JPH0473145B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and 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. 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 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 develop as the time passes for the layer to stand 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 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 The layer structure of a photoconductive member having a photoconductive layer composed of "a-Si (H, Photoconductive materials not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially as photoconductive materials for electrophotography. It is based on the findings that the The electrical, optical, and photoconductive properties of the present invention are virtually always stable regardless of the usage environment, are extremely resistant to light fatigue, and do not deteriorate even after repeated use, and are 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 excellent adhesion between a layer provided on a support and the support and between laminated layers, a dense and stable structural arrangement, and a quality layer. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied very effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. Still another object of the present invention is to provide high density images without any image defects or blurring during long-term use.
An object of the present invention is to provide a photoconductive member for electrophotography in which it is possible to easily obtain 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 having high signal-to-noise ratio characteristics and high voltage resistance. The photoconductive member of the present invention includes a support for the photoconductive member, an auxiliary layer made of an amorphous material containing silicon atoms Si as a matrix and nitrogen atoms N as constituent atoms, and a support layer composed of an amorphous material containing nitrogen atoms N as constituent atoms. The first amorphous layer [a-
Si(H,X)], and the first amorphous layer has
A first layer region containing an oxygen atom as a constituent atom and a second layer region containing an atom belonging to a group of the periodic table as a constituent atom, which share at least a part of each other. and is internalized on the support side in contact with the auxiliary layer, where the layer thickness of the second layer region is _tB , and the layer thickness of the first amorphous layer and the second layer region If the difference between the layer thickness t _B and the layer thickness t B is T, then the relationship t _B /(T + t _B )≦0.4 is established, and silicon atoms, carbon atoms, and halogen atoms are formed on the first amorphous material. It is characterized by having a second amorphous layer made of an amorphous material containing 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 good resistance to light fatigue and repeated use, 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 tough 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 a first amorphous layer ( ) 103 and a second amorphous layer ( ) 108 that exhibit 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 has an affinity with both the support 101 and the amorphous layer 103. In addition, it is made of a material having the characteristics described below. The auxiliary layer in the photoconductive member of the present invention has a silicon atom (Si) as a matrix and a nitrogen atom (N) as a constituent atom.
and an amorphous material (hereinafter referred to as "a-SiN (H,
(denoted as “X)”). a-SiN(H,X) is silicon atom Si
An amorphous material whose matrix is a nitrogen atom N and whose constituent atoms are a nitrogen atom N (hereinafter referred to as "a-SiaN _1-a "), an amorphous material whose matrix is a silicon atom Si and whose constituent atoms are a nitrogen atom N and a hydrogen atom H quality material (hereinafter referred to as “a-(SibN _1-b )”)
cH _1-c ), an amorphous material whose constituent atoms are a silicon atom Si as a matrix, a nitrogen atom N, a halogen atom
(SidN _1-d )e(H,X) _1-e ). In the present invention, specific examples of the halogen atom X contained in the auxiliary layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can do it. Layer forming methods when the auxiliary layer is composed of the above-mentioned amorphous material include a glow discharge method, a sputtering method, an ion implantation method, an ion brating method, an 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 and, if necessary, hydrogen atoms and halogen atoms into the auxiliary layer for manufacturing, etc. 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. In order to form an auxiliary layer composed of a-SiN (H, Introducing the raw material gas 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 reduced in pressure to generate a glow discharge in the deposition chamber,
What is necessary is to 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 source gas for introducing nitrogen atoms is If necessary, it 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. 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 . By using a target composed of the following, nitrogen atoms N can be introduced into the auxiliary layer formed. On this occasion,
If the aforementioned raw material gas for introducing nitrogen atoms N is also used, it is easy to control its flow rate and arbitrarily control the amount of nitrogen atoms N introduced into the auxiliary layer. The content of nitrogen atoms N introduced into the auxiliary layer is
The flow rate when the raw material gas for introducing nitrogen atoms N is introduced into the deposition chamber is controlled, or the proportion of nitrogen atoms N contained in the target for introducing nitrogen atoms N is controlled when the target is created. It can be arbitrarily controlled as desired by preparing it as desired, or by preparing both. The starting materials used as raw material gas for supplying Si used in the present invention include Si ₂ H ₄ , Si ₂ H ₆ , Si ₃
Silicon hydride (silanes) in a gaseous state or which can be gasified, such as H ₆ , Si ₄ H ₁₀ , etc., can be effectively used.
SiH ₄ and Si ₂ H ₆ are preferred in terms of supply efficiency. By using these starting materials, it is possible to introduce H as well as Si into the auxiliary layer formed by appropriately selecting the layer forming conditions. In addition to the above-mentioned silicon hydride, halogen atoms
silicon compounds containing so-called halogen atom-substituted silane derivatives, specifically, for example, SiF ₄ , Si ₂
Preferred examples include silicon halides such as F ₆ , SiCl ₄ and SiBr ₄ . Furthermore, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and SiHBr ₃ ,
Gaseous or gasifiable halides containing hydrogen atoms as one of their constituents can also be mentioned as starting materials for supplying Si for the formation of effective auxiliary layers. Even when these silicon compounds containing halogen atoms
can be introduced. In the silicon halide compound containing a hydrogen atom in the above-mentioned starting material, when forming an auxiliary layer, a hydrogen atom H, which is extremely effective in controlling electrical or photoelectric properties, is also introduced at the same time as a halogen atom X is introduced into the layer. Therefore, in the present invention, it is used as a suitable starting material for introducing halogen atom X. In addition to the above-mentioned materials, effective starting materials that serve as raw material gases for introducing halogen atoms X used in forming the auxiliary layer in the present invention include, for example, 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. Starting materials that are effectively used as raw material gases for introducing nitrogen atoms used in forming the auxiliary layer include those containing N as a constituent atom or those containing N.
and H as constituent atoms, such as nitrogen N ₂ , ammonia NH ₃ , hydrazine H ₂ NNH ₂ , hydrogen azide
Mention may be made of gaseous or gasifiable nitrogen such as HN ₃ , ammonium azide NH ₄ N ₅ , nitrogen compounds such as nitrides and azides. In addition to this, halogenated nitrogen compounds such as nitrogen trifluoride F ₃ N and nitrogen tetrafluoride F ₄ N ₂ can be mentioned, since in addition to introducing nitrogen atoms N, halogen atoms X can also be introduced. I can do it. In the present invention, the diluent gas used when forming the auxiliary layer by the glow discharge method or the sputtering method includes so-called rare gases 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 with properties 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 optimum 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 formation of the auxiliary layer requires the composition of atoms constituting each layer, which can be formed continuously in the same system, including the auxiliary layer, amorphous layer, amorphous layer, and even other layers as necessary. Glow discharge method and sputtering method are advantageous because delicate control of ratio and layer thickness is relatively easy compared to other methods, but these layer formation methods When forming an auxiliary layer, discharge power and gas pressure during layer formation can be mentioned as important factors that influence the characteristics of the auxiliary layer formed, as well as the support temperature described above. The discharge power conditions for effectively producing the auxiliary layer with the characteristics necessary to achieve 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. The formation of the auxiliary layer is a critical factor in obtaining 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 in consideration of the above layer formation conditions so that the object of the present invention can be effectively achieved. It is arbitrarily determined according to desire. When the auxiliary layer is composed of a-SiaN _1-a , the content of nitrogen atoms in the auxiliary layer is preferably 1×10 ^-3
~60 atomic%, more preferably 1-50 atomic%,
The value a is preferably 0.4 to 0.99999, more preferably 0.5 to 0.99. In the case of a-(SibN _1-b )cH _1-c , the content of nitrogen atoms N is preferably 1×10 ³
~55 atomic%, more preferably 1-55 atomic%,
The content of hydrogen atoms is preferably 2 to 2.
35 atomic%, more preferably 5 to 30 atomic%, and if expressed as b and c, b is usually 0.43 to 30 atomic%.
0.99999, more preferably 0.43 to 0.99, c usually 0.65 to 0.98, preferably 0.7 to 0.95, and a-
(SidN _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. When expressed as d and e, d is preferably 0.43 to 0.99999, more preferably 0.43 to 0.99,
It is desirable that e is preferably 0.8 to 0.99, more preferably 0.85 to 0.98. The thickness of the auxiliary layer constituting the photoconductive member in the present invention is appropriately determined as desired depending on the thickness of the 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 30 Å to 2 μm, preferably 40 Å to 1.5 μm, and most preferably 50 Å to 1.5 μm. The first amorphous layer ( ) 103 in the photoconductive member 100 shown in FIG. a second layer region 105 containing a group atom), and a second layer region 10
5 and a layer region 107 containing no oxygen atoms or group atoms. The layer region 106 provided between the first layer region O104 and the layer region 107 contains group group atoms but does not contain oxygen atoms. The oxygen atoms contained in the first layer region O104 or the group atoms contained in the second layer region 105 are continuously and uniformly distributed in the layer thickness direction in each layer region, and are supported. Preferably, it is distributed continuously and substantially uniformly in a plane substantially parallel to the surface of body 101. In the photoconductive member of the present invention, such as the example shown in FIG. (corresponds to the surface layer region 107 shown in )
However, it is not necessary to provide a layer region (layer region 106 shown in FIG. 1) that contains group atoms but does not contain oxygen atoms. That is, for example, in FIG. 1, the first layer region 104O and the second layer region 105 may be the same layer region, or the second layer region O104 may be the same layer region. A region 105 may also be provided. In the photoconductive member of the present invention, the first layer region O contains oxygen atoms to provide a high dark resistance and a gap between the first amorphous layer and the auxiliary layer on which the first amorphous layer is directly provided. The focus was on improving the adhesion of the film, and the layer region on the upper surface side was focused on increasing sensitivity by not containing oxygen atoms. In particular, like the photoconductive member 100 shown in FIG.
The amorphous layer 103 includes a first layer region O104 containing oxygen atoms, a second layer region 105 containing group atoms, a layer region 106 containing no oxygen atoms, and oxygen atoms and group atoms. Better results can be obtained in the case of a layer structure having a layer region 107 that does not contain O1 and a layer region shared by the first layer region O104 and the second layer region 105. In the photoconductive member of the present invention, the first layer region O, which constitutes a part of the first amorphous layer and contains oxygen atoms, is partially connected to the auxiliary layer of the amorphous layer. For the purpose of improving adhesion, the second layer region that constitutes a part of the amorphous layer and contains group atoms is, in part, located on the free surface side of the amorphous layer. In order to prevent charge from being injected into the amorphous layer from the support side when the amorphous layer is subjected to charging treatment, the support and the amorphous layer are formed as part of the amorphous layer, respectively. The bonding layer regions are provided in a structure in which at least a portion of the two layers are shared. In addition, in order to more effectively improve the adhesion between the second layer region and the auxiliary layer or the layer region provided directly on the second layer region,
The first layer region O is provided from the contact interface with the auxiliary layer to include the second layer region. It is preferable that the first layer region O is provided in the amorphous layer so as to have a layer structure including layer regions. In the present invention, P (phosphorus), As
(boron), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferably used. In the present invention, the content of group atoms contained in the second layer region is appropriately determined as desired in order to effectively achieve the object of the present invention. , usually 30~5× ¹⁰⁴
atomic ppm, preferably 50 to 1×10 ⁴ atomic
ppm, preferably 100 to 5×10 ³ atomic ppm. The amount of oxygen atoms contained in the first layer region O can be determined as desired depending on the characteristics required of the photoconductive member to be formed, but is usually 0.001 to 50 atoms.
%, preferably 0.002-40atomic%, optimally
A desirable range is 0.003 to 30 atomic%. In the photoconductive member of the present invention, the layer thickness t _B of the layer region containing group atoms (the layer thickness of the layer region 104 in FIG. 1) and the layer thickness t The layer thickness T of the layer area (layer area 106 in FIG. 1) excluding the area is determined so that the relationship thereof satisfies the relational expression shown above, but more preferably It is desirable that the value of the relational expression shown above be 0.35 or less, and optimally 0.3 or less. In the present invention, the layer thickness t _B of the layer region containing group atoms is usually 30 Å to 5 μ, preferably
It is desirable that the thickness be 40 Å to 4 μ, most preferably 50 Å to 3 μ. The sum of the layer thickness T and the layer t _B (T+t _B ) is usually 1 to 100 μm, preferably 1 to 80 μm, and most preferably 2 to 50 μm. The layer thickness _tO of the layer region O containing oxygen atoms is appropriately determined according to the desired purpose in relation to the layer thickness _tB of the layer region sharing at least a part of the layer region. It is desirable to That is, if the purpose is to strengthen the adhesion between a layer region and an auxiliary layer that is in direct contact with the layer region, the layer region O
is only required to be provided at least in the layer region at the end of the layer region on the side of the support, so the layer thickness t O of the layer region _O only needs to be equal to the layer thickness t _B of the layer region at most. Furthermore, if the aim is to strengthen the adhesion between a layer region and a layer region provided directly on the layer region (corresponding to the layer region 107 in FIG. 1), the layer region O is a layer region. It is sufficient that it is provided at least in the end layer region opposite to the side where the support is provided, so the layer thickness t _O of the layer region O only needs to be equal to the layer thickness t _B of the layer region at most. . Furthermore, considering the case where the above two points are satisfied, the layer thickness t O of the layer region _O must be at least equal to the layer thickness t _B of the layer region. It is necessary to have a layer structure in which layer regions are provided. In order to more effectively measure the adhesion between a layer region and a layer region provided directly on the layer region, the layer region O should be extended above the layer region (in the direction opposite to the side on which the support is located). It is preferable to have it present. In the present invention, when a portion containing no oxygen atoms is provided in the end layer region of the amorphous layer on the amorphous layer side, and the layer region O is locally unevenly distributed on the opposite side of the amorphous layer. In this case, the layer thickness _tO can be determined as desired while taking into account the above points, but it is usually 10 Å to 10 μ, preferably 20 Å to 8 μ, and optimally
It is desirable that the thickness be 30 Å to 5 μ. In the photoconductive member 100 shown in FIG. It is provided in order to achieve the purpose of the present invention in terms of usage characteristics, pressure resistance, usage environment characteristics, and durability. In the present invention, since each of the amorphous materials constituting the first amorphous layer and the second amorphous layer has a common constituent element of silicon atoms, there is no problem at the lamination interface. Chemical stability is sufficiently ensured. The second amorphous layer is an amorphous material [a
−(SixC _1-x )yX _1-y , where 0<x, y<1]. The second amorphous layer composed of a-(SixC _{1- x} )y It will 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. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having a photoconductive member, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second amorphous layer to be manufactured. Due to their advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second amorphous layer may be formed by using a glow discharge method and a sputtering method in the same apparatus system. To form the second amorphous layer by the glow discharge method, the raw material gas for forming a-(SixC _1-x )yX _1-y is mixed with a diluent gas at a predetermined mixing ratio as necessary The mixed gas is introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge to remove the deposits already formed on the support. a on the first amorphous layer
−(SixC _1-x )yX _1-y should be deposited. In the present invention, the raw material gas for forming a-(Six _1-x )yX _1-y is a gaseous substance containing at least one of Si, C, and Most gasified substances can be used. When using a raw material gas containing Si as one of Si, C, and X, for example, a raw material gas containing Si as a constituent atom, a raw material gas containing C as a constituent atom, and a raw material gas containing Alternatively, a raw material gas containing Si and a raw material gas containing C and X may be mixed at a desired mixing ratio. or with a raw material gas containing Si as a constituent atom,
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, C, and X. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing C as constituent atoms. In the present invention, preferred halogen atoms X contained in the second amorphous layer are F, Cl,
Br and I, with F and Cl being particularly preferred. In the present invention, the second amorphous layer is a-
Although it is composed of (SixC _1-x )yX _1-y , it can further contain a hydrogen atom. The inclusion of hydrogen atoms in the second amorphous layer makes it possible to share some of the raw material gas types when forming a continuous layer with the first amorphous layer, which reduces production costs. It's convenient. In the present invention, raw material gases that can be effectively used to form the second amorphous layer include those in a gaseous state at room temperature and normal pressure, or substances that can be easily gasified. I can list them. Such substances for forming the second amorphous layer include, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, Examples include simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, methane is a saturated hydrocarbon.
_CH4 , ethane _C2H6 , propane _{C3H6 ,} n _{- butane} n _{- C4H10} , pentane _{C5H12 ,} ethylene hydrocarbons include ethylene _{C2H4 ,} propylene _C3H6 ,
Butene-1C ₄ H ₆ , Butene-2C ₄ H ₆ , Isobutylene
C ₄ H ₆ , pentene C ₅ H ₁₀ , acetylene hydrocarbons include acetylene C ₂ H ₂ , methylacetylene
C ₃ H ₄ , butyne C ₄ H ₆ , simple halogens include halogen gases such as fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl, and HBr; interhalogen compounds include BrF, ClF, _ClF3 ,
ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include BiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃
Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂
Cl ₂ , SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ ,
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₆ ,
Examples include silanes such as Si ₃ H ₈ and Si ₄ H ₁₀ . In addition to these, CCl ₄ , CHF ₃ , CH ₂ H ₂ , CH ₃
Halogen-substituted paraffinic hydrocarbons such as F, CH ₈ Cl, CH ₃ Br, CH ₃ I, and C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ , Si( Alkyl silicides such as C ₂ H ₅ ) ₄ , SiCl (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₃ CH ₃ can also be mentioned as effective. These second amorphous layer forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second amorphous layer formed. They are selected and used as desired during the formation of the second amorphous layer. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiCl can contain halogen atoms. _{A- ( _ _} SixC _1-x )
A second amorphous layer consisting of y(Cl+H) _1-y can be formed. To form the second amorphous layer by the sputtering method, target a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and optionally hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing C and The Si wafer may be sputtered by forming plasma. Alternatively, sputtering can be carried out in a gas atmosphere containing at least halogen atoms by using separate targets for Si and C or by using a single target in which Si and C are mixed. It is accomplished by doing so. C and X, H as necessary
As the material serving as the raw material gas for introduction, the material for forming the second amorphous layer shown in the glow discharge example described above can also be used as an effective material in the sputtering method. In the present invention, the diluent gas used when forming the second amorphous layer by a glow discharge method or a sputtering method includes a so-called rare gas, for example.
Preferred examples include He, Ne, Ar, and the like. The second amorphous layer in the present invention is carefully formed to provide the desired properties. In other words, substances whose constituent atoms are Si, C, X, and optionally H have a structure ranging from crystalline to amorphous depending on the conditions of their creation, and electrical properties ranging from conductivity to semiconductor. In the present invention, a-
(SixC _1-x )yX _1-y is formed, and the conditions for its formation are strictly selected according to desire. For example, if the second amorphous layer is provided with the main purpose of improving voltage resistance, a-(SixC _1-x ) _y Created as a quality material. In addition, when a second amorphous layer is provided with 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 is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. A-(SixC _1-x )yX _1-y is created as a sensitive amorphous material. a-(SixC _1-x ) on the surface of the first amorphous layer
When forming the second amorphous layer consisting of yX _1-y ,
The temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, a-
It is desirable that the temperature of the support during layer formation be strictly controlled so that (SixC _1-x )yX _1-y can be formed as desired. In the present invention, the formation of the second amorphous layer is carried out by selecting an optimal range as appropriate in accordance with the method of forming the second amorphous layer in order to effectively achieve the desired purpose. However, in normal cases, the temperature is preferably 50 to 350°C, preferably 100 to 250°C. The glow discharge method is used to form the second amorphous layer because it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. However, when forming the second amorphous layer using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, is advantageous. Created a-(SixC _1-x )
It is one of the important factors that influences the characteristics of yX _1-y . The discharge power conditions for effectively producing a-(SixC _1-x ) _y
300W, preferably 20-200W. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the support temperature and discharge power for forming the second amorphous layer are preferably in the above-mentioned ranges, but these layer forming factors can be determined independently. The desired characteristic a-(SixC _1-x ) is not determined separately.
It is desirable that the optimum value of each layer formation factor be determined based on mutual organic relationship so that a second amorphous layer consisting of yX _1-y is formed. The amounts of carbon atoms and halogen atoms contained in the second amorphous layer in the photoconductive member of the present invention are as follows:
The conditions for forming the second amorphous layer are also important factors in forming the second amorphous layer that provides the desired properties to achieve the objects of the present invention. The amount of carbon atoms contained in the second amorphous layer in the present invention is usually 1×10 ^-3 to 90 atomic%, preferably 1 to 90 atomic%, and optimally 10 to 80 atomic%.
There are some things that are desirable to be expressed as %. The content of halogen atoms is usually 1 to
It is desirable that the halogen atom content be 20 atomic%, preferably 1 to 18 atomic%, and optimally 2 to 15 atomic%, and photoconductive members produced when the halogen atom content is in this range can be sufficiently applied in practice. It is possible to do so. The content of hydrogen atoms, which may be included as necessary, is usually 19 atomic %, preferably 13 atomic % or less. That is, the previous a-(SixC _1-x )y: x of X _1-y ,
When using y display, x is usually 0.1 to 0.99999, preferably
0.1 to 0.99, optimally 0.15 to 0.9, y usually 0.8 to
0.99, preferably 0.82 to 0.99, most preferably 0.85 to 0.98. When both a halogen atom and a hydrogen atom are included, a-(SixC _1-x )y as before
If expressed as (H+X) _1-y, the numerical range of x and y in this case is almost the same as the case of a-(SixC _1-x )yX _1-y . The numerical range of the layer thickness of the second amorphous layer in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. Furthermore, the thickness of the second amorphous layer has an organic relationship with the thickness of the first amorphous layer 103 depending on the characteristics required for each layer region. It is necessary to decide as appropriate under the following. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The thickness of the second amorphous layer in the present invention is as follows:
Usually 0.003-30μ, preferably 0.004-20μ, optimally
It is desirable that the thickness be 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, 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 ₂ +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 set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the present invention, the first amorphous layer composed of S-Si (H, It is done by law. For example, in order to form an amorphous layer composed of a-Si (H, Introducing a raw material gas for introducing hydrogen atoms H and/or for introducing halogen atoms X into a deposition chamber whose interior can be reduced in pressure,
By generating a glow discharge in the deposition chamber and forming a layer of a-Si (H, good. In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, 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, specific examples of the halogen atom X contained in the amorphous layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. I can list them. 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 ₆ , Si ₄ H ₁₀ is effective. Among these, 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. in gaseous or gasified form. Preferred examples include the halogen compounds obtained. 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,
Gases such as H ₂ and He are introduced into the deposition chamber where an amorphous layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. In some cases, it is possible to form an amorphous layer 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. A layer may be formed by doing so. 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. In order 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,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₂ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective. It can be mentioned as a starting material for forming an amorphous layer. 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 or SiH ₄ , Si ₂ H ₄ , Si ₃
This can also be done by causing a discharge by causing a silicon hydride gas such as H ₆ 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 first amorphous layer of the photoconductive member to be formed is a normal case 1~40atomic
%, preferably 5 to 30 atomic %. To control the amount of hydrogen atoms H and/or halogen atoms X contained in the first amorphous layer, for example, the support temperature or/and the amount used to contain hydrogen atoms H or halogen atoms The amount of starting material to be introduced into the deposition system, the discharge force, etc. may be controlled. To provide a layer region containing group atoms and a layer region O containing oxygen atoms in the amorphous layer,
When forming an amorphous layer by a glow discharge method, a reactive sputtering method, etc., a starting material for introducing group atoms and a starting material for introducing oxygen atoms are used together with the above-mentioned starting materials for forming an amorphous layer. do,
This is accomplished by controlling the amount of the compound contained in the formed layer. When using the glow discharge method to form the layer region O containing oxygen atoms and the layer region O containing group atoms constituting the first amorphous layer, the raw material gas for forming each layer region The starting materials for forming the amorphous layer include those selected as desired from the starting materials for forming the amorphous layer described above, and a starting material for introducing oxygen atoms and/or a starting material for introducing group atoms. 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 layer region O is to be formed, a raw material gas containing silicon atoms Si, a raw material gas containing oxygen atoms O, and hydrogen atoms H or/and halogen atoms X as necessary are used. A raw material gas containing atoms is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms Si and a raw material gas containing oxygen atoms O and hydrogen atoms H are used. This is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms Si as constituent atoms and a raw material gas containing three constituent atoms: silicon atoms Si, oxygen atoms O, and hydrogen atoms H are mixed. It can be used as 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 , nitrogen monoxide NO, nitrogen dioxide NO ₂ , nitrogen monooxide N ₂ O, nitrogen sesquioxide N ₂ O ₃ , Nitrogen tetroxide N ₂ O ₄ , pentoxide N ₂ O ₃ , nitrogen trioxide NO ₃ , silicon atom Si, oxygen atom O, and hydrogen atom H as constituent atoms, such as disiloxane H ₃ SiOSiH ₃ , trioxide Examples include lower siloxanes such as siloxane H ₃ SiOSiH ₂ OSiH ₃ and the like. When a layer region is formed using a glow discharge method, starting materials for introducing group group atoms that can be effectively used in the present invention include PH ₃ , P ₂ H ₄ and the like for introducing phosphorus atoms. Phosphorus hydride, PH ₄ I, PF ₃ ,
_PF5 , _PCl3 . PCl ₅ . Examples include phosphorus halides such as PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ . SbH ₃ , SbF ₃ , SbH 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. 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, the support temperature, It can be arbitrarily controlled by controlling the pressure in the deposition chamber, etc. To form the layer region O containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer, or a Si and
The sputtering may be carried out by targeting wafers containing a mixture of SiO ₂ and sputtering them 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 diluting 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 in the raw material gas shown in the glow discharge example mentioned above is
It can also be used as an effective gas in sputtering. In the present invention, a so-called rare gas, for example
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.
A first amorphous layer 203 has an upper auxiliary layer 202 therein which performs a similar function to the lower auxiliary layer 202-1.
-2. 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, comprising a first amorphous layer 203 and a second amorphous layer 208, the amorphous layer 203
is the first layer region O2 containing oxygen atoms
04, a second layer region 205 containing group atoms, and an upper auxiliary layer 202-2 between the layer region 206 and the layer region 207. The upper auxiliary layer 202-2 strengthens the adhesion between the layer region 205 and the layer region 207, makes the electrical contact uniform at the contact interface between the two, and is provided directly on the layer region 205. This makes the layer quality of the layer region 205 tough. 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 and the amorphous layer 208 are also similar to the amorphous layer 103 and the amorphous layer 10 shown in FIG.
8 and have similar characteristics and functions, and are created using the same layer creation procedure and conditions as in the case of FIG. In the photoconductive member of the present invention, layer region B (layer region 10 in FIG.
6) contains a substance that controls the conduction characteristics, so that the conduction characteristics of the layer region B can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-Si constituting the amorphous layer to be formed is used.
For (H, (Gallium), In (Indium), Tl
(thallium), etc., and B and Ga are particularly preferably used. In the present invention, the content of the substance controlling the conduction properties contained in the layer region B is determined by the conduction properties directly required for the layer region B, or the substance provided in direct contact with the layer region B. It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions and the relationship with the characteristics at the contact interface with the other layer regions. In the present invention, the content of the substance controlling conduction properties contained in layer region B is usually 0.001 to 1000 atomic ppm, preferably 0.05 to 1000 atomic ppm.
500atomic ppm, optimally 0.1-200atomic ppm
It is desirable that this is the case. In order to structurally introduce substances that control the conduction properties, for example atoms of the group group, into the layer region B, the starting materials for introducing the atoms of the group group are introduced in a gaseous state into the deposition chamber during layer formation. It may be introduced together with other starting materials for forming the layer. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as starting materials for introducing such group group atoms, B ₂ H ₆ , B ₄ are used for introducing boron atoms.
Boron hydrides such as H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₄ H ₁₂ , B ₆ H ₁₄ , boron halides such as BF ₃ , BCl ₃ , BBr _3, etc. . In addition, AlCl ₃ , GaCl ₃ ,
Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like can also be mentioned. In the photoconductive member of the present invention, as explained in the example shown in FIG. 1 and FIG. A preferred embodiment is a case in which the layer region O is locally unevenly distributed in the direction of the amorphous layer, but the present invention is not limited thereto. A layer may be formed. In this case, since the amorphous layer must be created to exhibit photoconductivity, the upper limit of the amount of oxygen atoms contained in the layer region O is usually
30atomic%, preferably 10atomic%, optimally
It is desirable to set it to 5 atomic%. In this case as well, the lower limit is of course set to the above value. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 3 shows an example of a photoconductive member manufacturing apparatus. 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 is a PH ₃ gas diluted with He (purity 99.999%, hereinafter abbreviated as PH ₃ /He) cylinder,
304 is SiF ₄ gas diluted with He (purity 99.99
%, hereinafter abbreviated as SiF ₄ /He. ) cylinder, 305 is
NO gas (99.999% purity) cylinder, 306 is C ₂ H ₄
It is a gas cylinder (99.999% purity). It goes without saying that the gases filled in each cylinder are of the type of gas required when forming each layer. For example, when forming an auxiliary layer, the cylinder 306 is filled with NH ₃ gas. I'll try to keep it that way. 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 open 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 and 333, the inlet valves 322 to 326, and the outlet valves 317 to 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 support 337, from the gas cylinder 302
SiH ₄ /He gas, NH ₃ gas from the gas cylinder 306 by opening the valves 322 and 326 and checking the outlet pressure gauge 3.
The pressure of 27, 331 is adjusted to 1 Kg/cm ³ , and the inflow valves 312, 316 are gradually opened to allow the water to flow into the mass flow controllers 307, 311. Subsequently, the outflow valves 317, 321 and the auxiliary valve 33
2 is gradually opened to allow each gas to flow into the reaction chamber 301. SiH ₄ /He gas flow rate and NH ₃ at this time
Adjust the outflow valves 317 and 321 so that the ratio to the gas flow rate becomes the desired value, and adjust the main valve 334 while watching the reading on the vacuum gauge 336 so that the pressure inside the reaction chamber 301 becomes the desired value. Adjust the aperture. Then, the temperature of the support body 337 becomes higher than that of the heating heater 3.
After confirming that the temperature is set in the range of 50 to 400° C. by step 38, the power source 340 is set to the desired power to generate a glow discharge in the reaction chamber 301 to spread the auxiliary layer on the support 337. Form. To introduce halogen atoms into the auxiliary layer to be formed,
For example, in the explanation of creating the auxiliary layer above, instead of SiH ₄ gas, use SiF ₄ gas,
This is done by adding SiF ₄ gas to SiH ₄ 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 can be controlled by controlling the flow rate of NH ₃ gas, and the content of halogen atoms can be controlled by
This is accomplished by adjusting the flow rate of SiF ₄ gas. Next, an example of forming the first amorphous layer on the support 337 will be given. The shutter 342 is closed and connected to be supplied with high voltage power from a power source 340. SiH ₄ /He gas from gas cylinder 302, PH ₃ / from gas cylinder 303
Open the valves 322, 323, 325 for He gas and NO gas from the gas cylinder 305, respectively, adjust the pressure of the outlet pressure gauges 327, 328, 330 to 1 Kg/cm ³ , and inflow valves 312, 313,
Gradually open 315 and install mass flow controller 3.
07,308,310. Subsequently, the outflow valves 317, 318, 320 and the auxiliary valve 332 are gradually opened to supply each gas to the reaction chamber 30.
1. The outflow valves 317 and 31 are adjusted so that the ratio of the SiH ₄ /He gas flow rate, PH ₃ /He gas flow rate, and NO gas flow rate at this time becomes the desired value.
8 and 320, respectively, and the reaction chamber 30.
Vacuum gauge 336 so that the pressure inside 1 reaches the desired value.
Adjust the opening of the main valve 334 while checking the reading. After confirming that the temperature of the support body 337 is set to a desired temperature in the range of 50 to 400°C by the heating heater 338, the power supply 347
is set to a desired power to generate a glow discharge in the reaction chamber 301 to first form a layer region containing boron and oxygen on the support 337. At this time, by blocking the introduction of PH ₃ /He gas or NO gas into the reaction chamber 301 by closing the valve of each corresponding gas introduction pipe, the layer region containing phosphorus or The layer thickness of the layer region containing oxygen can be arbitrarily controlled as desired. After the layer regions each containing phosphorus and oxygen are formed to a desired thickness as described above, the outflow valve 31
By closing each of 8 and 320 and continuing the glow discharge for a desired time, a layer region not containing phosphorus and oxygen is formed to a desired thickness on the layer region containing phosphorus and oxygen, respectively. With this, the formation of the first amorphous layer is completed. In the photoconductive member of the present invention, as described above, the layer region O and the layer region V that constitute the amorphous layer are:
Since at least part of the layer area is shared, when forming the amorphous layer, for example, PH ₃ gas and NO gas are simultaneously introduced into the reaction chamber 301 at a desired flow rate for a desired length of time. It is necessary to provide For example, as described above, PH ₃ gas and NO gas are introduced into the reaction chamber 301 for a desired time from the start of formation of the amorphous layer, and after the elapse of the time, either gas is introduced into the reaction chamber 301. By stopping the introduction into the layer region O or V, another layer region can be provided in either the layer region O or the layer region V. Alternatively, _PH3 gas may be used during the formation of the 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, thereby adding phosphorus and oxygen to the layer region containing either phosphorus or oxygen. It is possible to form a layer region containing both. Also, at this time, by stopping introducing either PH ₃ gas or NO gas into the reaction chamber 301 and continuing to introduce the other gas, a layer containing both phosphorus and oxygen can be formed. A layer region containing either phosphorus or oxygen can be formed on the region. As in the example of photoconductive member 200 shown in FIG.
2-2, during the formation of the amorphous layer 203, a layer similar to the lower auxiliary layer 202-1 formed by the method described above is formed. Therefore, an upper auxiliary layer can be provided in the amorphous layer. For example, the second amorphous layer can be formed on the first amorphous layer as follows. First, open the shutter 342. All gas supply valves are once closed, and the reaction chamber 301 is connected to the main valve 334.
The air is exhausted by fully opening. 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. SiF ₄ /He gas is supplied from the gas cylinder 304 to the reaction chamber 30.
1, 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 target, a second amorphous layer can be formed on the first amorphous layer. The amount of carbon atoms contained in the second amorphous layer can be determined by adjusting the sputter area ratio of the silicon wafer and graphite wafer and the mixing ratio of silicon powder and graphite powder when creating the target. By adjusting it, it can be controlled as desired. Another method for forming the second amorphous layer is to use, for example, SiH ₄ gas, SiF ₄ gas, C ₂
This is accomplished by diluting each of the H ₄ gases with a diluent gas such as He as necessary and flowing the diluted gas into the reaction chamber 301 at a desired flow rate ratio to generate glow discharge according to desired conditions. Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 301. valve 31
In order to avoid gas remaining in the gas piping leading from 7 to 321 into the reaction chamber 301, the outflow valve 31
7 to 321, open the auxiliary valve 332, fully open the main valve 334, and temporarily evacuate the system to a high vacuum, as necessary. Example 1 Using the manufacturing apparatus shown in FIG. 3, layers were formed on an aluminum substrate under the following conditions. The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 5KV 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 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 5KV for 0.2 seconds, and a light image was immediately irradiated. A light image was generated using a tungsten lamp, 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] 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, exposing and developing device, corona charging was performed at 5KV for 0.2 seconds, and a light image was immediately irradiated. A light image was generated using a tungsten lamp, 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 The content ratio of silicon atoms and carbon atoms in the amorphous layer is changed by changing the area ratio of the silicon wafer and graphite when forming the second amorphous layer. An image forming member was produced in the same manner as in Example 3 except for this. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for the image forming member thus obtained, image evaluation was performed.
The results shown in the table were obtained.

[Table] ◎〓Very good ○〓Good △〓Can be practically used ×〓Example that causes image defects 5 Completely the same method as Example 1 except for changing the layer thickness of the second amorphous layer An imaging member was prepared by. 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 methods for forming the auxiliary layer and the amorphous layer were changed as shown in Table 6 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 methods for forming the auxiliary layer and the amorphous layer were changed as shown in Table 7 below. Upon evaluation, good results were obtained.

[Table] Example 8 Using the manufacturing equipment shown in Figure 3, on an Al substrate,
Layer formation was carried out in the same manner as in the examples except that the conditions shown in Table 8 below were used. When the electrophotographic image forming member thus obtained was evaluated in the same manner as in Example 2, good results were obtained.

[Table] Example 9 Using the manufacturing apparatus shown in FIG. 3, a layer was formed on an Al substrate under the conditions shown in Table 9 below. Other conditions were the same as in Example 1. Regarding the image forming member thus obtained, Example 3
When the same evaluation as above was carried out, high quality images were obtained and the product was excellent in durability.

[Table] Example 10 An image forming member was prepared in the same manner as in Example 3, except that the amorphous layer was formed by sputtering under the following conditions. When evaluated, good results were obtained.

[Table] Example 11 Except that the layer creation conditions in the third and fourth layer creation stages of Example 8 were set to the conditions shown in Table 11 below,
Electrophotographic image forming members were produced according to the conditions and procedures shown in Example 8, and evaluated in the same manner as in Example 1. Good results were obtained.

【table】

【table】 [Brief explanation of drawings]

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 schematic layer structure diagram of the photoconductive member of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of an apparatus for manufacturing. 100,200...Photoconductive member, 101,20
1... Support, 102, 202-1, 202-2
...Auxiliary layer, 103,203...First amorphous layer, 104,204...First layer region O, 10
5,205...Second layer region V, 108,208
... second amorphous layer, 109,209 ... free surface.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, an auxiliary layer composed of an amorphous material containing silicon atoms as a matrix and nitrogen atoms as constituent atoms, and an amorphous material containing silicon atoms as a matrix. a first amorphous layer made of a transparent material and exhibiting photoconductivity; the first amorphous layer has a first layer region containing oxygen atoms as constituent atoms; and a second layer region containing atoms belonging to Group Group of the Periodic Table, which are in contact with the auxiliary layer and are internalized toward the support side, sharing at least a part of each other. If the layer thickness of the second layer region is t _B and the difference between the layer thickness of the first amorphous layer and the second layer region t _B is T, then t _B /( A second amorphous layer made of an amorphous material containing silicon atoms, carbon atoms, and halogen atoms as constituent atoms on the first amorphous layer, in which the relationship of T + t _B )≦0.4 is established. A photoconductive member characterized by having: