃ /H ₂ gas cylinder (99.999% purity) diluted to 10 vol % with H ₂ . The surface was then cleaned, Corning
7059 glass (1 mm thick, 4 x 4 cm, brightly polished) on one side by electron beam evaporation.
ITO was deposited to a thickness of 1000 Å and placed on the fixing member 303 of the same device as in Example 1 (FIG. 3) with the ITO deposited surface facing upward. The intermediate layer and photoconductive layer were formed by the same operations and procedures as in Example 1, except that the N ₂ gas cylinder was replaced with an NH ₃ /H ₂ gas cylinder and the molybutin substrate was replaced with an ITO substrate as described above. An image forming member was obtained. The image forming member thus obtained is placed in a charging exposure experiment device,
Corona charging was performed at 6.0 KV for 0.2 seconds, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source, and a light intensity of 1.0 lux.sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a 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. Further, even when the corona charge polarity was changed to 1 and the developer polarity was changed to 1, a clear and good image was obtained in the same manner as in Example 1. Example 9 315 SiH ₄ cylinders diluted to 10 vol% with H ₂ are added to undiluted Si ₂ H ₆ cylinders with 50 vol of H ₂
313 B ₂ H ₆ cylinders diluted to ppm with H ₂
An intermediate layer and a photoconductive layer were formed on a molybdenum substrate under the same conditions and procedures as in Example 1, except that the B ₂ H ₆ cylinder diluted to 500 vol ppm was used, and then taken out of the deposition chamber 301. Similar to 1, image formation was tested by placing the sample in an electrostatic exposure experimental device.
In the case of the 5.5 KV corona discharge, chargeable developer combination, very good quality, high contrast toner images were obtained on the transfer paper. Example 10 Using the apparatus shown in FIG. 4, an intermediate layer was formed on a molybdenum substrate by the following operations. A 0.5 mm thick, 10 cm square molybdenum plate (substrate) 402 whose surface was cleaned was firmly fixed to a fixing member 406 at a predetermined position in the deposition chamber 401 . Board 4
02 is heated with an accuracy of ±0.5° C. by a heater 407 within a fixed member 406. 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 427 is fully opened to exhaust the inside of the chamber 401.
The degree of vacuum was set at approximately 5×10 ^-6 torr. Thereafter, the input voltage of the heater 407 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 425, then the outflow valves 421, 424, and the inflow valves 417, 420 were fully opened, and the insides of the flow meters 432, 435 were also sufficiently degassed to a vacuum state. After closing the auxiliary valve 425, valves 417, 420, 421, 424,
Valve 416 of F ₃ N gas (99.999% purity) cylinder 412 and valve 413 of Ar gas cylinder 409
Open the outlet pressure gauges 428, 431 to 1.
Kg/cm ² , and the inflow valves 417 and 420 were gradually opened to allow F ₃ N gas and Ar gas to flow into the flow meters 432 and 435, respectively. Subsequently, the outflow valves 421 and 424 were gradually opened, and then the auxiliary valve 425 was gradually opened. At this time
The inflow valves 417 and 420 were adjusted so that the F ₃ N gas flow rate ratio was 1:1. Next, the opening of the auxiliary valve 425 was adjusted while observing the reading on the Pirani gauge 436, and the auxiliary valve 425 was opened until the inside of the chamber 401 reached 5×10 ⁻⁴ torr. After the internal pressure of the chamber 401 became stable, the main valve 427 was gradually closed and the opening was throttled until the reading on the Pirani gauge 436 became 1×10 ⁻² torr. Shutter operation rod 403,
After opening the shutter 408 and confirming that the flow meters 432 and 435 are stable, the high frequency power source 437 is turned on to generate a 13.56 MHz signal between the polycrystalline high purity silicon target 404 and the solid member 406. 100W AC power was input. Under these conditions, the layers were formed while performing matching so that stable discharge could continue. Continue discharging in this way for 2 minutes to form a 100 Å thick a-SixN _1-x :
F was formed. Thereafter, the high frequency power supply 437 was turned off to temporarily stop the discharge. Subsequently, the outflow valves 421 and 424 are closed, and the main valve 427
Fully open to remove the gas in chamber 401, and
Vacuum was applied to 10 ^-7 torr. Next, SiH ₄ /H ₂ gas (purity 99.999%) diluted to 10 vol% with H ₂ cylinder 4
10 valve 414 and the valve 415 of the B ₂ H ₆ /H ₂ gas cylinder 411 diluted with H ₂ to 50 vol ppm, the pressure on the outlet pressure gauges 429 and 430 was adjusted to 1 Kg/
cm ² and gradually open the inflow valves 418 and 149 to enter the flow meters 433 and 434.
SiH ₄ /H ₂ gas and B ₂ H ₆ /H ₂ gas were introduced.
Subsequently, the outflow valves 422, 423 were gradually opened, and then the auxiliary valve 425 was gradually opened. At this time, the inflow valves 418 and 14 are adjusted so that the SiH ₄ /H ₂ gas flow rate and B ₂ H ₆ /H ₂ gas flow rate ratio is 50:1.
9 was adjusted. Next, the opening of the auxiliary valve 425 was adjusted while observing the reading on the Pirani gauge 436, and the auxiliary valve 425 was opened until the inside of the chamber 401 reached 1×10 ⁻² torr. After the internal pressure of the chamber 401 became stable, the main valve 427 was gradually closed and the opening was throttled until the reading on the Pirani gauge 436 reached 0.5 torr. After confirming that the gas inflow is stable and the internal pressure is stable, close the shutter 408, then turn on the high frequency power source 437, and turn on the electrode 4.
Between 07 and 408, high frequency power of 13.56MHz was applied to generate glow discharge in the chamber 401, resulting in an input power of 10W. After continuing the glow discharge for 3 hours to form a photoconductive layer, the heating heater 407 is turned off.
After turning off the high frequency power supply 437 and waiting for the substrate temperature to reach 100°C, close the outflow valves 422, 423 and the inflow valves 418, 419, fully open the main valve 427, and open the chamber 40.
After reducing the inside of 1 to 10 ^-5 torr or less, main valve 42
7 was closed, the inside of the chamber 401 was brought to atmospheric pressure by the leak valve 426, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 9μ. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 6.0 KV for 0.2 seconds, and immediately irradiated with a light image. The optical image was created using a tungsten lamp light source, and a light intensity of 0.8 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the component by cascading a chargeable developer (including toner and carrier) onto the surface of the component. When the toner image on the member was transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the image forming member was corona charged at 5.5 KV for 0.2 seconds using a charging exposure experiment device, and image exposure was immediately performed at a light intensity of 0.8 lux sec, after which a charging developer was immediately applied to the surface of the member. When the image was transferred and fixed onto transfer paper, an extremely clear image was obtained. From the above results, it was found that the electrophotographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. Example 11 Six image forming members were formed using the same operations and conditions as in Example 1, and were firmly fixed to a fixing member 406 in the apparatus shown in FIG. 4 with the photoconductive layer facing down.
A substrate 402 was used. Upper layers A to F to be formed on the photoconductive layer were formed on each substrate under the conditions shown in Table 4, and six image forming members having each upper layer were produced. When forming the upper layer A by the sputtering method, the target 404 is a polycrystalline silicon target with a partially laminated graphite target, and when forming the upper layer E, the target is Si ₃ . Ar gas cylinder 409 for _N4 target
was replaced with a _N2 gas cylinder diluted to 50% with Ar. In addition, when forming the upper layer B by the glow discharge method, the B ₂ H ₆ gas cylinder 411 is replaced with a C ₂ H ₄ gas cylinder diluted with H ₂ to 10 vol%, and when forming the upper layer C, the B 2 H 6 gas cylinder 411 is _{2 H6} gas cylinder 411 with _H2 at 10vol%
Add the upper layer D to a Si(CH ₃ ) ₄ cylinder diluted to

[Table] When forming, follow the same steps as when forming upper layer B.
B ₂ H ₆ gas cylinder 411 to C ₂ H ₄ gas cylinder,
F ₃ N gas cylinder 412, SiF ₄ containing 10 vol% H ₂
When forming the upper layer F ₂ G on the gas cylinder, use F ₃ N
The gas cylinders were changed to N ₂ gas cylinders and NH ₃ gas cylinders diluted to 10 vol% with H ₂ . Six image forming members each having the same intermediate layer as in Example 1 and the photoconductive layer having intermediate layers A to F shown in Table 4 were subjected to image formation under the same operations and conditions as in Example 1 to form a transfer paper. When the toner images were transferred to a toner image, extremely clear toner images were obtained that were independent of charging polarity. Example 12 Six image forming members were formed using the same operations and conditions as in Example 8, and were firmly fixed to a fixing member 406 with the photoconductive layer facing down in the apparatus shown in FIG. did. The upper layer formed on the photoconductive layer was formed in the same manner as in Example 11. Six image forming members having upper layers A to F shown in Table 4 were each subjected to the same operations as in Example 1,
When images were formed under these conditions and transferred to transfer paper, very clear toner images were obtained that had no dependence on charging polarity. Example 13 Six image forming members were formed using the same operations and conditions as in Example 10, and were firmly fixed to a fixing member 406 with the photoconductive layer facing down in the apparatus shown in FIG. It was set to 402. Six image forming members each having upper layers A to F shown in Table 4, each having an upper layer formed on the photoconductive layer formed in the same manner as in Example 11, were imaged under the same operating conditions as in Example 1. When the toner images were formed and transferred to transfer paper, extremely clear toner images were obtained that were independent of charging polarity.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic configuration diagrams for explaining the configuration of preferred embodiments of the photoconductive member of the present invention, and FIGS. 3 and 4 each illustrate the manufacture of the photoconductive member of the present invention. FIG. 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 hydrogen atoms, and a photoconductive layer provided between these, from the support side into the photoconductive layer. an intermediate layer having a function of preventing carriers from being injected into the photoconductive layer 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; The photoconductive member is characterized in that the intermediate layer is made of an amorphous material whose constituent elements are silicon atoms, nitrogen atoms, and halogen atoms, and has a layer thickness of 30 to 1000 Å. Photoconductive member. 2. The upper surface of the photoconductive layer is made of an amorphous material that has silicon atoms as its base material and includes at least one of hydrogen atoms and halogen atoms, and at least one of carbon atoms, nitrogen atoms, and oxygen atoms. A photoconductive member according to claim 1, having a top layer of 3. The photoconductive member according to claim 1, which has an upper layer made of an inorganic insulating material or an organic insulating material on the upper surface of the photoconductive layer. 4. The photoconductive member according to claim 1, wherein a surface coating layer having a free surface serving as a charge image forming surface and having a layer thickness of 0.5 to 70 μm is provided on the upper surface of the photoconductive layer.