JPH0410620B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As an image forming member for electrophotography, application to a photoelectric conversion/reading device is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as usage environment characteristics. Although individual improvements have been made in terms of stability, stability over time, and durability, the reality is that there is still room for further improvement in terms of improving overall properties. . For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high darkening resistance at the same time, it has often been observed in the past that residual potential remains during use. When used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon in which an afterimage occurs. In addition, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In some cases, problems may arise in the electrical or photoconductive properties, pressure resistance, and durability of the formed layer. For example, when used as an electrophotographic image forming member, photocarriers generated in the formed photoconductive layer due to light irradiation may not have a sufficient lifespan in the layer, or charges may accumulate from the support side in dark areas. In many cases, the prevention of injection was insufficient. Furthermore, when the layer thickness exceeds 10-odd microns, the layer may lift or peel from the surface of the support, or cracks may occur as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it caused phenomena such as . This phenomenon occurs especially when the support is
There are issues that need to be resolved in terms of stability over time, as often occurs with drum-shaped supports used in the field of electrophotography. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X),
A photoconductive material composed of so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter "a-Si(H,X)" is used as a generic term for these). A photoconductive member designed and produced by specifying the layer structure of the photoconductive member as explained below not only exhibits extremely superior properties in practical use, but also has superior properties compared to conventional photoconductive members. This is based on the discovery that it is superior in all respects when compared, and that it has particularly excellent properties as a photoconductive member for electrophotography. The main object of the present invention is to provide a photoconductive member that is extremely resistant to light fatigue, exhibits excellent durability without causing deterioration even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. 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 comprises a support for the photoconductive member, an auxiliary layer composed of an amorphous material containing silicon atoms as a matrix and nitrogen atoms as constituent atoms, and a periodic A charge injection prevention layer made of an amorphous material containing atoms belonging to group 3 of the Table of Contents as constituent atoms, and an amorphous layer made of an amorphous material containing silicon atoms as a matrix and exhibiting photoconductivity. , the layer thickness t of the charge injection prevention layer is 30 Å or more and less than 0.3 μ, and the amount C _(v) of atoms belonging to group of the periodic table contained in the charge injection prevention layer is 30 atomic ppm or more, or t is 30 Å or more and C _(v) is 30 atomic
It is characterized by being more than ppm and less than 100 atomic ppm. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 has an auxiliary layer 102,
It includes a charge injection prevention layer 103 and an amorphous layer 104 having photoconductivity, and the amorphous layer 104 is formed on the free surface 1.
06. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103, and is designed to have affinity with both the support 101 and the charge injection prevention layer 103. , made of materials described below. The charge injection prevention layer 103 mainly has a function of effectively preventing charge from being injected into the amorphous layer 104 from the support 101 side. Amorphous layer 104
mainly has the function of generating photocarriers in the layer 104 upon irradiation with sensitive light and transporting the photocarriers in a predetermined direction. The auxiliary layer in the present invention is an amorphous material (hereinafter referred to as "a- It is composed of SiN(H,X)). a _{- SiN} (H, An amorphous material (hereinafter referred to as "a-Si _b N _1-b ) _c H _1-c " having an atom (Si) as a host and a nitrogen atom (N) and a hydrogen atom (H) as constituent atoms, An amorphous material (hereinafter referred to as "a-(Si _d N _1-d ) _e (H,
X) _1-e ''). In the present invention, specific examples of the halogen atom (X) contained in the auxiliary layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can list them. Layer forming methods when the auxiliary layer is composed of the above-mentioned amorphous material include glow discharge method, sputtering method, ion implantation method, ion plating method, electron beam method, and the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member that has silicon atoms, and it is easy to introduce nitrogen atoms, hydrogen atoms and halogen atoms as necessary into the auxiliary layer to be manufactured, along with silicon atoms. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the auxiliary layer may be formed by using both the glow discharge method and the sputtering method within the same apparatus system. By glow discharge method, a
- To form an auxiliary layer composed of SiN (H, Then, if necessary, a raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. , a-SiN is deposited on the surface of a predetermined support that has been placed in a predetermined position in advance.
It is sufficient to form an auxiliary layer consisting of (H,X). Further, when forming the auxiliary layer by sputtering method, for example, it is done as follows. Firstly, 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 nitrogen atoms (N) is used. may be introduced into a vacuum deposition chamber where sputtering is performed together with raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as required. Second, as a target for sputtering, a target composed of Si ₃ N ₄ or a Si
Nitrogen atoms (N) are added into the auxiliary layer formed by using two targets, one composed of Si ₃ N ₄ and one composed of Si ₃ N ₄ , or a target composed of Si and Si 3 N 4. can be introduced. At this time, if the aforementioned raw material gas for introducing nitrogen atoms (N) is also used, it is easy to arbitrarily control the amount of nitrogen atoms (N) introduced into the auxiliary layer by controlling its flow rate. It is. The content of nitrogen atoms (N) introduced into the auxiliary layer can be determined by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber. The proportion of nitrogen atoms (N) contained in the target can be controlled as desired by adjusting the proportion of nitrogen atoms (N) contained in the target when preparing the target, or by doing both. . The starting materials used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₃ ,
Gaseous silicon hydride (silanes) such as Si ₄ H ₁₀ , which is in a gaseous state or can be gasified, can be effectively used, especially in terms of ease of handling in layer creation work and good Si supply efficiency. Preferred examples include SiH ₄ and Si ₂ H ₆ . If these starting materials are used, the auxiliary layer formed by appropriately selecting the layer forming conditions will contain
H may also be introduced together with Si. In addition to the above-mentioned hydrogen silicon, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr ₄ and the like can be mentioned as preferred, and furthermore, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be mentioned as starting materials for supplying Si for the formation of effective auxiliary layers. Even when these silicon compounds containing halogen atoms (X) are used, as mentioned above, it is possible to introduce X together with Si into the auxiliary layer formed by appropriately selecting the layer forming conditions. The silicon halide compound containing hydrogen atoms in the starting material contains hydrogen atoms (H ) is also introduced, so it is used as a suitable starting material for introducing a halogen atom (X) in the present invention. In addition to the above-mentioned materials, examples of effective starting materials as raw material gases for introducing halogen atoms (X) used when forming the auxiliary layer in the present invention include halogen atoms such as fluorine, chlorine, bromine, and iodine. Gas, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ ,
Interhalogen compounds such as ICl, IBr, HF, HCl,
Examples include hydrogen halides such as HBr and HI. A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming the auxiliary layer is a starting material that has N as a constituent atom or has N and H as constituent atoms. Gaseous or gasifiable nitrogen, nitrides, such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. and nitrogen compounds such as azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced;
Examples include halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ). In the present invention, the diluent gas used when forming the auxiliary layer by the glow discharge method or sputtering method is a so-called rare gas, such as He, Ne,
Ar and the like can be cited as suitable examples. a-SiN(H,X) constituting the auxiliary layer of the present invention
The function of the auxiliary layer of the amorphous material is to strengthen the adhesion between the support and the charge injection prevention layer, and also to make the electrical contact between them uniform. The auxiliary layer is carefully selected and its manufacturing conditions are strictly selected so that the properties required for the auxiliary layer are imparted as desired. a-SiN having properties suitable for the purpose of the present invention
An important factor in the layer forming conditions for forming the auxiliary layer consisting of (H,X) is the temperature of the support during layer forming. That is, when forming an auxiliary layer made of a-SiN (H, In the present invention, the temperature of the support during layer formation is strictly controlled so that a-SiN(H,X) having the desired properties can be formed as desired. In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the auxiliary layer is selected as appropriate in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is carried out. However, in normal cases, the temperature is 50℃~
The temperature is desirably 350°C, preferably 100°C to 250°C. To form the auxiliary layer, it is possible to continuously form the auxiliary layer, the charge injection prevention layer, the amorphous layer, and even other layers formed on the amorphous layer as necessary in the same system. The glow discharge method and sputtering method are advantageous because it is relatively easy to finely control the composition ratio of atoms constituting each layer and control the layer thickness compared to other methods. However, when forming an auxiliary layer using these layer-forming methods, the discharge power and gas pressure during layer formation are important factors that affect the characteristics of the auxiliary layer created, as well as the support temperature described above. This can be cited as a major factor. The discharge power conditions for effectively producing an auxiliary layer having characteristics for achieving the objects of the present invention with good productivity are usually 1 to 300 W, preferably 2 to 150 W. Further, the gas pressure in the deposition chamber is usually 3×10 ^-3 to 5 Torr, preferably 8×10 ^-3 to
It is desirable to set it to about 0.5 Torr. The amount of nitrogen atoms contained in the auxiliary layer in the photoconductive member of the present invention and the amount of hydrogen atoms and halogen atoms contained as necessary achieve the purpose of the present invention as well as the conditions for producing the auxiliary layer. This is an important factor in forming an auxiliary layer that provides the desired properties. The amount of nitrogen atoms (N), the amount of hydrogen atoms (H), and the amount of halogen atoms contained in the auxiliary layer are determined according to the above layer formation conditions so that the object of the present invention can be effectively achieved. It can be arbitrarily determined according to consideration and desire. When the auxiliary layer is composed of a-Si _a N _1-a , the content of nitrogen atoms in the auxiliary layer is preferably 1×
10 ^-3 to 60 atomic%, more preferably 1 to 50 atomic%
In terms of % and a, it is preferably 0.4 to 0.99999, more preferably 0.4 to 0.99. In the case of a-(Si _b N _1-b ) _c H _1-c , the nitrogen atom (N) content is preferably 1×
10 ^-3 ~55 atomic%, more preferably 1 ~ 55 atomic%
%, the content of hydrogen atoms is preferably 2-
35 atomic%, more preferably 5 to 30 atomic%, and if expressed as b and c, b is usually 0.43 to 30 atomic%.
0.99999, more preferably 0.43 to 0.99, c usually 0.65 to 0.98, preferably 0.7 to 0.95, and a-
(Si _d N _1-d ) _e (H,X) _1-e , the nitrogen atom content is preferably from 1×10 ⁻³ to
The content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is preferably 1 to 60 atomic%, more preferably 1 to 60 atomic%.
The content of hydrogen atoms in this case is preferably 20 atomic%, more preferably 2 to 15 atomic%.
It is desirable that it be 19 atomic % or less, more preferably 13 atomic % or less. If it is shown in d and e,
It is desirable that d is preferably 0.43 to 0.99999, more preferably 0.43 to 0.99, and c is preferably 0.8 to 0.99, more preferably 0.85 to 0.98. The thickness of the auxiliary layer constituting the photoconductive member in the present invention is appropriately determined as desired depending on the thickness of the charge injection prevention layer provided on the auxiliary layer and the characteristics of the charge injection prevention layer. be done. In the present invention, the thickness of the auxiliary layer is usually 30 Å to 2 μm, preferably 40 Å to 1.5 μm, and most preferably 50 Å to 1.5 μm. The charge injection prevention layer constituting the photoconductive member of the present invention has a silicon atom (Si) as its base material, and preferably contains an atom belonging to a group of the periodic table (a group atom) and a hydrogen atom (H) or a halogen atom. (X), or both of these as constituent atoms (hereinafter referred to as "a-Si(V,H,X)"), the layer thickness t and the group atoms in the layer The content C _(v) is
The value is within the range described above. In the present invention, the layer thickness t and the content C _(v) of group atoms of the charge injection prevention layer are more preferably as follows:
40Åt<0.3μ and C _(v) is 40atomic ppm or more, or 40atomic ppmC _(v) <100atomic
ppm and t is 40 Å or more, optimally 50 Å t<
0.3 μ, and C _(v) is 50 atomic ppm or more,
Or, it is preferable that 50 atomic ppmC _(v) <100 atomic ppm and t is 50 Å or more. In the present invention, the atoms belonging to group of the periodic table contained in the charge injection prevention layer are P (phosphorus), As (arsenic), Sb (antimony), B
(bismuth), etc., and P and As are particularly preferably used. To form the charge injection prevention layer composed of a-Si (V, H, X), as in the case of forming the auxiliary layer,
For example, a vacuum deposition method using a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is employed. For example, a-Si(V,
In order to form a charge injection prevention layer composed of H, A raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. , and form a layer made of a-Si (V, H, In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce group atoms. The source gas for sputtering may be introduced into the deposition chamber for sputtering together with a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. In the present invention, the starting materials used as the raw material gas for forming the charge injection prevention layer are the same as the starting materials for forming the auxiliary layer, except for the starting material used as the raw material gas for introducing group atoms. Those are selected and used as desired. In order to structurally introduce group atoms into the charge injection prevention layer, during layer formation, a starting material for introducing group atoms is placed in a gaseous state in a deposition chamber in addition to other materials for forming the charge injection prevention layer. It may be introduced together with the starting material. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing phosphorus atoms include hydrogenated phosphorus such as PH ₃ and P ₂ H ₄ , PH ₄ I,
Examples include phosphorus halides such as PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , PI ₃ and the like. Other than these
AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ ,
SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ ,
BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. In the present invention, the group atoms contained in the charge injection prevention layer to provide charge injection prevention properties are
It is preferable that the charge injection prevention layer be distributed substantially uniformly in a plane substantially parallel to the layer thickness direction (a plane parallel to the surface of the support) and in the layer thickness direction. In the present invention, the content of group atoms introduced into the charge injection prevention layer is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, and the support. It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. In the present invention, the halogen atoms (X) that may be contained in the charge injection prevention layer if necessary include the same ones as described in the description of the auxiliary layer. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for Si supply that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A glow discharge is generated in the deposition chamber to form a layer of a-Si (H, That's fine. In addition, when forming by sputtering, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, as the halogen atom (X) contained in the amorphous layer as necessary, the same halogen atoms (X) as mentioned in the case of the auxiliary layer can be mentioned. In the present invention, the raw material gas for supplying Si used to form the amorphous layer includes SiH ₄ , which was mentioned when explaining the auxiliary layer and the charge injection prevention layer.
Gaseous or gasifiable silicon hydrides (silanes) such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ can be used effectively, and in particular, they are easy to handle in the layer creation process. SiH ₄ , Si ₂ H ₆
are listed as preferred. As in the case of the auxiliary layer, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer in the present invention, such as halogen gas, halides, and halogen atoms. Preferred examples include gaseous or gasifiable halogen compounds such as compounds and halogen-substituted silane derivatives. Further, silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms (Si) and halogen atoms (X) as constituent elements, are also mentioned as effective in the present invention. I can do it. In the present invention, the conductive properties of the amorphous layer can be controlled as desired by containing a substance that controls the conductive properties. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-
P gives P-type conduction characteristics to Si(H,X)
type impurities, specifically atoms belonging to groups of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), Tl
(thallium), among which B and Ga are particularly preferably used. In the present invention, the content of the substance that controls the conduction characteristics contained in the amorphous layer () is determined by the conduction characteristics required for the amorphous layer () or the layer ().
The layer can be appropriately selected depending on the organic relationship, such as the characteristics of other layers provided in direct contact with the layer and the relationship with the characteristics at the contact interface with the other layer. In the present invention, the content of the substance controlling the conduction properties contained in the amorphous layer () is usually 0.001 to 1000 atomic ppm, preferably 0.001 to 1000 atomic ppm.
50.05~500atomic ppm, optimally 0.1~
It is desirable that the content be 200 atomic ppm. In order to structurally introduce substances that control conduction properties, such as group atoms, into an amorphous layer, a starting material for introducing group atoms is introduced in a gaseous state into a deposition chamber during layer formation. It may be introduced together with other starting materials for forming the layer. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlCl ₃ ,
GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the present invention, hydrogen atoms contained in the charge injection prevention layer and the amorphous layer of the photoconductive member to be formed
Amount of (H) or amount of halogen atom (X) or hydrogen atom
The sum of the amounts of (H) and halogen atoms (X) (H+X) is usually 1 to 40 atomic%, preferably 5 to 40 atomic%.
It is desirable to set it to 30 atomic%. To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer,
For example, the temperature of the support, the amount of the starting material used to contain hydrogen atoms (H) or halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. In the present invention, the thickness of the amorphous layer is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 100 μm.
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, 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. Ru. 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, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that the desired photoconductive member is formed, but when flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 differs from the photoconductive member 100 shown in FIG.
An upper auxiliary layer 204 is provided between the charge injection prevention layer 203 and the amorphous layer 205 exhibiting photoconductivity. That is, the photoconductive member 200 includes a support 201 and a lower auxiliary layer 2 laminated in this order on the support 201.
02, charge injection prevention layer 203, upper auxiliary layer 204
and an amorphous layer 205, the amorphous layer 205
has a free surface 206. Upper auxiliary layer 204
This strengthens the adhesion between the charge injection prevention layer 203 and the amorphous layer 205 and makes the electrical contact uniform at the contact interface between both layers. By providing the charge injection prevention layer 203, the layer quality of the charge injection prevention layer 203 is made strong. The lower auxiliary layer 202 and the upper auxiliary layer 204 constituting the photoconductive member 200 shown in FIG.
Auxiliary layer 1 constituting the photoconductive member 100 shown in the figure
Using the same amorphous material as in the case of 02, it is formed by the same layer forming procedure and conditions so as to provide similar properties. The charge injection prevention layer 203 and the amorphous layer 205 have the same characteristics and functions as the charge injection prevention layer 103 and the amorphous layer 104 shown in FIG. 1, respectively, and are formed in the same manner as in the case of FIG. Formed by procedures and conditions. Next, a method for manufacturing a photoconductive member formed by a glow discharge decomposition method will be described. FIG. 3 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. Gas cylinders 302, 303, 304, and 305 in the figure are sealed with raw material gases for forming the respective layers of the present invention. For example, 302 is SiH ₄ gas diluted with He. (Purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 3
03 is _PH3 gas diluted with He (99.999% purity,
Hereinafter abbreviated as PH ₃ /He. ) cylinder, 304 is NH ₃ gas (purity 99.9%) (purity 99.99%) cylinder, 305
is a SiF ₄ gas (purity 99.999%, hereinafter abbreviated as SiF ₄ /He) diluted with He. In order to flow these gases into the reaction chamber 301, the valves 322 to 32 of the gas cylinders 302 to 305 are used.
5. Check that the leak valve 335 is closed, and check that the inflow valves 312 to 315, the outflow valves 317 to 320, and the auxiliary valve 332 are open, and first open the main valve 334 to drain the reaction chamber. 301, and exhaust the inside of the gas pipe.
Next, when the reading on the vacuum gauge 336 reaches approximately 5×10 ^-6 torr, the auxiliary valve 332 and the outflow valve 317
~Close 320. To give an example of forming a layer on the base cylinder 337, SiH ₄ /
He gas and PH ₃ /He gas from the gas cylinder 303, respectively, by opening the valves 322, 323 and adjusting the pressure of the outlet pressure gauges 327, 328 to 1 Kg/cm ² , gradually opening the inflow valves 312, 313, It flows into the mass flow controllers 307 and 308.
Subsequently, the outflow valves 317 and 318 and the auxiliary valve 332 are gradually opened to supply each gas to the reaction chamber 30.
1. At this time, the outflow valves 317 and 318 are adjusted so that the ratio of SiH ₄ /He gas flow rate and PH ₃ /He gas flow rate becomes the desired value, and the vacuum is adjusted so that the pressure inside the reaction chamber becomes the desired value. Total 336
Adjust the opening of the main valve 334 while checking the reading. After confirming that the temperature of the base cylinder 337 is set within the range of 50 to 400°C by the heating heater 338, the power supply 337
40 is set to a desired power to generate glow discharge in the reaction chamber 301 to form a desired layer on the base cylinder. When containing halogen atoms in the layer to be formed, for example,
SiF ₄ /He is further added and sent into the reaction chamber. It goes without saying that all outflow valves other than those for gases required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 301 and the outflow valves 317 to 320 are closed. In order to avoid remaining in the piping leading from to the reaction chamber 301, it is necessary to close the outflow valves 317 to 320, open the auxiliary valve 332, and fully open the main valve 334 to temporarily evacuate the system to a high vacuum. Do it accordingly. Further, during layer formation, the base cylinder 337 is operated by a motor 339 in order to ensure uniform layer formation.
rotates at a constant speed. Examples will be described below. Example 1 A layer was formed on a drum-shaped aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG. The electrophotographic image forming member thus obtained was placed in a copying machine, corona charged at 5 KV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux·sec. The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper, and the transferred image was of excellent quality. Toner remaining on the photosensitive drum without being transferred is cleaned by a rubber blade, and the toner is moved to the next copying process.
Even after repeating this process more than 100,000 times, no layer peeling occurred and the image remained good.

[Table] Example 2 A layer was formed in the same manner as in Example 1 except that the layer thickness and phosphorus content of the charge injection prevention layer were changed. The results are shown in FIG. The evaluation criteria are as follows. ◎ Excellent film strength and extremely good image quality.
Extremely durable for repeated use. 〇 Excellent film strength, good image quality, and the above-mentioned durability. ▲ Film peeling resistance is somewhat good, but image quality (density) is poor in practical use. ○†

Claims (1)

[Claims] 1. A support for a photoconductive member, an auxiliary layer made of an amorphous material containing silicon atoms as a base material and nitrogen atoms as constituent atoms, and an auxiliary layer composed of an amorphous material containing silicon atoms as a base material and atoms belonging to group of the periodic table. a charge injection prevention layer made of an amorphous material containing as constituent atoms, and an amorphous layer made of an amorphous material having silicon atoms as a matrix and exhibiting photoconductivity; When the thickness t of the charge injection prevention layer is 30 Å or more,
the amount C _(v) of atoms belonging to group of the periodic table contained in the charge injection prevention layer is less than 0.3 μ;
30 atomic ppm or more, or the above t is 30 Å
or more, and the above C _(v) is 30 atomic ppm or more.
A photoconductive member characterized by having a content of less than 100 atomic ppm.