JPH0454947B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, r-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 (Ip)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there is a need to improve overall characteristics in terms of usage environment characteristics and stability over time, and there are areas that can be further improved. 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 a so-called ghost phenomenon in which an afterimage occurs. Furthermore, for example, according to many experiments conducted by the present inventors, a-Si as a material constituting the photoconductive layer of an electrophotographic image forming member is superior to conventional inorganic photoconductive materials such as Se, CdS, and ZnO. It also has many advantages compared to organic photoconductive materials such as PVCz and TNF.
Charging treatment for forming an electrostatic image on the photoconductive layer of an electrophotographic imaging member having a single-layer photoconductive layer made of a-Si that has been given properties for use as a conventional solar cell. However, the dark decay is extremely fast even when the electrophotographic method is applied, making it difficult to apply normal electrophotography, and in a humid atmosphere, the above tendency is remarkable, and in some cases, the electrostatic charges may be retained until the development time. It has been found that there are some points that can be resolved, such as cases in which it is almost impossible to hold. Furthermore, when the photoconductive layer is composed of a-Si material, 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 this case, problems may arise in the electrical or photoconductive properties 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. This often occurs. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is also necessary to take measures to obtain the desired electrical, optical, and photoconductive properties as described above when designing photoconductive members. There is. 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 (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 It is designed to specify the layer structure of a photoconductive member having a photoconductive layer composed of amorphous silicon (hereinafter referred to as "a-Si(H,X)"). 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. This is based on the discovery that it has certain characteristics. The present invention is an all-environment type in which the electrical, optical, and photoconductive properties are almost always stable without being controlled by the usage environment, and it is extremely resistant to light fatigue and does not cause deterioration even after repeated use. The main object of the present invention is to provide a photoconductive member which has excellent durability and has no or almost no residual potential 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,
It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. 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 has a first layer region containing oxygen atoms as constituent atoms unevenly distributed in a partial region on the support side, and a region that decreases continuously in the layer thickness direction on the support side. The concentration distribution has a maximum concentration of 100 atomic ppm or more and a lower portion on the interface side on the second amorphous layer side than on the support side, with atoms belonging to Group V of the periodic table as constituent atoms. the first layer region and the second layer region are provided in contact with the support and share at least a part of each other with the first layer region. It is characterized by 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 a usage environment. Show characteristics. In particular, when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing, has no influence of residual potential on image formation, has stable electrical properties, and has high sensitivity. It has a high signal-to-noise ratio and is excellent in light fatigue resistance, repeated use characteristics, especially in a humid atmosphere, and is of high quality with high density, clear halftones, and high resolution. A visible image can be obtained. 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 to explain the layer structure of the photoconductive member of the present invention. The photoconductive member 100 shown in FIG. 1 has a-Si (H,
and an amorphous layer 102 exhibiting photoconductivity. The amorphous layer 102 includes a first layer region O103 containing oxygen atoms as constituent atoms, a second layer region V104 containing atoms belonging to group group of the periodic table (group atoms), and a second layer region O103 containing oxygen atoms as constituent atoms. On area V104,
It has a layer structure consisting of a layer region 106 that does not contain oxygen atoms and group group atoms. Layer region 105 provided between first layer region O103 and layer region 106 contains group group atoms but does not contain oxygen atoms. The group atoms contained in the second layer region V104 are continuously and non-uniformly distributed in the layer thickness direction, and
It is continuously and substantially uniformly distributed in a plane substantially parallel to the surface of the support 101. In the present invention, the oxygen atoms contained in the first layer region O103 are distributed so as to be substantially uniform in the layer thickness direction and in a plane parallel to the surface of the support 101. It is contained in the entire layer area of the first layer area O103. In the present invention, by containing oxygen atoms in the first layer region O, emphasis is placed on improving the adhesion between the first amorphous layer I and the support on which it is directly provided. is planned. In the photoconductive member of the present invention, such as the case shown in FIG. (corresponding to the layer region 106 shown in FIG.
5) does not necessarily need to be provided. That is, for example, in FIG. 1, the first layer region O
103 and the second layer region V104 may be the same layer region, or the second layer region V104 may be provided within the first layer region O103. In the photoconductive member of the present invention, the first layer region O that constitutes a part of the amorphous layer and contains oxygen atoms.
This is partly for the purpose of improving the adhesion of the amorphous layer with the support, and also because it is a second layer that constitutes a part of the amorphous layer I and contains group atoms. The area V is 1
In order to prevent charges from being injected into the amorphous layer from the support side when the amorphous layer is charged from the free surface side, As part of the layer region, the support and the amorphous layer are bonded to each other so as to share at least a portion of each other. In addition, in order to more effectively improve the adhesion between the support of the second layer region V or the layer region provided directly on the second layer region V,
The first layer region O is provided from the contact interface with the support to include the second layer region V, from the contact interface with the support to above the second layer region V,
It is preferable that the first layer region O is provided in the amorphous layer I so that the layer structure extends through the second region V. The group group atoms contained in the layer region V are continuous in the layer thickness direction and on the side opposite to the side where the support is provided (in FIG. It is contained in V in the layer region so that it is distributed more on the support side than on the surface side of the layer 106. In the present invention, the atoms belonging to group of the periodic table contained in the second layer region V constituting the amorphous layer are P (phosphorus), As (arsenic),
Sb (antimony), Bi (bismuth), etc. are used, and P and As are particularly preferably used. In the present invention, the distribution state of the group atoms contained in the layer region V is as described above in the layer thickness direction, and is substantially uniform in the direction parallel to the surface of the support. distribution state. 2 to 10 show typical examples of the distribution state of group group atoms in the layer thickness direction contained in the layer region V constituting the amorphous layer of the photoconductive member of the present invention. In the case of the present invention, oxygen atoms are uniformly contained in the above-mentioned distribution state throughout the entire layer region of the first layer region O. In the following, the layer region O containing oxygen atoms will not be mentioned unless a particular explanation is required. In FIGS. 2 to 10, the horizontal axis represents the content C of group atoms, and the vertical axis represents the layer region V containing group atoms provided in the amorphous layer exhibiting photoconductivity. thickness, t _B is the position of the interface on the support side,
t _T indicates the position of the interface on the opposite side to the support side. That is, in the layer region V containing group atoms, the layer is formed toward the t _T side rather than the t _B side. In the present invention, the layer region V containing group atoms is a-Si(H,X) constituting the photoconductive member.
It is unevenly distributed on the support side of the amorphous layer exhibiting photoconductivity. FIG. 2 shows a first typical example of the distribution state of group atoms contained in the layer region V constituting the amorphous layer in the layer thickness direction. In the example shown in FIG. 2, the interface position where the surface where the layer region V containing group atoms is formed (the surface of the support 101 in FIG. 1) and the surface of the layer region V are in contact with each other. From t _B to the position t ₁ , the distribution concentration C of the group group atoms takes a constant value of C ₁ , but the group atoms are contained in the layer region V where they are formed, and the position
From t ₁ onward, the distribution concentration C ₂ is gradually and continuously reduced up to the boundary surface position t _T . At the boundary surface position _tT , the distribution concentration C of group atoms is assumed to be _C3 . In the example shown in FIG. 3, the distributed concentration C of the contained group atoms gradually and continuously decreases from the distributed concentration C ₄ from position t _B to position t _T , and at position t _T the concentration C A distribution state of ₅ is formed. In the case of Fig. 4, the distribution concentration C of group atoms from position t _B to position t ₂ is a constant value of concentration C ₅ ,
Between the position t ₂ and the position t _T , the distribution concentration C is gradually and continuously decreased, and at the position t _T , the distribution concentration C is substantially zero. In the case of FIG. 5, the concentration of group atoms is gradually decreased from the distribution concentration _C8 from position _tB to position _tT , and becomes substantially zero at position _tT . In the example shown in FIG. 6, the distribution concentration C of group atoms is a constant value of distribution concentration C 9 between position t _B and position t ₃ , and distribution concentration C ₉ is a constant value at position t _T.
It is said to be C ₁₀ . Between the 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, from position t _B to position t ₄ , a constant value of distribution concentration C ₁₁ is taken, and from position t ₄ to position t _T , a linear function is applied from distribution concentration C ₁₂ to distribution concentration C ₁₃ . The distribution state is said to be decreasing. In the example shown in FIG. 8, from position t _B to position t _T
Until , the distribution concentration C of group atoms is the concentration C ₁₄
It decreases in a linear manner as it approaches zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C of group atoms decreases linearly from distribution concentration C ₁₅ to distribution concentration C ₁₆ ;
An example is shown in which the distribution concentration C ₁₆ is kept at a constant value between t ₅ and position t _T. In the example shown in FIG. 10, the distribution concentration C of group atoms is a distribution concentration C ₁₇ at position t _B , and is gradually decreased from this distribution concentration C ₁₇ until reaching position t ₆ . In the vicinity of the position t ₆ , it decreases rapidly and becomes the distribution concentration C ₁₈ at the position t ₆ . Between position t ₆ and position t ₇ , the distribution concentration is initially decreased rapidly, and then gradually decreased to become C ₁₉ at position t ₇ , and the distribution concentration between position t ₇ and position t ₈ is In between, the position is gradually reduced very slowly.
At t ₈ the distribution concentration C ₂₀ is reached. position t ₈ and position t _T
In between, the distribution concentration C ₂₀ is reduced 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 group atoms contained in the layer region V in the layer thickness direction, in the present invention, on the support side, Distribution concentration C of group atoms
On the interface _tT side, the layer region V containing group atoms becomes an amorphous layer, with a distribution state having a portion where the distribution concentration C is lower than that on the support side. It is provided. In the present invention, the layer region V containing group atoms constituting the amorphous layer is preferably localized region A containing group atoms at a high concentration toward the support side, as described above. has. The localized region A is provided within 5μ from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region A may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region A is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. Localized region A has a maximum value C _nax of the content distribution value (distribution concentration value) of group atoms contained therein in the layer thickness direction, which is usually 100 atomic ppm with respect to silicon atoms. Above, preferably
150 atomic ppm or more, optimally 200 atomic ppm
It is desirable that the layers be formed so that the distribution state described above can be obtained. That is, in the present invention, the layer region V containing the group group atoms has the maximum distribution concentration C _nax within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
is formed so that it exists. As described above, by providing the localized region A containing a high concentration of group group atoms on the support side in the layer region V, charge injection from the support side into the amorphous layer is facilitated. It can be prevented more effectively. In the present invention, the content of group atoms contained in the layer region V containing group atoms is appropriately determined as desired so that the object of the present invention is effectively achieved. But usually 30~5×
10 ⁴ 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 properties 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 V containing the group group atoms (the layer thickness of the layer region 103 in FIG. 1) and the layer thickness t B provided on the layer region V , the layer thickness T of the layer region B (layer region 106 in FIG. 1) excluding the layer region containing no group atoms, that is, the layer region V, is the first amorphous layer having the desired characteristics. The layer design is determined appropriately according to the purpose so that the quality layer I is formed on the support. In the present invention, the layer thickness t _B of the layer region V containing group atoms is usually 30 Å to 5 μ, preferably
40 Å to 4 μ, optimally 50 Å to 3 μ, layer region B
The layer thickness T is usually 0.2 to 95 μ, preferably 0.5
It is desirable that the thickness be ~76μ, optimally 1~47μ. Further, the sum of the layer thickness T and the layer thickness 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 _tp of the layer region O containing oxygen atoms is determined according to the desired purpose in relation to the layer thickness _tB of the layer region V sharing at least a part of the layer region. It is desirable to That is, if the purpose is to strengthen the adhesion between the layer region V and the support that is in direct contact with the layer region V, the layer region O is
Since it is sufficient that it is provided at least in the end layer region of the layer region V on the side of the support, the layer thickness t _p of the layer region O may be at most the layer thickness t _B of the layer region V. In addition, if it is intended to strengthen the adhesion between the layer region V and a layer region provided directly on the layer region V (corresponding to the layer region 106 in FIG. 1), the layer region O is , it suffices if it is provided at least in the end layer region of the layer region V opposite to the side where the support is provided, so the layer thickness t _p of the layer region O is at most the layer thickness t _B of the layer region V. All you need is enough. Furthermore, considering the case where the above two points are satisfied, the layer thickness t _p of the layer region O needs to be at least the layer thickness t _B of the layer region V, and in this case, the layer region O It is necessary to have a layered structure in which a layer region V is provided. In order to achieve more effective adhesion between the layer region V and the layer region provided directly on the layer region V, the layer region O should be placed above the layer region V (opposite to the side where the support is located). It is preferable to extend it in the direction (direction). In the present invention, it is necessary to provide a portion containing no oxygen atoms in the end layer region on the surface side of the amorphous layer, and to make the layer region O locally unevenly distributed on the support side of the amorphous layer I. Therefore, the layer thickness t _p of the layer region O is usually 10 Å to 10 μ, preferably 20 Å to
It is desirable that the thickness be 8μ, optimally 30Å to 5μ. In the present invention, for example, glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A-Si is introduced into a chamber to generate a glow discharge in the deposition chamber, and a-Si
A layer consisting of (H,X) may be formed. or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering. In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such. As the raw material gas for supplying Si used in the present invention, silicon hydride (silanes) in a gaseous state or that can be gasified such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ is effective. Among them, SiH ₄ and Si ₂ H ₆ are particularly preferred in terms of ease of layer preparation work and good Si supply efficiency. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
An amorphous layer made of a-Si containing halogen atoms can be formed on 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. However, in order to introduce hydrogen atoms, a predetermined amount of silicon compound gas containing hydrogen atoms is further mixed with these gases to form an amorphous layer on a predetermined support. 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. 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 carried out 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, HI, SiH ₂ F ₂ , SiH ₂
Halogenated silicon hydrides such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other gaseous or gasifiable halogen compounds 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 ₆ , Si ₃
This can also be achieved by causing a discharge by causing a silicon hydride gas such as 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 substrate. 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 Haken atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the amorphous layer of the photoconductive member to be formed is usually In the case of 1 to 40 atomic%,
The preferred range is 5 to 30 atomic %. Hydrogen atoms (H) contained in the amorphous layer or/
and the amount of halogen atoms (X) can be controlled by, for example, the support temperature or/and the introduction of hydrogen atoms (H) or the starting materials used to contain the halogen atoms (X) into the deposition system. What is necessary is to control the amount of discharge, the discharge force, etc. In order to provide the layer region V containing group V atoms and the layer region O containing oxygen atoms in the amorphous layer, a step is required when forming the amorphous layer by a glow discharge method, a reactive sputtering method, etc. A starting material for introducing group V atoms and a starting material for introducing oxygen atoms are used together with the above-mentioned starting materials for forming an amorphous layer, and the amounts thereof are controlled in the layer to be formed. done by. When the glow discharge method is used to form the layer region O containing oxygen atoms and the layer region V containing group V atoms, which constitute the amorphous layer, the raw material gas for forming each layer region and the layer region V containing group V atoms are used. As the starting material, a starting material for introducing an oxygen atom and/or a starting material for introducing a group V atom is added to the starting material selected from the above-mentioned starting materials for forming an amorphous layer as desired. Added. Such starting materials for introducing oxygen atoms or starting materials for introducing Group V atoms include:
Most gaseous substances or gasified substances containing at least oxygen atoms or Group V atoms as constituent atoms 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 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. A raw material gas containing atoms (H) as constituent atoms is also mixed at a desired mixing ratio, or
Alternatively, a raw material gas containing silicon atoms (Si) and silicon atoms (Si) and oxygen atoms (O)
and a raw material gas containing three hydrogen atoms (H) as constituent atoms can be used in combination. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms. Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and nitrogen monooxide (N ₂ O ), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si) and oxygen atoms (O )
and a hydrogen atom (H) as constituent atoms, such as disiloxane H ₃ SiOSiH ₃ and trisiloxane H ₃
Examples include lower siloxanes such as SiOSiH ₂ OSiH ₃ and the like. When the layer region V is formed using a glow discharge method, starting materials for introducing group V atoms that are effectively used in the present invention include PH ₃ and P ₂ H ₄ for introducing phosphorus atoms. Phosphorus hydride, PH ₄ I, PF ₃ , etc.
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , and _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing Group V atoms. The content of group V atoms introduced into the layer region V containing group V atoms is determined by the amount of group V atoms introduced into the layer region V containing group V atoms.
It can be arbitrarily controlled by controlling the gas flow rate of the starting material for group atom introduction, gas flow rate ratio, discharge power, support temperature, pressure in the deposition chamber, etc. To form the layer region O containing oxygen atoms by the sputtering method, single crystal or polycrystalline
Si wafer or _SiO2 wafer or Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a 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. Good. Alternatively, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, a so-called rare gas, such as He,
Preferable examples include Ne, Ar, and the like. 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 (H,
P-type impurities that give P-type conductivity characteristics to ), In (indium), Tl (thallium), etc. Particularly preferably used are:
B, Ga. In the present invention, the content of the substance that controls the conductive properties contained in the layer region B is determined by the conductive properties required for the layer region B or other substances 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 the layer region and the relationship with the characteristics at the contact interface with 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 material for introducing the atoms of the group group is 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, starting materials for introducing such group group atoms include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlCl ₃ ,
GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the photoconductive member of the present invention, as explained in the example shown in FIG. Although a preferred embodiment is a case in which it is locally unevenly distributed, the present invention is not limited to this,
For example, the amorphous layer may be formed so that the layer thickness of the layer region O is sufficiently thicker than that of the layer region that does not contain oxygen atoms. 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. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming each layer of the present invention is sealed, for example, 1102
is SiH ₄ gas (purity 99.999%,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_B2H6 gas diluted with (purity 99.999% _, hereinafter _B2
It is abbreviated as H ₆ /He. ) cylinder, 1104 is PH ₃ gas diluted with He (99.99% purity, hereinafter abbreviated as PH ₃ /He) cylinder, 1105 is SiF ₄ diluted with He
₁₁₀₆ is a NO gas (purity 99.99%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
1116, check that the outflow valves 1117 to 1121 and the auxiliary valve 1132 are open,
First, open the main valve 1134 to open the reaction chamber 110.
1. Evacuate the inside of the gas pipe. Next, the vacuum gauge 1136
When the reading reaches approximately 5×10 ⁻⁶ torr, the auxiliary valve 1132 and the outflow valves 1117 to 1121 are closed. 1 in the case of forming an amorphous layer on the base 1137
For example, SiH ₄ /
He gas, PH ₃ from gas cylinder 1104 /He gas, NO gas from gas cylinder 1106 at valve 1
Open 122, 1124, 1126 and set the pressure of outlet pressure gauges 1127, 1129, 1130 to 1Kg/cm ²
Adjust the inflow valves 1112, 1114, 11 to
16 gradually open, and the mass flow controller 11
07, 1109, and 1111, respectively.
Subsequently, the outflow valves 1117, 1119, 11
21. Gradually open the auxiliary valves 1132 and 1133 to allow each gas to flow into the reaction chamber 1101.
At this time, the outflow valves 1117, 1119, and 1121 are adjusted respectively so that the ratio of the SiH ₄ /He gas flow rate, PH ₃ /He gas flow rate, and NO gas flow rate becomes the desired value, and the While watching the reading on the vacuum gauge 1136 to ensure the pressure is at the desired value,
Adjust the opening of main valve 1134. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, PH ₃ /He gas is contained in a layer formed by operating a valve 1118 to gradually change the flow rate of PH 3 /He gas manually or by using an external drive motor or the like according to a pre-designed rate of change curve. The distribution concentration of phosphorus atoms (P) is controlled. First, layer regions P and O containing phosphorus atoms and oxygen atoms are formed on the substrate 1137 as described above. At this time, by blocking the introduction of PH ₃ /He gas or NO gas into the reaction chamber 1101 by closing the valve of each corresponding gas introduction pipe, the layer region containing phosphorus atoms or , the layer thickness of the layer region containing oxygen atoms can be arbitrarily controlled as desired. layer region P containing phosphorus atoms and oxygen atoms, respectively;
After O is formed to a desired thickness as described above, each of the outflow valves 1119 and 1121 is closed and glow discharge is continued for a desired time to form a layer containing phosphorus atoms and oxygen atoms, respectively. A layer region containing no phosphorus atoms and oxygen atoms is formed on the regions P and O to a desired thickness, and the formation of the amorphous layer is completed. 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, open the auxiliary valve 1132, and fully open the main valve 1134 to temporarily evacuate the system to a high vacuum, as necessary. Example 1 Using the manufacturing apparatus shown in FIG. 11, layers were formed on an aluminum substrate under the conditions shown in Table 1 below. 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 image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating the test over 150,000 times.

[Table] Example 2 Example 1 except that an amorphous layer was formed on the Al substrate using the production apparatus shown in FIG. 11 and using the content of phosphorus (P) in the layer as a parameter. I did the same thing. The common manufacturing conditions for each sample at this time are as shown in Table 2-1. 2-2
The table shows the distribution concentration of phosphorus atoms contained in the amorphous layer at each position in the layer thickness direction from the substrate surface and the evaluation results of the electrophotographic properties of the obtained sample. The numbers in the left column of the table indicate sample numbers. Each of the produced electrophotographic image forming members undergoes a series of electrophotographic processes including charging, image exposure, development, and transfer to improve the [density], [resolution], and [tone reproducibility] of the image visualized on the transfer paper. ] Comprehensive evaluation was made based on the merits and demerits.

【table】

[Table] Example 3 Using the manufacturing apparatus shown in FIG. 11, a layer was formed on an Al substrate under the conditions shown in Table 3 below. 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 tungsten lamp was used as the light source, and a light intensity of 1.0 lux.sec was irradiated using a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a charged developer (including toner and carrier) over the surface of the member. The toner image thus obtained was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration of the image was observed even after repeating the process over 100,000 times.

[Table] Example 4 Using the apparatus shown in FIG. 11, a layer was formed on an Al substrate under the conditions shown in Table 4 below. Other conditions were the same as in Example 1. The image forming member thus obtained was placed in a charging, exposure and developing device, corona discharge was performed at 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 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 5 An image forming member was prepared in the same manner as in Example 1, except that the method for forming the amorphous layer was changed as shown in Table 5 below, and evaluation was performed in the same manner as in Example 1. Good results were obtained.

[Table] Example 6 An image forming member was prepared in the same manner as in Example 1, except that the method for forming the amorphous layer was changed as shown in Table 6 below, and evaluation was performed in the same manner as in Example 1. As a result, good results were obtained.

[Table] Example 7 The conditions and procedures shown in Example 3 were followed except that the layer creation conditions in the second and third layer creation stages of Example 3 were set to the conditions shown in Table 7 below. Then, electrophotographic image forming members were prepared and evaluated in the same manner as in Example 1.
Good results were obtained in terms of image quality and durability.

【table】

【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 are layers containing Group V atoms constituting an amorphous layer, respectively. FIG. 11, an explanatory diagram for explaining the distribution state of group V atoms in region V, is a schematic explanatory diagram of the apparatus used in the present invention. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer I, 103...Layer region V, 104...Layer region B, 105...Second amorphous layer, 106...Free surface.

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, wherein the amorphous layer supports supporting atoms as constituent atoms. A first layer region containing unevenly distributed oxygen atoms in a partial region on the body side and a region that continuously decreases in the layer thickness direction, and a maximum concentration of 100 atomic ppm or more on the support side. a second layer region containing atoms belonging to Group V of the periodic table as constituent atoms, with a concentration distribution having a lower portion on the interface side on the second amorphous layer side than on the support side; The first layer region and the second layer region are provided in contact with the support and share at least a part of each other with the first layer region. Photoconductive member.