JPH0410624B2 - - 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,
It has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic wave to be irradiated, has fast photocompatibility, and has a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of 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/reading device 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 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 Whether boron atoms, phosphorus atoms, etc. are included as constituent atoms in the photoconductive layer for control purposes, or other atoms are included in order to improve other properties, and how these constituent atoms are contained. In the past, problems may arise in the electrical or photoconductive properties, pressure resistance, and durability of the formed layer. That is, when used as an electrophotographic image forming member, for example, the lifetime of photocarriers generated in the formed photoelectric layer by light irradiation may not be sufficient, or the charge transfer from the support side may occur in dark areas. If the injection is not sufficiently blocked, or if the image transferred to the transfer paper has image defects that are thought to be caused by a localized discharge breakdown phenomenon commonly called "white spots," for example, if a blade is used for cleaning, The so-called image defects, commonly referred to as "white stripes," appeared due to the rubbing.
Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as The layer structure of a photoconductive member having a photoconductive layer composed of "a-Si (H, The photoconductive member produced by this method not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive members in every respect, especially as a photoconductive member for electrophotography. This is based on the discovery that it has extremely 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 that has excellent moisture resistance and has no or almost no residual potential observed. Another object of the present invention is to provide a layer that has excellent adhesion between a layer provided on a support and a support and between each layer of laminated layers, is dense and stable in terms of structural arrangement, and It is an object of the present invention to provide a high quality photoconductive member. 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. The 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 includes a support for the photoconductive member, silicon atoms as a matrix, and constituent atoms.
An auxiliary layer made of an amorphous material containing less than 25 atomic% of nitrogen atoms and hydrogen atoms, and an amorphous material whose base material is silicon atoms and whose constituent atoms are atoms belonging to group 3 of the periodic table. a charge injection prevention layer with a layer thickness of 0.3 to 5μ, a first amorphous layer that is photoconductive and is made of an amorphous material with silicon atoms as a matrix, and the first amorphous layer. on the quality layer,
It is characterized by having a second amorphous layer made of an amorphous material containing silicon atoms and carbon atoms as constituent atoms. 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,
A charge injection prevention layer 103, a first amorphous layer ( ) 104 having photoconductivity, an amorphous material whose constituent atoms are silicon atoms and carbon atoms (hereinafter referred to as "a-Si _x
The _second amorphous layer ( ) 105 is composed of
has a free surface 106. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103, and has affinity with both the support 101 and the charge injection prevention layer 103. It is constructed from the 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. The amorphous layer ( ) 104 generates photocarriers in the layer 104 upon irradiation with sensitive light;
Its main function is to transport the photo carrier in a predetermined direction. The amorphous layer ( ) 105 is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, usage cycle characteristics, and durability. The auxiliary layer in the present invention has a silicon atom SC as a matrix, contains nitrogen atoms and hydrogen atoms as constituent atoms, and has a nitrogen atom content C _CN1 of 25 atomic
% (hereinafter a-(SiaN _1- a))
It is written as bH _1- b. However, it is composed of 0.6<a, 0.65≦b). The auxiliary layer composed of a-(SiaN _1- a) bH ₁ -b can be formed by glow discharge method, sputtering method, ion implantation method, ion plating method, electron beam method, etc. be done. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Although it is relatively easy to control the manufacturing conditions for manufacturing photoconductive members containing silicon atoms, glow discharge has the advantage that it is easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the auxiliary layer to be manufactured. A sputtering method or a sputtering method is preferably employed. Furthermore, in the present invention, the intermediate layer 102 may be formed by using a glow discharge method and a sputtering method in the same apparatus. To form the auxiliary layer by glow discharge method,
a-(SiaN _1- a) bH _1- Mix raw material gas for b formation with dilution gas at a predetermined mixing ratio as necessary, and add to a deposition chamber for vacuum deposition where a support is installed. The introduced gas is turned into gas plasma by causing glow discharge, and a-
It is sufficient to deposit (SiaN _1- a) bH _1- b. In the present invention, as the raw material gas for forming a-(SiaN _1- a) bH _1- b, a gaseous substance containing at least one of Si, N, and H as a constituent atom is a gaseous substance that can be gasified. Most gasified materials can be used. When using a raw material gas with Si as a constituent atom as one of Si, N, and H, for example, a raw material gas with Si as a constituent atom, a raw material gas with N as a constituent atom, and a raw material gas with H as a constituent atom. Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing N and H as constituent atoms may be mixed at a desired mixing ratio. Can be used by mixing. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, the starting materials that can be effectively used as raw material gas for forming the auxiliary layer are:
SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , whose constituent atoms are Si and H
Silicon hydrides such as silanes such as Si ₄ H ₁₀ ,
N as a constituent atom, or N and H as constituent atoms, such as nitrogen (N ₂ ), ammonia (NH ₃ ),
Mention may be made of gaseous or gasifiable nitrogen, such as hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), and nitrogen compounds such as nitrides and azides. In addition to these starting materials for forming the auxiliary layer, H ₂ is of course also effective as a raw material gas for introducing H. To form the auxiliary layer by the sputtering method, a single crystal or polycrystalline Si wafer or
Targeting Si ₃ N ₄ wafers or wafers containing a mixture of Si and Si ₃ N ₄ ,
These may be performed by sputtering in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing N and H, e.g.
H ₂ and N ₂ or NH ₃ are diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases to sputter the Si wafer. Just do it. Alternatively, a gas containing at least H atoms can be produced by using a target other than Si and Si ₃ N ₄ or by using a single target formed by mixing Si and Si ₃ N ₄ . This is done by sputtering in an atmosphere. As a raw material gas for introducing N or H, the starting material gas for forming the auxiliary layer shown in the glow discharge example described above can also be used as an effective gas in the case of sputtering. In the present invention, so-called rare gases such as He, Ne,
Ar and the like can be cited as suitable examples. a-(SiaN _1- a) constituting the auxiliary layer of the present invention
bH _1- b is an auxiliary layer because the function of the auxiliary layer is to strengthen the adhesion between the support and the charge injection prevention layer, and also to make the electrical contact between them uniform. The manufacturing conditions are strictly selected and carefully formed so as to provide the desired characteristics. a- having characteristics suitable for the purpose of the present invention;
An important factor in the production conditions for producing SiaN _1- a) bH _1- b is the temperature of the support during production. That is, on the surface of the support a-(SiaN _1- a) bH _1- b
The temperature of the support during layer formation is an important factor that influences the structure and properties of the layer formed. The temperature of the support during layer formation is strictly controlled so that -(SiaN _1- a)bH _1- b 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℃~
A temperature of 350°C, preferably 100°C to 250°C is desirable. 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. Yes, but
When forming an auxiliary layer using these layer forming methods,
Similar to the support temperature described above, the discharge power and gas pressure during layer formation are created a-(SiaN _1- a)
It is cited as an important factor that influences the characteristics of bH _1- b. The discharge power conditions for effectively forming a-(SiaN _1- a)bH _1- b having the characteristics to achieve the purpose of the present invention with good productivity are usually 1 to 300 W, It is preferably 2 to 100W. The gas pressure in the deposition chamber is usually about 0.01 to 5 Torr, preferably about 0.1 to 0.5 Torr when forming a layer by glow discharge, and usually about 10 ^- 0.0 Torr when forming a layer by sputtering. It is desirable to set it at about ³ to 5×10 ^-2 Torr, preferably about 8×10 ^-3 to 3×10 ^-2 Torr. The amount of nitrogen atoms (N) and hydrogen atoms (H) contained in the auxiliary layer in the photoconductive member of the present invention, as well as the conditions for forming the auxiliary layer, is determined to obtain the desired characteristics to achieve the object of the present invention. This is an important factor in the formation of an auxiliary layer. The amount C(N) of nitrogen atoms (N) contained in the auxiliary layer in the present invention is usually within the above-mentioned value range, but preferably 1×
10 ^-3 ≦C(N)<25, more preferably 1≦C(N)
<25, optimally 10≦C(N)<25. The amount of hydrogen atoms (H) is preferably 2 to 35 atnmic%, most preferably 5 to 30 atnmic%. When expressed as a and b in a-(SiaN _1- a) bH _1- b, the value of a is preferably 0.6<a≦0.99999, more preferably 0.6<a
≦0.99, optimally 0.6<a≦0.9, the value of b is
Preferably, 0.65≦b≦0.98, more preferably 0.7≦b
It is desirable that it be ≦0.95. The numerical range of the layer thickness of the auxiliary layer in the present invention is appropriately determined as desired so as to effectively achieve the object of the present invention. In order to effectively achieve the purpose of the present invention, the thickness of the auxiliary layer is usually 30 Å to 2 μ, preferably
It is desirable that the thickness be 40 Å to 1.5 μ, most preferably 50 Å to 1.5 μ. The charge injection prevention layer 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 an amorphous material (hereinafter referred to as "a-Si (V, H, X)") having both as constituent atoms,
The layer thickness t and the content of group atoms in the layer C(V)
is determined as desired so that the object of the present invention is effectively achieved. The layer thickness t of the charge injection prevention layer in the present invention is preferably 0.3 to 5μ, more preferably 0.5 to 2μ.
It is desirable that the content C(V) of group atoms is 1×10 ² to 1×
¹⁰⁵ atomic ppm, more preferably 5× ¹⁰² to 1
It is desirable to set it to ×10 ⁵ atomic ppm. In order to obtain a synergistic effect between the charge injection prevention layer and the auxiliary layer, it is preferable that the thickness of each layer and the content of Group Group atoms of the periodic table or nitrogen atoms be within the above ranges. This is important in order for the auxiliary layer to exhibit sufficient adhesion and for the charge injection prevention layer to exhibit sufficient charge injection prevention properties. Generally, when the charge injection prevention layer is made thinner, it is preferable to increase the number of Group Group atoms in the periodic table, and when it is made thicker, it is preferable to contain fewer atoms, but in the present invention, the adhesion with the auxiliary layer and the electrical properties After careful consideration, the content of nitrogen atoms in the auxiliary layer was
By setting the thickness to less than 25 atomic% and the thickness of the charge injection prevention layer within the above range, not only can improved adhesion and prevention of charge injection be achieved in a synergistic manner, but also the requirements for photoconductive materials can be achieved. It has been found that many of the desired characteristics can be fully satisfied. 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), Bi
(bismuth), etc., and P and As are particularly preferably used. In the present invention, specific examples of the halogen atom (X) contained in the charge injection prevention layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something. To form the charge injection prevention layer composed of a-Si (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. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level 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 producing a photoconductive member having silicon atoms, as well as group atoms, hydrogen atoms (H) and halogen atoms (X) as necessary in the charge injection prevention layer. The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily introduced. Furthermore, in the present invention, the charge injection prevention layer may be formed by using both the glow discharge method and the sputtering method in the same apparatus system. For example, a-Si(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. a on the surface of the auxiliary layer of a predetermined support that has been placed in a predetermined position and has already been provided with the auxiliary layer.
A layer consisting of -Si (V, H, X) may be formed. In addition, when forming by 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, the raw material gas for introducing group atoms may be replaced with hydrogen atoms as necessary. It may be introduced into a deposition chamber for sputtering together with a gas for introducing (H) or/and halogen atoms (X). The following are effective starting materials for the raw material gas used to form the charge injection prevention layer in the present invention. First, silicon hydride (silanes) in a gaseous state or capable of being gasified, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., is effectively used as the starting material for supplying Si. It is commonly used, especially in terms of ease of layer creation work and good Si supply efficiency.
Preferred examples include SiH ₄ and Si ₂ H ₆ . If these starting materials are used, the auxiliary layer formed by appropriately selecting the layer forming conditions will contain
H may also be introduced together with Si. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Preferred examples include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ ;
SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ ,
Halogen-substituted silicon hydrides such as SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also cited as starting materials for supplying Si for forming an effective charge injection prevention layer. I can do things. 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 charge injection prevention layer formed by appropriately selecting the layer formation conditions. I can do it. 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, examples of effective starting materials as raw material gases for introducing halogen atoms (X) used in forming the auxiliary layer in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine. , BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ ,
Interhalogen compounds such as ICl, IBr, HF, HCl,
Examples include hydrogen halides such as HBr and HI. In order to structurally introduce group atoms into the charge injection prevention layer, during layer formation, 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 introducing such a group atom, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. As a starting material for the introduction of such group atoms,
Specifically, for introducing phosphorus atoms, PH ₃ ,
Hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Examples include phosphorus halides such as PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, 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 as follows:
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. When forming a charge injection prevention layer by sputtering, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, A raw material gas for introducing group atoms may be introduced into a vacuum deposition chamber in which sputtering is performed together with a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. In the present invention, the content of group atoms introduced into the charge injection prevention layer is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, and the support. It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. In the present invention, examples of the halogen atom (X) that may be contained in the charge injection prevention layer as necessary include the same halogen atoms (X) as described in the description of the auxiliary layer. In the present invention, the diluent gas used when forming the charge injection prevention layer by a glow discharge method or a sputtering method is a so-called rare gas, for example.
Preferred examples include He, Ne, Ar, and the like. In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the first amorphous layer () composed of a-Si(H,X). It is made by vacuum deposition method. For example, to form an amorphous layer composed of a-Si (H, At the same time, 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 in the deposition chamber, and a on the charge injection prevention layer that has already been formed on the surface of a predetermined support installed in
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by sputtering, 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, if necessary, an amorphous layer ()
As the halogen atom (X) contained therein, the same ones as mentioned in the case of the auxiliary layer can be mentioned. In the present invention, the raw material gases for supplying Si used to form the amorphous layer () include those mentioned when explaining the auxiliary layer and the charge injection prevention layer.
Silicon hydride (silanes) in a gaseous state or which can be gasified, such as SiH 4 , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H _{10 ,} etc., can be effectively used, especially in layer creation work. SiH ₄ ,
Si ₂ H ₆ is preferred. In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer (), as in the case of the auxiliary layer, such as halogen gas, halides, Preferred examples include halogen compounds in a gaseous state or which can be gasified, such as interhalogen compounds and halogen-substituted silane derivatives. 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 (Si) and a halogen atom (X), can also be mentioned as an effective compound in the present invention. 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 a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium),
Among them, 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.
0.05~500atomic ppm, optimally 0.1~200atomic
It is preferable to set it in ppm. In order to structurally introduce a substance that controls conduction properties, such as a group atom, into an amorphous layer, a starting material for introducing a group atom 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 introducing the subject atom, 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 , InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the charge injection prevention layer and the amorphous layer () of the photoconductive member to be formed, or the amount of hydrogen atoms (H) and halogen The sum (H+X) of the amounts of atoms (X) is usually 1 to 40 atomic %, preferably 5 to 30 atomic %. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer (), for example, the support temperature or/and the hydrogen atoms (H), Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, the diluting gas used when forming the amorphous layer () by the glow discharge method or the sputtering gas used when forming the amorphous layer by the sputtering method includes a so-called rare gas, For example, He, Ne, Ar, etc. can be cited as suitable examples. In the present invention, the layer 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 1.
It is desirable that the thickness be 100μ, preferably 1 to 80μ, optimally 2 to 50μ. In the photoconductive member of the present invention, the second amorphous layer () provided on the first amorphous layer ()
is formed of an amorphous material (a-Si _x C _1-x , where 0<X<1) composed of silicon atoms and carbon atoms, so the amorphous layer ( ) and the second amorphous layer Since each of the amorphous materials forming the crystalline layer (2) has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. a-Second amorphous layer composed of Si _x C _1-x ()
is formed by a sputtering method, an ion plantation method, an ion plating method, an electron beam method, or 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 with silicon atoms, and carbon atoms can be easily introduced into the second amorphous material () to be manufactured. A zuttering method, an electron beam method, or an ion plating method is preferably employed. To form the second amorphous layer by the sputtering method, target a single crystal or polycrystalline Si wafer and a C wafer, or a wafer containing a mixture of Si and C. , these may be performed by sputtering in various gas atmospheres. For example, when using Si wafers and C wafers as targets, He, Ne, Ar
A sputtering gas such as the above may be introduced into a sputtering deposition chamber to form a gas plasma, and the Si wafer and C wafer may be sputtered. Alternatively, by using a single target containing a mixture of Si and C, a gas for sputtering is introduced into the equipment system, and sputtering is performed in the gas atmosphere. will be accomplished. When using the electron beam method, single-crystal or polycrystalline high-purity silicon and high-purity graphite are placed in two evaporation boats, and each is independently co-deposited by an electron beam or simultaneously deposited. Silicon and graphite placed in a boat at a desired mixing ratio may be deposited using a single electron beam. The content ratio of silicon and carbon contained in the second amorphous layer ( ) is controlled in the former case by changing the acceleration voltage of the electron beam with respect to silicon and graphite, and in the latter case In this case, it is controlled by determining the amount of silicon and graft mixed in advance. When using the ion blating method, various gases are introduced into the deposition tank, and a high-frequency electric field is applied to a coil placed around the tank to create a glow, and then Si and C are deposited using the electron beam method. It can be vapor-deposited. The second amorphous layer ( ) in the present invention is carefully formed so as to provide the desired properties. In other words, materials whose constituent atoms are Si and C can have structural forms ranging from crystalline to amorphous, depending on the conditions of their creation, and electrical properties ranging from conductive to semiconductive to insulating. In the present invention, a-Si _x C _1-x having desired properties depending on the purpose is used. As it is formed,
The selection of the production conditions is made strictly according to desire. For example, to provide the second amorphous layer () with the main purpose of improving voltage resistance, a-Si _x C _1-x is an amorphous material that exhibits remarkable electrically insulating behavior in the usage environment Created as. In addition, if a second amorphous layer () is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to some extent, and it will be more effective against the irradiated light. a-Si _x C _1-x is produced as an amorphous material having a certain degree of sensitivity. When forming the second amorphous layer ( ) consisting of a-Si _x C _1-x on the surface of the first amorphous layer ( ), the temperature of the support during layer formation is It is an important factor that influences the structure and properties, and in the _{present invention} , the temperature of the support at the time of layer formation is It is desirable that the In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the second amorphous layer () should be adjusted according to the method of forming the second amorphous layer (). The second amorphous layer () is formed by appropriately selecting an optimal range, preferably 20 to 300°C,
The optimal temperature is preferably 20 to 250°C. In order to form the second amorphous layer (), sputtering is used because fine control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. It is advantageous to adopt the zuttering method or the electron beam method, but when forming the second amorphous layer () using these layer forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. A discharge power of a
It can be cited as one of the important factors that influence the characteristics of -Si _x C _1-x . The discharge power condition for effectively producing a-Si _x C _1-x having the characteristics to achieve the object of the present invention with good productivity is preferably 50W-
250W, optimally 80W to 150W is desirable. In the present invention, the preferable numerical ranges of the support temperature and discharge power for creating the second amorphous layer ( ) include the values in the above-mentioned ranges,
These layer creation factors are not determined independently and separately, but rather the desired characteristics a-Si _x C _1-x
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that a second amorphous layer ( ) consisting of is formed. The amount of carbon atoms contained in the second amorphous layer (2) in the photoconductive member of the present invention is determined as desired to achieve the object of the present invention, similar to the manufacturing conditions of the second amorphous layer (2). This is an important factor in forming a layer that provides the following characteristics. The amount of carbon atoms contained in the second amorphous layer () in the present invention is usually 1×10 ^-3 to 90 atomic based on the sum of silicon atoms and carbon atoms.
%, preferably 1~80atomi%, optimally 10~
A desirable value is 75 atomic%.
That is, if we represent x in a-Si _x C _1-x above, x
is usually 0.1 to 0.99999, preferably 0.2 to 0.99, optimally 0.25 to 0.9. The numerical range of the layer thickness of the second amorphous layer (2) in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the purpose of the present invention. In addition, the layer thickness of the second amorphous layer () is also determined in relation to the amount of carbon atoms contained in the layer () and the layer thickness of the first amorphous layer (). It needs to be appropriately determined as desired based on organic relationships depending on the characteristics required for each layer region. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and productivity. The layer thickness of the second amorphous layer ( ) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ,
The optimum value is 0.005 to 10μ. 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, ceramics, 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. 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 20
4. Comprising a first amorphous layer ( ) 205 and a second amorphous layer ( ) 206, the amorphous layer ( ) 2
06 has a free surface 207. Upper auxiliary layer 20
4 is a charge injection prevention layer 203 and an amorphous layer () 20
5, and uniform electrical contact at the contact interface between both layers.At the same time, by providing the charge injection prevention layer 203 on top of the charge injection prevention layer 203, the charge injection prevention layer 203 It is made to be layered and 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 02, it is formed by similar layering procedures and conditions to provide similar properties. The charge injection prevention layer 203, the amorphous layer () 205, and the amorphous layer () are also
It has the same characteristics and functions as the charge injection prevention layer 103, the amorphous layer () 104, and the amorphous layer () 105 shown in FIG. It is formed as a result. Next, a method for manufacturing a photoconductive member using the vacuum deposition apparatus shown in FIG. 3 will be described. Each gas cylinder 302 to 306 in the figure is sealed with a gas used to form each layer of the present invention. As an example, cylinder 302 contains SiH ₄ diluted with He. Gas (purity
99.999%, hereinafter abbreviated as SiH ₄ /He. ) is cylinder 3
03 contains _PH3 gas diluted with He (purity 99.999
%, hereinafter abbreviated as PH ₃ /He. ) is in cylinder 304.
SiF ₄ gas diluted with He (purity 99.999% or less)
Abbreviated as SiF ₄ /He. ), but cylinder 305 contains NH ₃
Gas (99.999% purity) is in cylinder 306.
Each is filled with gas (99.999% purity).
It goes without saying that the type of gas filled in these cylinders may be changed as appropriate depending on the type of layer to be formed. In order to flow these gases into the reaction chamber 301, the valves 322 to 3 of the gas cylinders 302 to 306 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 33.
4 to exhaust the reaction chamber 301 and gas piping. Next, the reading on the vacuum gauge 336 is approximately 5×10 ^-6 torr.
The auxiliary valve 332 and the outflow valve 3
Close 17-321. 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 outline of an example of producing a photoconductive member having the configuration shown in FIG. 1 will be described. The valve 32 supplies SiH ₄ /He gas from the gas cylinder 302 and NH ₃ gas from the gas cylinder 305.
2,325 open and outlet pressure gauge 327,330
The pressure is adjusted to 1 Kg/cm ² , respectively, and then the inflow valves 312 and 315 are gradually opened to allow the flow into the mass flow controllers 307 and 310, respectively. Subsequently, the outflow valves 317, 32
0. Gradually open the auxiliary valve 332 to allow each gas to flow into the reaction chamber 301. At this time,
The openings of the outflow valves 317 and 320 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 vacuum is adjusted so that the pressure inside the reaction chamber 301 becomes the desired value. Adjust the opening of the main valve 334 while checking the reading of total 336. Then, the temperature of the support body 337 becomes higher than that of the heater 33.
After confirming that the temperature is set in the range of 50 to 400°C by step 8, the power source 340 is set to the desired power to generate glow discharge in the reaction chamber 301, and this glow discharge is maintained for a desired time. An auxiliary layer of a desired thickness is created on the support. The charge injection prevention layer can be formed on the auxiliary layer in the following manner, for example. After the formation of the auxiliary layer is completed, the power supply 340 is turned off to stop the discharge, and once the valves of the entire system of gas introduction piping of the apparatus are closed, the gas remaining in the reaction chamber 301 is discharged to the outside of the reaction chamber 301. to the specified degree of vacuum. After that, SiH ₄ /He gas is supplied from the gas cylinder 302, PH ₃ /He gas is supplied from the gas cylinder 303,
The valves 322 and 323 are opened to adjust the pressures of the outlet pressure gauges 327 and 328 to 1 Kg/cm ² , respectively, and the inflow valves 312 and 313 are gradually opened to allow the fluid to flow into the mass flow controllers 307 and 308, respectively. Subsequently, the outflow valves 317, 318,
The auxiliary valve 332 is gradually opened to allow each gas to flow into the reaction chamber 301. SiH ₄ /He at this time
The outflow valves 317 and 318 are adjusted so that the ratio of the gas flow rate and the PH ₃ /He gas flow rate becomes the desired value, and the reading of the vacuum gauge 336 is adjusted so that the pressure inside the reaction chamber 301 becomes the desired value. Adjust the opening of the main valve 334 while watching. and support 337
After confirming that the temperature of the reaction chamber 3 is set in the range of 50 to 400°C by the heating heater 338, the power supply 340 is set to the desired power and the reaction chamber 3 is heated.
A glow discharge is generated within 0.01 hours, and the glow discharge is maintained for a predetermined period of time to form a charge injection prevention layer of a desired thickness on the auxiliary layer. The first amorphous layer ( ) is formed by using, for example, SiH ₄ /He gas filled in the cylinder 302 and following the same procedure as in the case of the auxiliary layer and the charge injection prevention layer described above. It can be done. In addition to SiH 4 /He gas, the raw material gas species used in forming the first amorphous layer () include SiH ₄ /He gas, and especially
Si ₂ H ₆ /He gas is effective for improving the layer formation rate. To form the second amorphous layer ( ) on the first amorphous layer ( ), for example, the following procedure is performed.
First, open the shutter 342. All gas supply valves are once closed, and the reaction chamber 301 is evacuated by fully opening the main valve 334. A target is provided on the electrode 341 to which high-voltage power is applied, in which a high-purity silicon wafer 342-1 and a high-purity graphite wafer 342-2 are placed in advance at a desired area ratio. Ar gas is introduced into the reaction chamber 301 from the gas cylinder 306, and the internal pressure of the reaction chamber 301 is 0.05~
Adjust the main valve 334 so that the pressure is 1 Torr. By turning on the high voltage power supply 340 and sputtering the first target, the second amorphous layer ( ) can be formed on the first amorphous layer ( ). When containing halogen atoms (X) in the auxiliary layer, the charge injection prevention layer, and the first amorphous layer, the gas used to form each of the layers described above may contain, for example, SiF ₄ /He. is further added to reaction chamber 3.
01. Example 1 Layers were formed on an aluminum substrate using the manufacturing apparatus shown in FIG. 3 under the following conditions. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5 kV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 2 A layer was formed on an Al substrate under the following conditions using the manufacturing apparatus shown in FIG. Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5 kV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the process over 100,000 times.

【table】

[Table] Example 3 A layer was formed on an Al substrate under the following conditions using the apparatus shown in FIG. Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging, exposure and developing device, corona discharge was performed at 5 kV for 0.2 seconds, and a light image was immediately irradiated. A tungsten lamp was used as the light source, and a light intensity of 1.0 lux·sec was irradiated using a transmission type test chart. Immediately thereafter, a charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner image with extremely high density on the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 4 When forming the amorphous layer (), the area ratio of the silicon wafer and graphite was changed to increase the content ratio of silicon atoms and carbon atoms in the second amorphous layer (). An image forming member was prepared in the same manner as in Example 1 except for the following changes. The image forming member thus obtained was subjected to image evaluation after repeating the steps of image formation, development, and cleaning approximately 50,000 times as described in Example 1, and the results shown in Table 4 were obtained.

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur Example 5 An image forming member was prepared in the same manner as in Example 1 except that the thickness of the amorphous layer ( ) was changed. The steps of image formation, development, and cleaning as described in Example 1 were repeated to obtain the following results.

[Table] Example 6 An image forming member was prepared in the same manner as in Example 1, except that the method of forming layers other than the amorphous layer () was changed as shown in the table below. When the evaluation was carried out, good results were obtained.

[Table] Example 7 An image forming member was prepared in the same manner as in Example 1, except that the method of forming layers other than the amorphous layer () was changed as shown in the table below. Upon evaluation, good results were obtained.

[Table] Example 8 In Examples 1, 2, 3, 6, and 7, the conditions and procedures in each example were followed except that the formation of the amorphous layer () was performed under the conditions shown in the table below. Therefore, when an image forming member was prepared and evaluated in the same manner as in each example, good results were obtained.

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are schematic layer configuration diagrams schematically showing the layer structure of preferred embodiments of the photoconductive member of the present invention, and FIG. 3 is a diagram showing the fabrication of the photoconductive member of the present invention. FIG. 100,200...Photoconductive member, 101,20
1...Support, 102,202,204...Auxiliary layer, 104,205...First amorphous layer (),
105,206...second amorphous layer (), 10
6,207...Free surface.

Claims (1)

[Claims] 1. A support for a photoconductive member, an auxiliary layer made of an amorphous material containing silicon atoms as a matrix and less than 25 atomic% of nitrogen atoms and hydrogen atoms as constituent atoms, and a support layer containing silicon atoms as a matrix. , a charge injection prevention layer with a layer thickness of 0.3 to 5μ, which is made of an amorphous material containing atoms belonging to group 3 of the periodic table as constituent atoms, and an amorphous material whose matrix is silicon atoms, a first amorphous layer exhibiting photoconductivity; and a second amorphous layer made of an amorphous material containing silicon atoms and carbon atoms as constituent atoms on the first amorphous layer. A photoconductive member characterized by having a layer.