JPH0456306B2 - - 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 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,
High signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, fast photoresponse formation, and 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 this point, 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. Although individual improvements have been made in terms of stability, stability over time, and durability, the reality is that there is still room for further improvement in terms of improving overall properties. It is. For example, when applied to electrophotographic image forming members, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed 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 the so-called ghost phenomenon, which causes afterimages. 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, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In some cases, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. There were cases where this occurred. 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 ``hydrogenated amorphous silicon''] "a-Si(H,X)" is used as a generic notation for The produced photoconductive member not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive members in all respects, especially as a photoconductive member for electrophotography. It is based on the fact that it has been found to have certain characteristics. The electrical, optical, and photoconductive properties of the present invention are almost unaffected by the usage environment, are always stable, are extremely resistant to light fatigue, do not deteriorate even after repeated use, are highly durable, and have excellent durability. The main objective is to provide a photoconductive member in which no or almost no potential is observed. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. 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 pressure resistance. The photoconductive member of the present invention includes a support for the photoconductive member and an amorphous layer having photoconductivity and made of an amorphous material having silicon atoms as a matrix, The layer is continuous in the layer thickness direction and contains oxygen atoms as constituent atoms at a maximum concentration of 500 atomic ppm or more within a layer thickness of 5 μm from the support side, and the concentration on the surface side is relatively lower than that on the support side, and a first layer region having a region in which the distribution concentration is gradually and continuously reduced; and a second layer region containing atoms belonging to Group Group of the Periodic Table as constituent atoms; The layer region is unevenly distributed in a partial region of the amorphous layer on the support side, and the layer thickness T _B of the second layer region and the layer thickness of the amorphous layer are smaller than the second layer region. It is characterized in that the layer thickness _T of the layer region excluding the layer thickness T has a relationship such that T _B /T≦1. 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, and photoconductive properties, and high 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 properties are stable, it is highly sensitive, and it is highly sensitive.
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. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic structural diagram schematically shown for explaining the layer structure of the photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has a-Si (H,
The amorphous layer 102 has a photoconductive amorphous layer 102 consisting of oxygen atoms as constituent atoms in a distribution state that is continuous in the layer thickness direction and is distributed more toward the support 101. a first layer region containing
It has a layer structure configured to have (O) 103 and a second layer region ( ) 104 containing a second atom as a constituent atom. In the example shown in Figure 1,
The first layer region (O) 103 is the second layer region () 10
4, the first layer region
(O) 103 and the second layer region () 104 are present below the surface of the amorphous layer 102. The upper layer region 105 of the amorphous layer 102 does not contain oxygen atoms, which are considered to be factors that affect humidity resistance and corona ion resistance. Contained only in 1st
The layer region (O) 103 has a high dark resistance due to the inclusion of oxygen atoms, and the amorphous layer 10 with the support 101.
2, the upper layer region 1
In 05, high sensitivity is focused on without containing oxygen atoms. Oxygen atoms contained in the first layer region (O) 103 are continuously and non-uniformly distributed in the layer thickness direction, and are distributed between the support 101 and the amorphous layer 102.
In the plane parallel to the interface with the first layer region (O) 103, the first layer region (O) 103 has a substantially uniform distribution. In the present invention, the group atoms contained in the second layer region ( ) 104 that constitutes the amorphous layer 102 and contain group atoms include B (boron),
These include Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. In the present invention, the second layer region ( ) 104
The group atoms contained in the support 101 are distributed substantially uniformly in the layer thickness direction and in a plane parallel to the surface of the support 101. The layer thickness of the first layer region (O) 103 and the upper layer region 105 is one of the important factors for effectively achieving the object of the present invention. Great care must be taken in the design of the photoconductive member to ensure that the properties are adequate. In the present invention, the upper limit of the layer thickness T _B of the second layer region ( ) 104 is usually 50 μm or less, preferably 30 μm or less, and optimally 10 μm or less. Further, the lower limit of the layer thickness T _B of the upper layer region 105 is usually 0.5 μ or more, preferably 1 μ or more, and optimally 3 μ or more. The lower limit of the layer thickness T _B of the second layer region ( ) 104 and the upper limit of the layer thickness T of the upper layer region 105 are determined by the characteristics required for both layer regions and the characteristics required for the entire amorphous layer 102. It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the two. In the present invention, the lower limit of the layer thickness T _B and the upper limit of the layer thickness T are usually set to appropriate values for each, so as to satisfy the relationship T _B /T≦1. selected. In selecting the numerical values of layer thickness T _B and layer thickness T, more preferably T _B /T≦0.9, optimally T _B /T≦
Layer thickness T _B and layer thickness T so that the relationship 0.8 is satisfied
It is desirable that the value of . In the photoconductive member of the present invention shown in FIG.
Second layer region 104 containing group atoms
Although the first layer region 103 is formed therein, the first layer region (O) 103 and the second layer region (O) may be the same layer region. Further, the case where the second layer region ( ) is formed within the first layer region O can also be cited as one of the preferred embodiments. The amount of oxygen atoms contained in the first layer region (O) can be determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001 to 50 atomic%. , preferably 0.002~
It is desirable that the content be 40 atomic%, optimally 0.003 to 30 atomic%. If the layer thickness T ₀ of the first layer region (O) is sufficiently thick or the ratio of the amorphous layer to the total layer thickness exceeds two-fifths or more, the first layer region (O ), the upper limit of the amount of oxygen atoms contained in
30 atomic% or less, preferably 20 atomic% or less,
Optimally, it is desirable to set it to 10 atomic% or less. In the present invention, the thickness of the amorphous layer is as follows:
From the viewpoint of obtaining desired electrophotographic properties and economical efficiency, the thickness is usually 1 to 100 µm, preferably 1 to 80 µm, and most preferably 2 to 50 µm. 2 to 10 show the distribution state of oxygen atoms in the layer thickness direction contained in the layer region (O) containing oxygen atoms constituting the amorphous layer of the photoconductive member of the present invention. A typical example is shown. In the examples shown in FIGS. 2 to 10, the layer region () containing group atoms may be the same layer region as the layer region (O) or include the layer region (O). , or a part of the layer region (O) may be shared, so in the following explanation, for the layer region () containing group atoms,
Do not mention unless specific explanation is required. 2 to 10, the horizontal axis represents the distribution concentration C of oxygen atoms, and the vertical axis represents the layer region (O) that constitutes the amorphous layer exhibiting photoconductivity and contains oxygen atoms. The thickness t is shown, t _B is the position of the interface on the support side, and t _T is the position of the interface on the opposite side to the support side. That is,
The layer region (O) containing oxygen atoms is formed as a layer from the t _B side toward the t _T side. In the present invention, the layer region (O) containing oxygen atoms is a-Si(H,X) constituting the photoconductive member.
occupies a part of the amorphous layer that exhibits photoconductivity. In the present invention, the layer region (O) is preferably provided in the lower layer region of the amorphous layer 102 including the surface of the amorphous layer on the support 101 side, as shown in the example of FIG. It is. FIG. 2 shows a first typical example of the distribution state of oxygen atoms contained in the layer region (O) in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B to the position t ₁ where the surface where the layer region (O) containing oxygen atoms is formed and the surface of the layer region (O) are in contact, oxygen is present. While the distribution concentration C of atoms takes a constant value of _C1 , oxygen atoms are contained in the layer region (O) where they are formed, and the position
From t ₁ onwards, the distribution concentration C gradually and continuously decreases from C ₂ until reaching the interface position t _T . At the interface position _tT , the distribution concentration C of oxygen atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the contained oxygen atoms gradually and continuously decreases from C ₄ to position t _T from position t _B to position t _T.
A distribution state such as C ₅ is formed. In the case of Fig. 4, the distribution concentration C of oxygen atoms is constant at _C6 from position t _B to position t ₂ , and at position t ₂
It is gradually and continuously decreased between and the position _tT , and becomes substantially zero at the position _tT . In the case of Figure 5, the oxygen atom is located at a position lower than position t _B.
Until t _T , the distribution concentration C is gradually decreased continuously from C ₈ and becomes substantially zero at the position t _T . In the example shown in FIG. 6, the distribution concentration C of oxygen atoms is a constant value of _C9 between position _tB and position _t3 , and _C10 at position _tT . position t ₃
and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of _C11 from position _tB to position _t4 , and
From t ₄ to position t _T, the distribution state decreases linearly from C ₁₂ to C ₁₃ . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of oxygen atoms decreases linearly from C ₁₄ to zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C of oxygen atoms decreases linearly from C ₁₅ to C ₁₆ , and between position t ₅ and t _T. , C ₁₆ are shown as constant values. In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is C ₁₇ at position t _B , and gradually decreases from this C ₁₇ until reaching position t ₆ ,
Near the position of t ₆ , the position is rapidly decreased and
C ₁₈ at t ₆ . Between position t ₆ and position t ₇ , the distribution concentration C
is decreased rapidly at first, and then slowly and gradually decreased to C ₁₉ at position t ₇ , and between positions t ₇ and t ₈ , it is decreased very gradually and gradually to position t ₈ . , reaching C ₂₀ . Position with position t ₈
During t _T , the distribution concentration C is reduced from C ₂₀ to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of oxygen atoms contained in the layer region (O) in the layer thickness direction, in the present invention, on the support side , a layer region containing oxygen atoms in a distributed state, which has a portion where the distribution concentration C of oxygen atoms is high, and has a portion where the distribution concentration C is relatively lower on the interface _tT side than on the support side.
(O) is provided in the amorphous layer. In the present invention, the layer region (O) containing oxygen atoms constituting the amorphous layer is the localized region (A) containing oxygen atoms at a relatively high concentration toward the support side as described above. ), and in this case, the adhesion between the support and the amorphous layer can be further improved. If the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (A) be provided within 5 μm from the interface position t _B. In the present invention, the localized region (A) may be the entire layer region L _T up to 5μ thick from the interface position t _B , or may be a part of the layer region L _T. be. Whether the localized region (A) is a part or all of the layer region L _T is appropriately determined according to the characteristics required of the amorphous layer to be formed. The local region (A) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of oxygen atoms is usually 500 atomic ppm or more, preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more.
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the maximum value Cmax of the distribution concentration C exists in the layer region (O) containing oxygen atoms, within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B) . It is desirable that it be formed as follows. In the present invention, the content of group atoms contained in the layer region () containing oxygen atoms is appropriately determined as desired so as to effectively achieve the object of the present invention. Usually 0.01~5×
10 ⁴ atomic ppm, preferably 0.5 to 1×10 ⁴ atomic
ppm, preferably 1 to 5×10 ³ atomic ppm. 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, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The support may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 shown in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for Si supply that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A-Si(H,
What is necessary is to form a layer consisting of. In addition, when forming by sputtering, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₂ , 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 a predetermined support. When forming an amorphous layer containing halogen atoms according to the glow discharge method, basically silicon halide gas, which is a raw material gas for supplying Si, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber in which an amorphous layer is to be formed at a predetermined mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases. Therefore, an amorphous layer can be formed on a predetermined support, but in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is also mixed with these gases to form a layer. It may be formed. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form an amorphous layer 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 a deposition chamber for sputtering to form a plasma atmosphere of the gas. Just do it. 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 and HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc., and halides that have a hydrogen atom as one of their constituents in a gaseous state or can be gasified are also included. It can be mentioned as an effective starting material for forming an amorphous layer. These halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or optical properties, at the same time as halogen atoms are introduced into the layer when forming an amorphous layer. It is used as a suitable raw material for introducing halogen atoms. In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
This can also be done by causing a discharge by causing a hydrogen silicon gas such as Si ₃ H ₈ or Si ₄ H ₁₀ to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. As a result, an amorphous layer made of a-Si(H,X) is formed on the support. Furthermore, it is also possible to introduce a gas such as B ₂ H ₆ to also serve as impurity doping. 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 contained in the amorphous layer of the photoconductive member to be formed is usually 1 ~40 atomic%, preferably 5~
It is desirable to set it to 20 atomic%. To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer, for example, the support temperature and/or the hydrogen atoms (X) or halogen atoms (X) What is necessary is to control the amount of the starting material used to contain the material introduced into the deposition system, the discharge force, etc. In order to provide a layer region containing group group atoms ( ) and a layer region containing oxygen atoms (O) in the amorphous layer, when forming the amorphous layer by a glow discharge method, a reactive sputtering method, etc. , a starting material for introducing a group atom and a starting material for introducing an oxygen atom are used together with the above-mentioned starting material for forming an amorphous layer, and the amounts thereof are controlled in the layer to be formed. accomplished by things. Layer region containing oxygen atoms (O) and layer region containing group atoms () constituting the amorphous layer
When using the glow discharge method to form each layer, the starting materials that serve as the raw material gas for forming each layer region are:
A starting material for introducing oxygen atoms and/or a starting material for introducing group atoms is added to those selected as desired from among the starting materials for forming an amorphous layer described above. Such starting materials for introducing oxygen atoms or starting materials for introducing group atoms include gaseous substances containing at least oxygen atoms or group atoms, or gasified substances that can be gasified. Most can be used. For example, if a 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 a raw material gas whose constituent atoms are halogen atoms (X) at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen. atom
A raw material gas containing (H) as a constituent atom is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and oxygen atoms ( It is possible to use a mixture of a raw material gas having three constituent atoms: O) and hydrogen atoms (H). Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monooxide (N ₂ O ), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si) and oxygen atoms (O )
For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) having a hydrogen atom (H) and a hydrogen atom (H) as constituent atoms can be mentioned. When the layer region () is formed using a glow discharge method, B ₂ H ₆ and B ₄ are effectively used in the present invention as starting materials for introducing group group atoms. _H10 , _{B5H9 , B5H11 ,}
Boron hydride such _{as B6H10} , _B6H12 , _{B6H14 , BF3 ,}
Examples include boron halides such as BCl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ etc. can also be mentioned. The content of group atoms introduced into the layer region ( ) containing group atoms is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, the support It can be arbitrarily controlled by controlling the temperature, the pressure inside the deposition chamber, etc. To form a layer region (O) containing oxygen atoms by sputtering, a single crystal or polycrystalline
Si wafer or _SiO2 wafer or 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 diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, by using a target other than Si and SiO ₂ or a mixed target of Si and SiO ₂ , it is possible to use a sputtering gas in an atmosphere of diluent gas or at least hydrogen. This is accomplished by sputtering in a gas atmosphere containing atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, the dilution 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 include so-called rare gases, e.g.
Preferred examples include He, Ne, Ar, and the like. Next, an outline of an example of a method for manufacturing a photoconductive member produced by a glow discharge decomposition method will be explained. FIG. 11 shows an example of an apparatus for manufacturing photoconductive members using the glow discharge decomposition method. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming each layer region of the present invention is sealed, and as an example, 11
02 is SiH ₄ gas diluted with He (purity 99.999
%, hereinafter abbreviated as SiH ₄ /He. ) cylinder, 1103
1104 is a cylinder of B ₂ H ₆ gas diluted with He (purity 99.999%, hereinafter referred to as B ₂ H ₆ /He), and 1104 is a cylinder of Si ₂ H ₆ gas diluted with He (purity 99.99%, hereinafter referred to as B 2 H 6 /He).
Abbreviated as Si ₂ H ₆ /He. ) cylinder, 1105 is NO gas (purity 99.999%) cylinder, 1106 is SiF ₄ gas diluted with He (purity 99.999%, hereafter SiF ₄ /
Abbreviated as He. ) It is a cylinder. In order to cause these gases to flow into the reaction chamber 1101, the valves of gas cylinders 1102 to 1106, 11
22 to 1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112
~1116, confirming that the outflow valves 1117~1121 and auxiliary valves 1132, 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and gas piping. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valve 1
Close 117-1121. Next _, to give an example of forming a photoconductive member having an amorphous layer having the layer structure shown in FIG.
B ₂ H ₆ /He gas from gas cylinder 1105
Gas valves 1122, 1123, 1125 respectively
Open the outlet pressure gauges 1127, 1128, 11
Adjust the pressure of 30 to 1Kg/cm ² respectively, and open the inflow valve 1.
112, 1113, 1115, respectively, gradually open the mass flow controllers 1107, 1108,
1110 respectively. Subsequently, the outflow valves 1117, 1118, 1120 and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 11.
01. _At this time, _the outflow valves ₁₁₁₇ and 11
18 and 1120, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure in the reaction chamber reaches the desired value.
After confirming that the temperature of the base cylinder 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power supply 1140
is set to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the flow rate of NO gas is controlled manually or by an external drive motor or the like to control the valve 112 according to a pre-designed rate of change curve.
By performing an operation of gradually changing 0, the distribution concentration of oxygen atoms contained in the formed layer in the layer thickness direction is controlled. As described above, when the layer region (B, O) containing boron atoms and oxygen atoms is formed to the desired layer thickness, the outflow valves 1118 and 1120 are closed, and B ₂ H is discharged into the reaction chamber 1101. By continuing layer formation under the same conditions except for blocking the inflow of ₆ /He gas and NO gas, a desired layer region containing no oxygen atoms and boron atoms is formed on the layer region (B, O). The layer thickness is as follows. In this way, an amorphous layer with desired characteristics can be formed on the substrate 1137. The layer region () containing boron atoms is converted into B ₂ H ₆ /He at an appropriate point during the formation process of the amorphous layer.
By cutting off the flow of gas into the reaction chamber 1101, a desired layer thickness can be formed, and when the layer region () occupies the entire layer region (O) or a part thereof. Both of these can be achieved. For example, in the above example, layer regions (B, O)
When the layer is formed to the desired thickness, the layer is formed by continuing to form the layer under the same conditions except that the inflow of NO gas into the reaction chamber 1101 is completely shut off by completely closing the outflow valve 1120. Area (B, O)
A layer region containing boron atoms but not oxygen atoms can be formed as part of the amorphous layer. Further, when forming a layer region that does not contain boron atoms but contains oxygen atoms, the layer may be formed using, for example, NO gas and SiH ₄ /He gas. When halogen atoms are contained in the amorphous layer, SiF ₄ /He, for example, is further added to the above gas and fed into the reaction chamber 1101 . It goes without saying that all outflow valves for gases other than those required for forming each layer are closed, and
When forming each layer, the gas used to form the previous layer is released into the reaction chamber 1101 and the outflow valves 1117 to 1.
121 to the reaction chamber 1101, the outflow valves 1117 to
1121 is closed, auxiliary valves 1132 and 1133 are opened, and main valve 1134 is fully opened to temporarily evacuate the system to a high vacuum, as necessary. During layer formation, the base 1137 is rotated at a constant speed by a motor 1139 to ensure uniform layer formation. Example 1 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen concentration distribution as shown in FIG. 12 in the first layer was manufactured under the conditions shown in Table 1. The image-forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 KV for 0.2 seconds, and a light image was immediately irradiated using a tungsten lamp light source, transmitting a light amount of 1.5 lux・sec. It was irradiated through a mold 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. When the toner image on the member was transferred to transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

[Table] Example 2 Using the manufacturing equipment shown in Fig. 11, the first and second
An imaging member having an oxygen distribution concentration in the layer as shown in FIG. 13 was prepared under the conditions shown in Table 2. Other conditions were the same as in Example 1. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 3 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen distribution concentration as shown in FIG. 14 in the first layer was produced under the conditions shown in Table 3. Other conditions were the same as in Example 1.
When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

[Table] Example 4 Completely the same method as Example 1 except that when forming the first layer, the flow rate ratio of B ₂ H ₆ and SiH ₄ was changed to change the content ratio of boron atoms in the first layer. The imaging member was formed by. For each of the obtained image forming members, the image quality of the transferred image was evaluated in the same manner as in Example 1. As a result, the results shown in the table below were obtained.

[Table] ◎ Very good ○ Good example 5 Same method as Example 1 except that the total layer thickness of the image forming member was fixed at 10μ and the layer thickness ratio of the first layer and the second layer was relatively changed. An image forming member was prepared and evaluated in the same manner as in Example 1, and the results shown in the table below were obtained.

[Table] ◎ Very good
○ Good Example 6 Layers were formed in the same manner as in Example 1, except that the method of forming the first and second layers was changed as shown in the table below, and image quality evaluation was performed in the same manner as in Example 1. Good results were obtained. was gotten.

【table】 [Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 respectively show layer regions containing oxygen atoms constituting the amorphous layer ( FIG. 11 is an explanatory diagram for explaining the distribution state of oxygen atoms in O), and FIG. 11 is a schematic explanatory diagram of the apparatus used in the present invention. FIG. 2 is an explanatory diagram showing the distribution state of oxygen atoms. 100...Photoconductive member, 101...Support, 1
02...Amorphous layer, 103...First layer region (O),
104...Second layer region (), 105...Upper layer region.

Claims (1)

[Claims] 1. A support for a photoconductive member, and an amorphous layer having photoconductivity and made of an amorphous material having silicon atoms as a matrix, the amorphous layer being arranged in a layer thickness direction. It is continuous and contains oxygen atoms as constituent atoms at a maximum concentration of 500 atomic ppm or more within a layer thickness of 5μ from the support side, the concentration on the surface side is relatively lower than that on the support side, and the distribution concentration is gradually continuous. a first layer region having a reduced area; and a second layer region containing atoms belonging to group 3 of the periodic table as constituent atoms; The layer thickness is unevenly distributed in a part of the support side of the layer, and the layer thickness of the second layer region is unevenly distributed.
T _B and the layer thickness T of the portion excluding the layer thickness T _B of the second layer region from the layer thickness of the amorphous layer, T _B /T≦1
A photoconductive member characterized by having the following relationship.