JPH0210941B2 - - 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.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as use environment characteristics. In terms of stability, stability over time, and durability, each individual property has been improved, but the reality is that there is still room for further improvement in terms of overall property improvement. be. For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use, and this type of photoconductive member When used repeatedly for a long time, fatigue accumulates due to repeated use, resulting in so-called ghost development, which causes afterimages. When the photoconductive layer is made 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 or voltage resistance of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, or ,
For example, there may be image defects commonly called "white spots" on images transferred to transfer paper, which are thought to be caused by localized discharge breakdown phenomena, or defects that may be caused by rubbing when a blade is used for cleaning, for example. A so-called image defect called "white stripe" may occur. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may occur as the time elapses after it is left in the air after being removed from the vacuum deposition chamber for layer formation. You can win by causing phenomena such as ``happening''. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive material 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), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] "a-Si(H,X)" is used as a generic notation for The photoconductive material produced by this method not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, and is particularly effective as a photoconductive material for electrophotography. This is based on the discovery that it has excellent properties. The electrical, optical, and photoconductive properties of the present invention are virtually always stable regardless of the environment in which it is used, and it is extremely resistant to light fatigue and does not deteriorate even after repeated use, making it durable and durable. The main object of the present invention is to provide a photoconductive member for electrophotography which has excellent moisture resistance 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 for electrophotography having high properties. 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 for electrophotography having excellent electrophotographic properties. Still another object of the present invention is to provide high density images without any image defects or blurring during long-term use.
It is an object of the present invention to provide a photoconductive member for electrophotography that can easily produce high-quality images with clear halftones and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member for electrophotography having high signal-to-noise ratio characteristics and high voltage resistance. The photoconductive member for electrophotography of the present invention includes a support for a photoconductive member for electrophotography (hereinafter referred to as a "photoconductive member"), and an amorphous material having silicon atoms as a matrix and containing nitrogen atoms as constituent atoms. an auxiliary layer made of a solid material, and an amorphous material that has silicon atoms as its base material and contains at least one of hydrogen atoms or halogen atoms as constituent atoms,
a first layer region containing oxygen atoms as constituent atoms; These layer regions share at least a part of each other and are in contact with the auxiliary layer toward the support side, and the layer thickness of the second layer region is tB. If T is the difference between the layer thickness of the amorphous layer and the layer thickness tB of the second layer region, the following relationship holds true: tB/(T+tB)≦0.3. 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 is made of a-Si(H,X) and has an amorphous layer 103 that exhibits photoconductivity. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the amorphous layer 103, and is designed to have affinity with both the support 101 and the amorphous layer 103. , made of a material having the characteristics described below. The auxiliary layer in the photoconductive member of the present invention is based on silicon atoms (Si) and contains nitrogen atoms (N) as constituent atoms, and hydrogen atoms (H) and halogen atoms (X) as necessary. It is made of an amorphous material (hereinafter referred to as "a-SiN(H,X)"). a-SiN(H,X) is silicon (Si)
Amorphous material whose base material is nitrogen atom (N) and constituent atoms (hereinafter referred to as "a-Si _a N _1-a "), whose base material is silicon atom (Si), and nitrogen atom (N) and hydrogen atom Amorphous material whose constituent atoms are (H) (hereinafter referred to as "a")
― (Si _b N _1-b ) _c H _1-c ), a silicon atom (Si) as a base, a nitrogen atom (N), a halogen atom (X), and a hydrogen atom (H) as necessary. Amorphous material whose constituent atoms are (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. To form an auxiliary layer composed of a-SiN (H, N) Introducing the raw material gas for introduction and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) into a deposition chamber whose interior can be made to have a reduced pressure. It is sufficient to generate a glow discharge in a room and form an auxiliary layer made of a-SiN (H, Further, when forming the auxiliary layer by sputtering, the following procedure is performed, for example. 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 necessary. Second, as a sputtering target, a target made of Si ₃ N ₄ , or a target made of Si and a target made of Si ₃ N ₄ , or a target made of Si and Si ₃ N ₄ . Nitrogen atoms (N) can be introduced into the auxiliary layer formed by using a target composed of the following. 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 ₈ ,
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, H as well as Si can be introduced into the formed auxiliary layer by appropriately selecting the layer forming conditions. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ can be mentioned as preferred, and furthermore,
SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ ,
Halogenated silicon hydrides such as SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be cited as starting materials for supplying Si for the formation of effective auxiliary layers. I can do it. Even when these silicon compounds containing halogen atoms (X) are used, X can be introduced together with Si into the auxiliary layer formed by appropriately selecting the layer forming conditions, as described above. Among the above-mentioned starting materials, silicon halide compounds containing hydrogen atoms are hydrogen atoms ( Since H) is also introduced, 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, effective starting materials that serve as raw material gases for introducing halogen atoms (X) used when forming the auxiliary layer in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine. , BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ ,
Interhalogen compounds such as ICl, IBr, HF, HCl,
Examples include hydrogen halides such as HBr and HI. 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, such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (NH ₃ ), ammonium azide (NH ₄ N ₃ ), nitride Nitrogen compounds such as compounds and azides can be mentioned. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Mention may be made of halogenated nitrogen compounds. 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 in this amorphous material is to strengthen the adhesion between the support and the amorphous 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 characteristics suitable for the purpose of the present invention
An important factor in the layer formation conditions for forming the auxiliary layer consisting of (H,X) is the temperature of the support during layer formation. 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. The auxiliary layer can be formed continuously in the same system from the auxiliary layer to the amorphous layer and, if necessary, to other layers formed on the amorphous layer. 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 an auxiliary layer using these layer forming methods, the discharge power and gas pressure during layer formation, as well as the support temperature described above, are
This can be cited as an important factor that influences the characteristics of the auxiliary layer created. 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 300W, preferably 2 to 150W. 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 (X) contained in the auxiliary layer are determined so that the objects of the present invention can be effectively achieved. It is arbitrarily determined according to desire while considering the production conditions. 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 ~
60 atomic%, more preferably 1-50 atomic%, a
It is preferably 0.4 to 0.99999, more preferably 0.5 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, e 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,
d is preferably 0.43 to 0.99999, more preferably 0.43 to 0.99, and c is preferably 0.8
-0.99, more preferably 0.85-0.98. 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 amorphous layer provided on the auxiliary layer and the characteristics of the amorphous layer. be done. In the present invention, the thickness of the auxiliary layer is usually 30A° to 2μ, preferably 40A° to 1.5μ, and optimally 50A° to 1.5μ. The amorphous layer 103 in the photoconductive member 100 shown in FIG. ) a second layer region () 105, and a second layer region () 10
5 and a surface layer region 107 that does not contain oxygen atoms and group atoms. First layer region (O) 104 and surface layer region 107
The layer region 106 provided between the two layers contains group group atoms but no oxygen atoms. The oxygen atoms contained in the first layer region (O) 104 or the group group atoms contained in the second layer region (O) 105 are continuously uniform in the layer thickness direction in each layer region. Preferably, the particles are distributed continuously and substantially uniformly in a plane substantially parallel to the surface of the support 101. In the photoconductive member of the present invention as shown in FIG. 1, the surface portion of the amorphous layer 103 has
It has a layer region (corresponding to the surface layer region 107 shown in FIG. 1) that does not contain oxygen atoms and group group atoms, but it has a layer region that contains group atoms but does not contain oxygen atoms (corresponding to the surface layer region 107 shown in FIG. 1). Layer area 10 shown
6) does not necessarily need to be provided. That is, for example, in FIG.
04(O) and the second layer region () 105 may be the same layer region, or the second layer region () 105 may be provided in the first layer region (O) 104. It's a good thing. In the photoconductive member of the present invention, the first layer region (O) has a high dark resistance due to the inclusion of oxygen atoms, and the amorphous layer is in close contact with the auxiliary layer on which it is directly provided. In addition, efforts were made to further improve moisture resistance, corona ion resistance, and high sensitivity without containing oxygen atoms in the surface layer region. In particular, like the photoconductive member 100 shown in FIG.
The amorphous layer 103 includes a first layer region (O) 104 containing oxygen atoms, a second layer region (O) 105 containing group group atoms, a layer region 106 containing no oxygen atoms, and a layer region 106 containing no oxygen atoms. A surface layer region 107 containing no atoms or group atoms, a first layer region (O) 104 and a second layer region () 1
Better results are obtained in the case of a layer structure having a layer area shared with 05. In the photoconductive member of the present invention, the first layer region (O) that constitutes a part of the amorphous layer and contains oxygen atoms is, in part, due to the close contact with the auxiliary layer of the amorphous layer. For the purpose of improving the properties of the amorphous layer, the second layer region (), which constitutes a part of the amorphous layer and contains group atoms, is, in part, formed on the free surface of the amorphous layer. In order to prevent charge from being injected into the amorphous layer from the support side when charging is performed from the side, the support and the amorphous layer are respectively formed as part of the amorphous layer. The layer region where the two are bonded is provided in a structure in which at least a portion of the layer is shared with each other. In addition, in order to more effectively improve the adhesion between the auxiliary layer of the second layer region () or the layer region provided directly on the second layer region (), it is necessary to The first layer region (O) is provided from the contact interface with the auxiliary layer to include the second layer region (), and extends from the contact interface with the auxiliary layer to above the second layer region (). The second layer area ()
It is preferable that the first layer region (O) is provided in the amorphous layer so as to have a layer structure including the following. In the present invention, the atoms belonging to group of the periodic table contained in the second layer region ( ) constituting the amorphous layer are B (boron), Al (aluminum), Ga ( gallium), In (indium),
Tl (thallium), etc., and particularly preferably used are B and Ga. In the present invention, the content of group atoms contained in the second layer region (2) may be appropriately determined as desired so as to effectively achieve the object of the present invention. ), usually 30~
5×10 ⁴ atomic ppm, preferably 50-1×
10 ⁴ atomic ppm, optimally 100 to 5×10 ³ atomic
It is preferable to set it in ppm. The amount of oxygen atoms contained in the first layer region (O) can be determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001~ 50atomic%, preferably
0.002-40atomic%, optimally 0.003-30atomic%
It is desirable that this is the case. In the photoconductive member of the present invention, the layer thickness tB of the layer region () containing group group atoms and (the first
The layer thickness T of the layer region (layer region 106 in FIG. 1) provided on the layer region () except for the layer region () (layer region 106 in FIG. 1) is the relationship between is determined so as to satisfy the relational expression shown above, but more preferably, the value of the relational expression shown above is 0.35 or less, optimally 0.3 or less. In the present invention, the layer thickness tB of the layer region ( ) containing group atoms is usually 30 Å to 5 μ,
The thickness is preferably 40 Å to 4 μ, most preferably 50 Å to 3 μ. The sum of the layer thickness T and the layer thickness tB (T+tB) is usually 1 to 100 μm, preferably 1 to 80 μm, and most preferably 2 to 50 μm. Layer thickness tO of layer region (O) containing oxygen atoms
It is desirable that the thickness be determined in accordance with the desired purpose in relation to the layer thickness tB of the layer region () that shares at least a part of the layer region.
That is, if the purpose is to strengthen the adhesion between the layer region () and the auxiliary layer that is in direct contact with the layer region (), the layer region (O) is the edge of the layer region () on the side of the support. Since it is sufficient that it is provided at least in the partial layer region, the layer region (O) and the layer thickness tO only need to be equal to the layer thickness tB of the layer region () at most. In addition, if the aim is to strengthen the adhesion between the layer region () and the layer region provided directly on the layer region () (corresponding to the layer region 107 in FIG. 1), the layer region Since it is sufficient that (O) is provided at least in the end layer region of the layer region () opposite to the side where the support is provided, the layer thickness tO of the layer region (O) is at most the layer region ( ) is sufficient for the layer thickness tB. Furthermore, considering the case where the above two points are satisfied, the layer thickness tO of the layer region (O) must be at least equal to the layer thickness tB of the layer region (); O) Layer region in ()
It is necessary to have a layered structure with In order to more effectively measure the adhesion between the layer region () and the layer region provided directly on the layer region (), place the layer region (O) above the layer region () (where the support is It is preferable to extend it in the direction opposite to the side. In the present invention, the layer thickness tO can be appropriately determined as desired while taking into account the above points, but is usually 10 Å to 10 μ, preferably 20 Å to 8 μ, and optimally 30 Å to 5 μ. is desirable. 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. . 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 it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A-Si is introduced into the chamber to generate a glow discharge in the deposition chamber, and the a-Si
A layer consisting of (H,X) may be formed. or,
For example, when forming by sputtering method,
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 hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering. In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
An amorphous layer made of a-Si containing halogen atoms can be formed on an auxiliary layer already provided on a predetermined support. When forming an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber in which an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, an amorphous layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases to form a layer. It may be formed. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form an amorphous layer made of a-Si (H, In the case of the ion plating method, polycrystalline silicon or single crystal silicon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam method (EB method). This can be done by heating and evaporating the flying evaporated material using a method such as the method (method), etc., and passing the flying evaporated material through a predetermined gas plasma atmosphere. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, Hcl, HBr,
Hydrogen halides such as HI, SiH ₂ F ₂ , SiH ₂ I ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also effective amorphous materials. Mention may be made as starting materials for layer formation. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer, so the present invention It is used as a suitable raw material for introducing halogen atoms. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be done by causing a discharge by causing a silicon hydride gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, an amorphous layer made of a-Si(H,X) is formed on the auxiliary layer. Furthermore, a gas such as B ₂ H ₆ can also be introduced for doping with impurities. In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the amorphous layer of the photoconductive member to be formed is usually 1 to 40 atomic
%, preferably 5 to 30 atomic %. Hydrogen atoms (H) contained in the amorphous layer or/
and the amount of halogen atoms (X) can be controlled by, for example, the support temperature or/and the introduction of hydrogen atoms (H) or the starting materials used to contain the halogen atoms (X) into the deposition system. What is necessary is to control the amount of discharge, the discharge force, etc. In order to provide a layer region containing group group atoms ( ) and a layer region containing oxygen atoms (O) in the amorphous layer, when forming the amorphous layer by a glow discharge method, a reactive sputtering method, etc. , a starting material for introducing a group atom and a starting material for introducing an oxygen atom are used together with the above-mentioned starting material for forming an amorphous layer, and the amounts thereof are controlled in the layer to be formed. accomplished by things. When a glow discharge method is used to form the layer region containing oxygen atoms (O) and the layer region containing group atoms () constituting the amorphous layer, the raw materials for forming each layer region. As the starting material to become a gas, a starting material for introducing an oxygen atom or/and a starting material for introducing a group atom is selected as desired from among the starting materials for forming an amorphous layer described above. is added. Such starting materials for introducing oxygen atoms or starting materials for introducing group atoms include gaseous substances or gasified substances whose constituent atoms are at least oxygen atoms or group atoms. Most can be used. For example, if a layer region (O) is to be formed, a raw material gas containing silicon atoms (Si) as constituent atoms,
A raw material gas containing oxygen atoms (O) as constituent atoms and a raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as necessary are mixed at a desired mixing ratio and used. Or, a raw material gas containing silicon atoms (Si) and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) are also mixed at a desired mixing ratio. ,
Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si) and oxygen atoms (O)
and a raw material gas containing three hydrogen atoms (H) as constituent atoms can be used in combination. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms. Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monooxide (N ₂ O ), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si) and oxygen atoms (O )
and a hydrogen atom (H) as constituent atoms, for example,
Disiloxane H ₃ SiOSiH ₃ , Trisiloxane
Examples include lower siloxanes such as H ₃ SiOSiH ₂ OSiH ₃ and the like. When the layer region () is formed using a glow discharge method, B ₂ H ₆ and B ₄ are effectively used in the present invention as starting materials for introducing group group atoms. H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ ,
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ etc. can also be mentioned. The content of group atoms introduced into the layer region ( ) containing group atoms 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 material. It can be arbitrarily controlled by controlling the temperature, the pressure inside the deposition chamber, etc. To form the layer region (O) containing oxygen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer or a SiO ₂ wafer, or a Si
This can be carried out by sputtering a wafer containing a mixture of SiO 2 and SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. 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 amorphous layer 203 is formed therein, a lower auxiliary layer 202-
The second embodiment has an upper auxiliary layer 202-2 that performs the same function as 1. That is, the photoconductive member 200 includes a support 201 and a lower auxiliary layer 2 laminated in this order on the support 201.
02-1, an amorphous layer 203, the amorphous layer 203 has a first layer region (O) 204 containing oxygen atoms and a second layer region (O) 204 containing group atoms. It has a layer region ( ) 205 and an upper auxiliary layer 202-2 between the layer region 206 and the layer region 207. The upper auxiliary layer 202-2 has a layer region () 205
At the same time, by providing the layer region (205) directly on the layer region (205), the adhesion between the layer region (207) and the layer region (207) is strengthened, and the electrical contact at the contact interface between the two is made uniform. The layer quality is strong. A lower auxiliary layer 202-1 and an upper auxiliary layer 202-2 constituting the photoconductive member 200 shown in FIG.
Using the same amorphous material as the auxiliary layer 102 constituting the photoconductive member 100 shown in FIG. It is formed. The amorphous layer 203 is also the same as the amorphous layer 10 shown in FIG.
It has the same characteristics and functions as those shown in FIG. Next, FIG. 3 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. 302, 303, 304, 305, 30 in the diagram
The raw material gas for forming each layer region of the present invention is sealed in the gas cylinder No. 6.
For example, 302 was diluted with He.
SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ /He) cylinder, 303 B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /He) diluted with He cylinder, 304 is _SiF4 gas diluted with He (purity
99.99%, hereinafter abbreviated as SiF ₄ /He. ) cylinder, 30
5 is NO gas (99.999% purity) cylinder, 306 is
It is a _NH3 gas (99.999% purity) cylinder. In order to flow these gases into the reaction chamber 301, valves of gas cylinders 302 to 306, 322 to 3 are used.
26. Check that the leak valve 335 is closed, and check that the inflow valves 312 to 316, the outflow valves 317 to 321, and the auxiliary valve 332 are open, and then first close the main valve 334.
is opened to exhaust the reaction chamber 301 and gas piping.
Next, when the reading on the vacuum gauge 336 reaches approximately 5×10 ^-6 torr, the auxiliary valves 332, 333, inlet valves 322-326, and outlet valves 317-321 are closed. Thereafter, a desired gas is introduced into the reaction chamber 301 by operating the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 301 as prescribed. Next, an example of producing a photoconductive member having a structure similar to that shown in FIG. 1 will be outlined. First, to give an example of forming an auxiliary layer on the base cylinder 337, SiH ₄ /He gas is supplied from the gas cylinder 302 and NH ₃ gas is supplied from the gas cylinder 306 by opening the valves 322 and 326 and adjusting the outlet pressure gauges 327 and 331. The pressure is adjusted to 1 Kg/cm ² , and the inflow valves 312 and 316 are gradually opened to allow the flow into the mass flow controllers 307 and 311. Subsequently, the outflow valves 317, 321 and the auxiliary valve 3
32 and 333 are gradually opened to allow the respective gases to flow into the reaction chamber 301. At this time, the outflow valves 317 and 321 are adjusted so that the ratio of the SiH ₄ /He gas flow rate to the NH ₃ gas flow rate becomes the desired value, and the pressure inside the reaction chamber 301 is adjusted to the desired value. Adjust the opening of the main valve 334 while checking the reading on the vacuum gauge 336. After confirming that the temperature of the base cylinder 337 is set to a temperature in the range of 50 to 400°C by the heating heater 338, the power source 340 is set to the desired power to generate glow discharge in the reaction chamber 301. to form an auxiliary layer on the base cylinder 337 (support). In order to introduce a halogen atom into the auxiliary layer to be formed, for example, in the explanation of the creation of the auxiliary layer above,
Instead of SiH ₄ gas, use SiF ₄ gas or SiH ₄
This is done by adding SiF ₄ gas to the gas to form a layer. The content of nitrogen atoms, hydrogen atoms, and halogen atoms contained in the auxiliary layer can be determined by adjusting the flow rate when introducing the starting material for forming the auxiliary layer containing these atoms into the reaction chamber 301. controlled by. For example, the content of nitrogen atoms is controlled by adjusting the flow rate of NH ₃ gas, and the content of halogen atoms is controlled by adjusting the flow rate of SiF ₄ gas. Subsequently, as described above, the base cylinder 337 is
To give an example of forming a layer region () constituting an amorphous layer on the auxiliary layer formed above, SiH ₄ /He gas is supplied from the gas cylinder 302, and B ₂ H ₆ /He gas is supplied from the gas cylinder 303. , valve 322,3
23 respectively to adjust the pressure of the outlet pressure gauges 327 and 328 to 1Kg/cm ² , and open the inflow valves 312 and 31 respectively.
3 gradually open the mass flow controller 30.
7,308. Subsequently, the outflow valves 317 and 318 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 301. At this time, the outflow valve 31 is adjusted so that the ratio between the SiH ₄ /He gas flow rate and the B ₂ H ₆ /He gas flow rate becomes a desired value.
7 and 318, and also adjust the opening of the main valve 334 while checking the reading on the vacuum gauge 336 so that the pressure inside the reaction chamber 301 reaches the desired value. After confirming that the temperature of the base cylinder 337 is set to a temperature in the range of 50 to 400°C by the heating heater 338, the power supply 340 is turned on and set to the desired power to cause glow discharge in the reaction chamber 301. to form a layer region ( ) on the auxiliary layer. To form the layer region (O), NO gas is used instead of or in addition to the B ₂ H ₆ /He gas used in forming the layer region (O). In the photoconductive member of the present invention, since the layer region (O) and the layer region () constituting the amorphous layer share at least a part of the layer region, the amorphous layer When forming, for example, it is necessary to provide a desired length of time for simultaneously introducing B ₂ H ₆ gas and NO gas into the reaction chamber 301 at desired flow rates.
For example, a desired time from the start of formation of the amorphous layer,
B ₂ H ₆ gas and NO gas are introduced into the reaction chamber 301, and after the elapse of the specified time, either gas is introduced into the reaction chamber 301.
By stopping the introduction into layer 01, another layer region can be provided in either layer region (O) or layer region (). Alternatively, B ₂ H ₆ gas may be used to form an amorphous layer.
Either one of the NO gases is supplied to the reaction chamber 30 for a desired period of time.
1 and then the other is further introduced into the reaction chamber 301 to form a layer for a desired time.
A layer region containing both boron and oxygen can be formed on a layer region containing either boron or oxygen. Also, at this time, by stopping introducing either B ₂ H ₆ gas or NO gas into the reaction chamber 301 and continuing to introduce the other gas, both boron and oxygen can be contained. A layer region containing either boron or oxygen can be formed on the layer region containing either boron or oxygen. Layer region 107 of photoconductive member 100 shown in FIG.
In order to form a layer region corresponding to (), for example, without introducing into the reaction chamber 301 a gas for introducing group atoms, such as B ₂ H ₆ gas, used in forming the layer region () described above. , _{SiH4 gas} , _Si2H6 gas, _SiF4
This is accomplished by introducing a gas or a mixed gas thereof into the reaction chamber 301 when forming the amorphous layer. In the case of a photoconductive member having an upper auxiliary layer 202-2 in the amorphous layer 203, as in the example of the photoconductive member 200 shown in FIG. The upper auxiliary layer can be provided in the amorphous layer by forming the same layer as the lower auxiliary layer 202-1. In the above, it goes without saying that all outflow valves for gases other than those required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is In order to avoid remaining in the piping from the outflow valves 317 to 321 to the reaction chamber 301, the outflow valve 317
321 are closed, the auxiliary valves 332 and 333 are opened, and the main valve 334 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. Also, during layer formation, the base cylinder 337 is operated by a motor 339 in order to ensure uniform layer formation.
rotate at a constant speed. Example 1 A layer was formed on a cylindrical aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG.

[Table] 〓

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, an auxiliary layer made of an amorphous material containing silicon atoms as a matrix and nitrogen atoms as constituent atoms, and a support for a photoconductive member for electrophotography; is made of an amorphous material containing at least either a hydrogen atom or a halogen atom as a constituent atom, and has an amorphous layer exhibiting photoconductivity, the amorphous layer containing oxygen atoms as a constituent atom. and a second layer region containing atoms belonging to group 1 of the periodic table as constituent atoms, which share at least a part of each other and are similar to the auxiliary layer. The layer thickness of the second layer region is
An electrophotographic device characterized in that, where tB is the difference between the layer thickness of the amorphous layer and the layer thickness tB of the second layer region, the following relationship holds: tB/(T+tB)≦0.3. Photoconductive materials for use.