JPH0452462B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
It has a high signal-to-noise ratio [photocurrent (I _P )/dark current (Id)], has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, and has a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use and being able to easily dispose of afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion 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 are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in a so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases, etc. There were many cases where problems occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when the commonly used halogen lamps and fluorescent lamps are used as light sources, there remains room for improvement in that they cannot effectively use light on the long wavelength side. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Alternatively, 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 contained in the photoconductive layer as constituent atoms to control the properties of the photoconductive layer, and other atoms are included in the photoconductive layer to improve properties. In the past, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, or For example, there may be image defects commonly called "white spots" on images transferred to transfer paper, which are thought to be caused by localized discharge breakdown phenomena, or defects that may be caused by rubbing when a blade is used for cleaning, for example. A so-called image defect called "white stripe" may occur. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. You can win by causing phenomena such as ``happening''. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms (Si) and a germanium atom (Ge) as a matrix, and an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium , or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to generically as "a-
The structure of a photoconductive member having an amorphous layer exhibiting photoconductivity composed of "SiGe (H, Photoconductive materials not only exhibit extremely superior properties in practical use, but also exceed conventional photoconductive materials in every respect, especially as photoconductive materials for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed. Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having sufficient performance. 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. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Still another object of the present invention is to provide high density images without any image defects or blurring during long-term use.
An object of the present invention is to provide a photoconductive member for electrophotography in which it is possible to easily obtain high-quality images with clear halftones and high resolution. a support for a photoconductive member; a first photoconductive amorphous layer made of an amorphous material containing silicon atoms and germanium atoms; and a first amorphous layer containing silicon atoms and carbon atoms. and a second amorphous layer made of an amorphous material in this order from the support side, and the distribution concentration of oxygen atoms in the first amorphous layer is 500 atomic on the support side.
It is characterized in that it has a portion where the temperature is higher than ppm and a portion which is considerably lower on the second amorphous layer side of the first amorphous layer than on the support side. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and pressure resistance. and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is tough and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 is made of a-SiGe (H,
A first amorphous layer ( ) 102 having photoconductivity and a second amorphous layer ( ) 103 made of X). The germanium atoms contained in the first amorphous layer ( ) 102 are continuously arranged in the layer thickness direction of the first amorphous layer ( ) 102 and in the in-plane direction parallel to the surface of the support 101 . It is contained in the first amorphous layer ( ) 102 so as to be uniformly distributed. In the photoconductive member of the present invention, the first amorphous layer () containing germanium atoms has a layer region (PN) containing a substance (C) that controls conductivity on the support side. By providing this, the conductive properties of the layer region (PN) can be arbitrarily controlled as desired. Such substances (C) include so-called impurities in the semiconductor field, and in the present invention, a-SiGe (C) constituting the first amorphous layer () to be formed is used. H,
Type impurities can be mentioned. Specifically, P
Type impurities include atoms belonging to the group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc. Preferably used are:
B, Ga. As the n-type impurity, atoms belonging to the group of the periodic table (group atoms), such as P
(phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and particularly preferably used are:
P, As. In the present invention, the content of the substance that controls the conduction characteristics contained in the layer region (PN) provided in the first amorphous layer () is determined according to the conductivity required for the layer region (PN). The layer region (PN) can be appropriately selected depending on the organic relationship, such as the properties or the relationship with the properties at the contact interface with the support with which the layer region (PN) is provided in direct contact. In addition, the inclusion of a substance that controls the conduction characteristics is taken into consideration, taking into account the characteristics of other layer regions provided in direct contact with the layer region and the characteristics at the contact interface with the other layer regions. The amount is selected accordingly. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is as follows:
Usually 0.01 to 5×10 ⁴ atomic ppm, preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5×
10 ³ atomic ppm is desirable. In the present invention, the content of the substance (C) that controls conductivity in the layer region (PN) containing the substance (C) is usually 30 atomic ppm or more, preferably
50atomic ppm or more, optimally 100atomic ppm
By doing the above, for example, the substance to be included
When (C) is the above-mentioned P-type impurity, when the free surface of the second amorphous layer () is subjected to a polar charging treatment, the inside of the first amorphous layer () from the support side is It is possible to effectively prevent the injection of electrons into the
When the substance (C) to be contained is the n-type impurity, when the free surface of the second amorphous layer () is subjected to polar charging treatment, the first amorphous layer is removed from the support side. Injection of holes into () can be effectively prevented. In the above case, the layer region (Z) excluding the layer region (PN) has conduction of a polarity different from the polarity of the substance that controls the conduction characteristics contained in the layer region (PN). A substance that controls the properties may be contained, or a substance that controls the conduction properties of the same polarity may be contained in an amount much smaller than the actual amount contained in the layer region (PN). It is something. In such a case, the content of the substance (C) that controls the conduction characteristics contained in the layer region (Z) depends on the polarity and content of the substance contained in the layer region (PN). It is determined appropriately according to the desired results, but in normal cases, the range is 0.001 to 1000 atomic.
ppm, preferably 0.05-500atomic ppm, optimally
It is desirable that the content be 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the first
A layer region containing a substance controlling conductivity having one polarity in the amorphous layer () and a layer region containing a substance controlling conductivity having the other polarity are brought into direct contact. It is also possible to provide a so-called depletion layer in the contact region. For example, in the first amorphous layer, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in direct contact with each other to form a so-called P- n
A junction can be formed to provide a depletion layer. In the present invention, the content of germanium atoms contained in the first amorphous layer ( ) is appropriately determined as desired so as to effectively achieve the object of the present invention, but usually 1～9.5× ¹⁰⁵ atomic
ppm, preferably 100 to 8.0×10 ⁵ atomic ppm, optimally 500 to 7×10 ⁵ atomic ppm. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and increasing dark resistance, and further improving the adhesion between the support and the first amorphous layer,
Oxygen atoms are contained in the first amorphous layer ( ). The oxygen atoms contained in the amorphous layer are
It may be contained and unevenly distributed in the entire layer region of the first amorphous layer () or only in a part of the layer region of the first amorphous layer (). The distribution state of oxygen atoms is the distribution concentration C
(O) is distributed in the thickness direction of the first amorphous layer (2) The concentration C(O) may be non-uniform in the layer thickness direction. In the present invention, a layer region (O) containing enzyme atoms provided in the first amorphous layer ()
is provided so as to occupy the entire layer area of the first amorphous layer () when the main purpose is to improve photosensitivity and dark resistance.
When the main purpose is to strengthen the adhesion between the first amorphous layer and the first amorphous layer, it is provided so as to occupy the end layer region of the first amorphous layer on the side of the support. In the former case,
The content of oxygen atoms contained in the layer region (O) is relatively small in order to maintain high photosensitivity,
In the latter case, it is desirable that the amount be relatively large in order to ensure enhanced adhesion to the support. or,
In order to achieve both the former and the latter at the same time, it is necessary to distribute it at a relatively high concentration on the support side.
Either oxygen atoms are distributed at a relatively low concentration on the free surface side of the first amorphous layer (), or oxygen atoms are actively distributed in the surface layer region on the free surface side of the first amorphous layer (). Specifically, it is sufficient to form a distribution state of oxygen atoms in the layer region (O) such that oxygen atoms are not contained therein. In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the first amorphous layer () depends on the characteristics required for the layer region (O) itself or the layer region. When (O) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (O), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in the layer region (O) is determined as desired depending on the properties required of the photoconductive member to be formed, but is usually 0.001 to 50 atomic%, preferably 0.001 to 50 atomic%. , 0.002~40atomic%, optimally 0.003~
A desirable value is 30 atomic%. In the present invention, whether the layer region (O) occupies the entire area of the first amorphous layer () or even if the layer region (O) does not occupy the entire area of the first amorphous layer (), the layer region (O)
If the ratio of the first amorphous layer () to the layer thickness T of the layer thickness T _O is sufficiently large, the upper limit of the content of oxygen atoms contained in the layer region (O) is smaller than the above value. It is desirable that the amount be sufficiently reduced. In the case of the present invention, when the ratio of the layer thickness T _O of the layer region (O) to the layer thickness T of the first amorphous layer ( ) is two-fifths or more, The upper limit of the amount of oxygen atoms contained in the layer region (O) is usually 30 atomic% or less, preferably
It is desirable that it be 20 atomic % or less, optimally 10 atomic % or less. 2 to 10 show typical examples of the distribution state of oxygen atoms contained in the layer region (O) of the photoconductive member in the present invention in the layer thickness direction. 2 to 10, the horizontal axis shows the distribution concentration C of oxygen atoms, the vertical axis shows the layer thickness of the layer region (O), and t _B is the position of the end surface of the layer region (O) on the support side. , t _T indicates the position of the end surface of the layer region (O) on the side opposite to the support side. That is, in the layer region (O) containing oxygen atoms, the layer is formed from the t _B side toward the t _T side. 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 _tB where the surface where the layer region (O) containing oxygen atoms is formed and the surface of _the layer region (O) contact, the oxygen A layer region (O) where oxygen atoms are formed while the atomic distribution concentration C takes a constant value of _C1 .
The concentration C2 is higher than the concentration C2 than the position _t1 , and the interface position _tT is higher than the concentration _C2 .
has been gradually and continuously reduced until . 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 the concentration C ₄ from the position t _B to the position t _T , and reaches the concentration C ₅ at the position t _T. It forms a distribution state like this. In the case of Fig. 4, from position t _B to position t ₂ , the distribution concentration C of oxygen atoms is a constant value of concentration C ₆ ,
The distribution concentration C is gradually and continuously reduced between position _t2 and position _tT , and at position _tT , the distribution concentration C is substantially zero (here, substantially zero means that the concentration is below the detection limit). ). In the case of Fig. 5, the distribution concentration C of oxygen atoms is gradually decreased continuously from the concentration C ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of oxygen atoms is constant at a concentration _C9 between the position _tB and the position _t3 , and the concentration _C10 at the position _tT .
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, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . 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 the concentration C ₁₄ to substantially zero. In FIG. 9, from position _tB to position _t5 , the distribution concentration C of oxygen atoms is lower than the concentration ₁₅ .
An example is shown in which the concentration C ₁₆ is linearly decreased to C 16 and the concentration C ₁₆ is kept at a constant value between the position t ₅ and the position t _T. In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is ₁₇ at position _tB ;
Until reaching t ₆ , the concentration is slowly decreased from C ₁₇ at first, and near the position t ₆ , it is rapidly decreased to the concentration C ₁₈ at position t ₆ . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 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 , has a portion where the distribution concentration C of oxygen atoms is high, and on the interface _tT side, the distribution state of oxygen atoms has a portion where the distribution concentration C is considerably lower than that on the support side. It is set in. In the present invention, the layer region (O) containing oxygen atoms constituting the first amorphous layer () contains oxygen atoms at a relatively high concentration toward the support side, as described above. It is desirable to provide the support with localized regions (B), and in this case, the adhesion between the support and the first amorphous layer () can be further improved. The localized region (B) is desirably provided within 5 μm from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region (B) 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 ). In some cases, it may be done. Whether the localized region 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. The localized region (B) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax 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 to form a layer in such a way that a distribution state of ppm or more can be achieved. That is, in the present invention, the layer region (O) containing oxygen atoms has the maximum distribution concentration within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the structure be formed so that Cmax exists. In the present invention, specific examples of the halogen atom (X) contained in the first amorphous layer (X) include fluorine, chlorine, bromine, and iodine, especially fluorine, if necessary. Preferred examples include chlorine and chlorine. In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used to form the first amorphous layer ( ) made of a-SiGe (H,X). It is made by vacuum deposition method. For example, in order to form an amorphous layer composed of a-SiGe (H, and germanium atoms (Ge), and if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X), the internal pressure of which is reduced. A gas made of a-SiGe (H, It is sufficient to form a layer. In addition, when forming by a sputtering method, for example, a target made of Si, or a target made of Si and Ge in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. Using two of the prepared targets or using a mixed target of Si and Ge, source gas for supplying Ge diluted with a diluent gas such as He or Ar as necessary. If necessary, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and the raw material gas for supplying Ge The target may be sputtered while controlling the gas flow rate according to a desired rate of change curve.
In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the EB method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for supplying Ge include GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ ,
Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ ,
Germanium hydride in a gaseous state or that can be gasified, such as Ge ₉ H ₂₀ , can be effectively used. In particular, GeH _{4 , Ge2H8 , Ge3H8}
are listed as preferred. 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 hydride 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 using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first amorphous layer ( ) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing the first amorphous layer ( ) containing halogen atoms according to the glow discharge method, basically, for example, silicon halide is used as a raw material gas for supplying Si, and raw material gas for supplying Ge is mixed. Germanium hydride and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form the first amorphous layer ().
An amorphous layer can be formed on a desired support by introducing a hydrogen gas into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. In order to more easily control the rate of introduction of atoms, a layer may be formed by mixing a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms with these gases. 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 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 form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ , GeH ₂ F ₂ ,
GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ , GeH ₃ Cl,
GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂
Germanium hydrogenated halides such as I ₂ , GeH ₃ I,
Halides containing hydrogen atoms as one of their constituent elements, such as GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ ,
Germanium halides such as GeCl ₂ , GeBr ₂ , GeI ₂ , and other gaseous or gasifiable substances can also be mentioned as useful starting materials for forming the first amorphous layer. Halides containing hydrogen atoms in these substances are hydrogen atoms that are extremely effective for controlling electrical or photoelectric properties at the same time as halogen atoms are introduced into the layer during the formation of the first amorphous layer. Since halogen is also introduced, it is used as a suitable raw material for halogen introduction in the present invention. In order to structurally introduce hydrogen atoms into the first amorphous layer (2), in addition to the above, H ₂ , SiH ₄ , Si ₂
Silicon hydride such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ,
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si are allowed to coexist in the deposition chamber. This can also be done by causing electrical discharge. In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first amorphous layer () of the photoconductive member to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the quantities (H+X) is usually 0.01 to 40 atomic%, preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first amorphous layer (), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms The amount of the starting material used to contain the atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In order to structurally introduce a substance that controls conduction properties, for example, group atoms or group atoms into the layer region constituting the first amorphous layer, group atoms are introduced during layer formation. The starting material for the purpose of forming the amorphous layer or the starting material for introducing the group atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the amorphous 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 ₄ H ₁₀ , B ₅ H ₉ , B ₅
Boron hydride such as H ₁₁ , B ₆ H ₁₀ , B ₆ H12, B ₆ H ₁₄ ,
Examples include 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 can also be mentioned. In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _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 atoms. The layer thickness of the first amorphous layer () in the photoconductive member of the present invention is determined as desired so that photocarriers generated in the first amorphous layer () are efficiently transported. It is determined as appropriate, usually 1 to 100μ,
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In the present invention, the layer thickness of the layer region constituting the first amorphous layer ( ), containing a substance that controls conduction properties, and provided unevenly on the support side is defined as the layer thickness between the layer region and the layer region. It is appropriately determined as desired depending on the characteristics required of the first amorphous layer formed on the layer region and other layer regions constituting the first amorphous layer (), but the lower limit thereof is as follows: Generally, the thickness is desirably 30 Å or more, preferably 40 Å or more, and optimally 50 Å or more. In addition, if the content of the substance that controls conduction properties contained in the layer region is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region is usually
It is desirable that the thickness be 5μ or less, preferably 4μ or less, and optimally 3μ or less. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the first amorphous layer (), it is necessary to prepare a layer region (O) containing oxygen atoms during the formation of the first amorphous layer (). The starting material may be used together with the above-mentioned starting material for forming the first amorphous layer (2), and the amount thereof may be controlled and contained in the layer to be formed. When a glow discharge method is used to form the layer region (O), oxygen atoms are introduced into a material selected as desired from among the starting materials for forming the first amorphous layer () described above. The starting materials for are added.
As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas whose constituent atoms are silicon atoms, Si, a raw material gas whose constituent atoms are oxygen atoms (O), and a raw material gas whose constituent atoms are hydrogen atoms (H) or halogen atoms (X) as necessary. or a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing oxygen atoms (O) and hydrogen atoms (H) in a desired mixing ratio. , also by mixing at a desired mixing ratio, or by mixing a raw material gas containing silicon atoms (Si) with three atoms: silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used by mixing with the raw material gas which is the constituent atoms. 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, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), 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), oxygen atoms (O), and hydrogen atoms (H), such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H Examples include lower siloxanes such as ₃ SiOSiH ₂ OSiH ₂ ). To form the first amorphous layer () containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer,
Alternatively, sputtering may be carried out by targeting a wafer containing a mixture of Si and SiO ₂ and sputtering them in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluting gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. 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, when a layer region (O) containing oxygen atoms is provided when forming the first amorphous layer (), the distribution of oxygen atoms contained in the layer region (O) In order to form a layer region (O) having a desired depth profile in the layer thickness direction by changing the concentration C(O) in the layer thickness direction, in the case of glow discharge, the distribution concentration C(O ) is introduced into the deposition chamber while the gas flow rate of the starting material for introduction of oxygen atoms to be changed is appropriately changed according to a desired rate of change curve. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (O) is formed by a sputtering method, the distribution concentration of oxygen atoms in the layer thickness direction C(O)
In order to change the depth profile of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, the starting point for introducing oxygen atoms is This is accomplished by using the substance in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be achieved by changing the mixing ratio of Si and SiO ₂ in advance in the layer thickness direction of the target. In the photoconductive member 100 shown in FIG.
The amorphous layer ( ) 103 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability. Further, in the present invention, the first amorphous layer ()
102 and the second amorphous layer ( ) 103 each have a common constituent element of silicon atoms, ensuring chemical stability at the laminated interface. It is fully accomplished. The second amorphous layer () in the present invention comprises silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
(hereinafter referred to as "a-(Si _x C _1-x ) _y
( _H ,
Consists of. The second composed of a-(Si _x C _1-x ) _y (H,X) _1-y
The amorphous layer ( ) is formed by a glow discharge method, a sputtering method, an ion plantation method, an ion plating method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having the above-mentioned photoconductive member. a second amorphous layer () that creates carbon atoms and halogen atoms along with silicon atoms;
The glow discharge method or the sputtering method is preferably employed because of the advantage that it can be easily introduced into the interior. Furthermore, in the present invention, the second amorphous layer ( ) may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the second amorphous layer () by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y (H,X) _1-y is added as necessary. The gas is mixed with a diluted gas at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. What is necessary is to deposit a-(Si _x C _1-x ) _y (H,X) _1-y on the first amorphous layer ( ) already formed on the support. In the present invention, a-(Si _x C _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Carbon atom (C), hydrogen atom (H), halogen atom (X)
Most gaseous substances or gasified substances containing at least one of the following atoms may be used. When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as necessary. Depending on the situation, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si and C and H may be used. The raw material gas containing constituent atoms and/or the raw material gas containing C and and H as constituent atoms, or a raw material gas containing Si, C, and X as constituent atoms can be mixed and used. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. Raw material gases serving as constituent atoms may be mixed and used. In the present invention, F, Cl, Br, and I are preferable as the halogen atoms (X) contained in the second amorphous layer ( ), with F and Cl being particularly preferable. In the present invention, raw material gases that can be effectively used to form the second amorphous layer include those that are in a gaseous state at room temperature and pressure, or those that can be easily gasified. Can list substances. In the present invention, Si and H are effectively used as raw material gases for forming the second amorphous layer ().
SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ whose constituent atoms are
Silicon hydride gas such as silanes such as H ₁₀ , whose constituent atoms are C and H, for example, carbon number 1
~4 saturated hydrocarbons, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, Examples include silicon hydride. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-butane (n- _C4H10 ) _, pentane ( _C5H12 ), ethylene ( _C2H4 ) as _an ethylene _hydrocarbon
Propylene (C ₃ H ₆ ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylenic hydrocarbons. ,
Acetylene (C ₂ H ₂ ), Methylacetylene (C ₃
H ₄ ), butyne (C ₄ H ₆ ), and halogen alone:
Halogen gases such as fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH, HI, HCl, HBr,
Interhalogen compounds include BrF, ClF, ClF ₃ ,
ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr Silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br,
SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ ,
SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ ,
Examples of silicon hydride include silanes such as SiH ₄ , Si ₂ H ₈ , and Si ₄ H ₁₀ . In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
CH ₂ F ₂ , CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I, C ₂
Halogen-substituted paraffinic hydrocarbons such as H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ ,
Alkyl silicides such as Si(C ₂ H ₅ ) ₄ and SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be cited as effective. These second amorphous layer () forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second amorphous layer () to be formed. the second so that the atoms are contained
It is selected and used as desired when forming the amorphous layer (). For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiH can contain halogen atoms. ₂ Cl ₂ , SiCl ₄ , or SiH ₃ Cl, etc. at a predetermined mixing ratio and introduced in a gaseous state into the apparatus for forming the second amorphous layer () to generate a glow discharge. −(Si _x
A second amorphous layer ( ) consisting of C _1-x ) _y (Cl+H) _1-y can be formed. To form the second amorphous layer () by the sputtering method, target a single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C; These may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary. For example, if a Si wafer is used as a target, the raw material gas for introducing C and H or/and The Si wafer may be sputtered by forming a gas plasma of the above gas. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as needed by using Si and C as separate targets or by using a single mixed target of Si and C. This is done by sputtering inside.
As the material gas for introducing C, H and can be used as In the present invention, so-called rare gases such as He, Ne, Ar, etc. can be used as the diluting gas when forming the second amorphous layer () by the glow discharge method or the sputtering method. It can be mentioned as a suitable one. The second amorphous layer ( ) in the present invention is carefully formed so as to provide the desired properties. In other words, substances containing Si, C, and optionally H or/and In the present invention, it exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive. a
-(Si _x C _1-x ) _y ( _H , For example, to provide the second amorphous layer () with the main purpose of improving pressure resistance, a-(Si _x C _1-x ) _y
( _H , In addition, when a second amorphous layer () is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it becomes more resistant to the irradiated light. As an amorphous material with a certain degree of sensitivity, a-(Si _x C _1-x ) _y
(H,X) _1-y is created. a−(Si _x C _1-x ) _y on the surface of the first amorphous layer ()
When forming the second amorphous layer () consisting of ( _H, In the present invention, the temperature of the support during layer formation is controlled so that a-(Si _x C _1-x ) _y (H,X) _1-y having the desired properties can be formed as desired. It is desirable to have strict control. In the present invention, an optimal range is appropriately selected in accordance with the method of forming the second amorphous layer () in order to effectively achieve the desired purpose, and the second amorphous layer () is formed. formation is performed, but typically 20~
400℃, preferably 50-350℃, optimally 100-300℃
It is desirable that this is the case. For the formation of the second amorphous layer (2012), we use a glow method because it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. It is advantageous to adopt the discharge method or the sputtering method, but when forming the second amorphous layer () using these layer forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. A discharge power of a-(Si _x C _1-x ) _y (H,X) ₁ is created.
-It is one of the important factors that influences the characteristics of _y . As a discharge power condition for effectively producing a-(Si _x C _{1-x ) y} (H, is typically 10-300W, preferably 20-250W, optimally 50W
~200W is desirable. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the support temperature and discharge power for forming the second amorphous layer (2) are preferably within the ranges described above, but these layer formation factors are independent of each other. The desired characteristics a−(Si _x C _1-x ) _y
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the second amorphous layer ( ) consisting of (H,X) _1-y is formed. The amount of carbon atoms contained in the second amorphous layer ( ) in the photoconductive member of the present invention achieves the object of the present invention, as do the conditions for forming the second amorphous layer ( ). This is an important factor in the formation of the second amorphous layer () that provides the desired properties. The amount of carbon atoms contained in the second amorphous layer (2) in the present invention can be determined as appropriate depending on the type and characteristics of the amorphous material constituting the second amorphous layer (2). It can be decided according to the That is, the general formula a-(Si _x C _1-x ) _y (H,X) _1-y
The amorphous material represented by can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ", where 0<a<1) ,
Amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C _1-b ) _c H _1-c ". However, 0<b, c<1) , an amorphous material (hereinafter referred to as "a-(Si _d
C _1-d ) _e (H,X) _1-e ”. However, 0<d,e
<1). In the present invention, the second amorphous layer () is a-
When composed of Si _a C _1-a , the second amorphous layer ()
The amount of carbon atoms contained in is usually 1×
10 ^-3 to 90 atomic%, preferably 1 to 80 atomic%,
Optimally, it is desirable to set it to 10 to 75 atomic%. That is, if we use the representation of a in a-Si _a C _1-a above, a is usually 0.1 to 0.99999, preferably 0.2
~0.99, optimally 0.25-0.9. In the present invention, the second amorphous layer () is a-
(Si _b C _1-b ) _c H _1-c , the amount of carbon atoms contained in the second amorphous layer () is usually 1×
10 ^-3 ~90 atomic%, preferably 1 ~
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is usually 1 to 40 atomic%, preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%. The photoconductive member thus prepared is of excellent practical application. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is usually 0.1 to 0.99999, preferably 0.1 to 0.99, optimally 0.15 to 0.9, and c is usually 0.6. ~0.99, preferably
It is desirable that it be between 0.65 and 0.98, most preferably between 0.7 and 0.95. The second amorphous layer () is a-(Si _d C _1-d ) _e
When composed of ⁽ _H , It is desirable that the content be 1 to 90 atomic%, optimally 10 to 80 atomic%. The content of halogen atoms is usually 1 to 20 atomic%, preferably 1 to 18 atomic%, and optimally 2 to 15 atomic%.
%, and photoconductive members prepared when the halogen atom content is within these ranges can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is usually 19 atomic% or less, preferably 13 atomic%.
The following is desirable. That is, d of the previous a-(Si _d C _1-d ) _e (H,X) _1-e ,
If expressed as e, d is usually 0.1 to 0.99999, preferably 0.1 to 0.99, optimally 0.15 to 0.9, and e is usually
0.8~0.99, preferably 0.82~0.99, optimally 0.85~
A value of 0.98 is desirable. In the present invention, the range of the layer thickness of the second amorphous layer (2) is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. In addition, the layer thickness of the second amorphous layer () is also determined in relation to the amount of carbon atoms contained in the layer () and the layer thickness of the first amorphous layer (). It needs to be appropriately determined as desired based on organic relationships depending on the characteristics required for each layer region. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The layer thickness of the second amorphous layer ( ) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ,
The optimum value is 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Tt, Pb, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal. , imparts conductivity to its surface. The shape of the support body is cylindrical,
The photoconductive member 100 shown in FIG. 1 may be used as an image forming member for electrophotography, for example, if the photoconductive member 100 of FIG. 1 is used as an electrophotographic image forming member. In the case of copying, it is desirable to have an endless belt shape or a cylindrical shape. 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. Next, an outline of one 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 the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (purity 99.99%, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is NO gas (purity
99.999%) cylinder, 1106 is C ₂ H ₄ gas (purity
99.999%) cylinder. In order to cause these gases to flow into the reaction chamber 1101, the valves of gas cylinders 1102 to 1106, 11
22-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valves 1112-1126 are closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 to 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming the first amorphous layer () on the cylindrical substrate 1137, SiH ₄ /He gas is supplied from the gas cylinder 1102, GeH ₄ /He gas is supplied from the gas cylinder 1103, and the first amorphous layer () is formed from the gas cylinder 1102.
From 05, NO gas is supplied to valves 1122, 1123,
Open 1124 and check the outlet pressure gauges 1127, 112
Adjust the pressure of 8, 1129 to 1 Kg/cm ² , gradually open the inflow valves 1112, 1113, 1114, and mass flow controllers 1107, 1108,
1109 respectively. Subsequently, the outflow valves 1117, 1118, 1119 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 ₁
118, 1119, and reaction chamber 1101.
Vacuum gauge 1136 so that the pressure inside reaches the desired value.
Adjust the opening of the main valve 1134 while checking the reading. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the 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, NO gas is contained in a layer formed by gradually changing the opening of the valve 1119 manually or by using an external drive motor or the like to gradually change the flow rate of NO gas according to a pre-designed change rate curve. Controls the distribution concentration of oxygen atoms. In this manner, a first amorphous layer () made of a-SiGe (H,X) in which oxygen atoms are non-uniformly distributed is formed on the substrate 1137. When a halogen atom is contained in the first amorphous layer (), for example, SiF ₄ gas may be further added to the above gas to generate glow discharge. Furthermore, when the first amorphous layer (2) contains halogen atoms instead of hydrogen atoms, instead of the SiH ₄ /He gas and GeH ₄ /He gas,
SiF ₄ /He gas and GeF ₄ /He gas may be used. In order to form the second amorphous layer ( ) on the first amorphous layer ( ) formed to have a desired layer thickness as described above, it is necessary to For example, SiH ₄ gas, C ₂ H ₄
This is accomplished by diluting each of the gases with a diluent gas such as He as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the second amorphous layer, for example, use SiF ₄ gas and C ₂ H ₄ gas, or add SiH ₄ gas thereto and form the second amorphous layer in the same manner as above. This is done by forming a stratum (). Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 1101. Valve 1
In order to avoid gas remaining in the gas piping leading from 117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, and the auxiliary valve 11
32, 1133 and fully open the main valve 1134 to temporarily evacuate the system to high vacuum, as necessary. For example, the amount of carbon atoms contained in the second amorphous layer ( ) is determined by adjusting the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas introduced into the reaction chamber 1101 as desired in the case of glow discharge. Therefore, when forming a layer by sputtering, the sputtering area ratio of the silicon wafer and the graphite wafer should be changed when forming the target, or the mixing ratio of the silicon powder and the graphite powder should be changed. It can be controlled as desired by molding the target. The amount of halogen atoms (X) contained in the second amorphous layer (2) is determined when the raw material gas for introducing halogen atoms, for example SiF ₄ gas, is
This is accomplished by adjusting the flow rate when introduced into 101. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 11, samples were prepared on a cylindrical Al substrate under the conditions shown in Tables 1 to 4 according to the rate of change curves of the gas flow rate ratio shown in FIGS. 12 to 15. Then, each first amorphous layer ( ) was formed on each substrate by changing the gas flow rate ratio of NO and (SiH ₄ +GeH ₄ ) with the elapsed layer formation time, and then,
A second amorphous layer ( ) was formed on each first amorphous layer ( ) under the conditions shown in Table 5 to obtain each of the electrophotographic image forming members (Samples Nos. 101 to 104). Ta. Each of the image forming members thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 2 Using the production apparatus shown in FIG. 11, NO and (SiH ₄ +GeH ₄ ) to form a first amorphous layer () by changing the gas flow rate ratio with the elapsed layer formation time, and then form a second amorphous layer () on the first amorphous layer () under the conditions shown in Table 5. An electrophotographic image forming member was obtained by forming an amorphous layer (). The image-forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source to transmit a light amount of 2 lux sec to a transmission type. It was irradiated through a test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0kV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 3 Under the layer creation conditions in Table 2 of Example 1, the first
2 except that the layer thickness was changed as shown in Table 7.
A first amorphous layer () was formed under the same conditions as shown in Table 5, and then a second amorphous layer () was formed under the conditions shown in Table 5 to form each of the electrophotographic image forming members (). Samples No. 301 to 305) were obtained. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 7 were obtained. Example 4 Under the layer creation conditions in Table 2 of Example 1, B ₂
The first amorphous layer () was formed in the same manner as in Table 2 except that the flow rate ratio of H ₆ /He gas was changed as shown in Table 8, and then in accordance with the conditions in Table 5. A second amorphous layer ( ) was formed to obtain electrophotographic image forming members (Samples Nos. 401 to 405). For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 8 were obtained. Example 5 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mw) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image was evaluated using an electrophotographic image forming member prepared under the same conditions as described above, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. Example 6 The second amorphous layer () was created under the conditions shown in Table 9, and the first amorphous layer () was created under the conditions shown in Tables 1 to 4 of Example 1. Each of the electrophotographic image forming members (sample No. 12-201 to 12-
208, 12-301 ~ 12-308, 12-401 ~ 12-402, 12
-501 to 12-508) were created. Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine, and
Corona charging was performed for a while, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux, sec. The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper. The transferred image was extremely good.
Toner remaining on the electrophotographic imaging member without being transferred was cleaned with a rubber blade. Even after repeating this process over 100,000 times, no image deterioration was observed in any case. Table 9A shows the results of the overall image quality evaluation of the transferred image of each sample and the durability evaluation by repeated continuous action. Example 7 The conditions for creating the amorphous layer () were as shown in Table 1 of Example 1, and when forming the amorphous layer (), a sputtering method was adopted, and a silicon wafer and graphite were formed. By changing the target area ratio of the eye,
Each of the image forming members was produced in exactly the same manner as in Example 1, except that the content ratio of silicon atoms and carbon atoms in the amorphous layer (2) was changed. For each of the imaging members thus obtained,
After repeating the steps of image formation, development, and cleaning as described in Example 1 about 50,000 times, image evaluation was performed, and the results shown in Table 10 were obtained. Example 8 When forming the amorphous layer (), SiH ₄ gas and C ₂
An image forming member was formed by the same method as in Example 7 except that the content ratio of silicon atoms and carbon atoms in the amorphous layer was changed by changing the flow rate ratio of H ₄ gas. It was created. For each image forming member thus obtained, the steps up to transfer were repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 11 were obtained. Example 9 When forming the amorphous layer (), SiH ₄ gas,
The method was exactly the same as in Example 9 except that the flow rate ratio of SiF ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the amorphous layer (). Then, each of the image forming members was prepared. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed and the results shown in Table 12 were obtained. Example 10 Each of the image forming members was prepared in exactly the same manner as in the case of sample No. 103 in Example 1, except that the layer thickness of the amorphous layer ( ) was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 13.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] ◎: Excellent ○: Good △: Adequate for practical use

[Table] ◎: Excellent ○: Good

【table】

【table】

【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Produces image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Produces image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

[Table] Common layer forming conditions in the above embodiments of the present invention are shown below. Substrate temperature: Germanium atom (Ge) containing layer... approx. 200°C Germanium atom (Ge) non-containing layer... approx.
250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[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 diagrams for explaining the distribution state of oxygen atoms in the amorphous layer. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 12 to 15 are explanatory diagrams showing the rate of change curves of the gas flow rate ratio in the embodiments of the present invention, respectively. It is. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 103...Second
amorphous layer ().

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, a first amorphous layer exhibiting photoconductivity made of an amorphous material containing silicon atoms and germanium atoms as a matrix, and a silicon and a second amorphous layer made of an amorphous material having atoms and carbon atoms as a matrix, in this order from the support side, and the distribution concentration of oxygen atoms in the first amorphous layer. is 500atomic on the support side
1. A photoconductive member characterized in that the first amorphous layer has a portion having a high temperature of ppm or more and a portion that is considerably lower on the second amorphous layer side of the first amorphous layer than on the support side. 2. The photoconductive member according to claim 1, wherein the first amorphous layer contains hydrogen atoms. 3. The photoconductive member according to claim 1, wherein the amorphous layer contains halogen atoms. 4. The photoconductive member according to claim 1, wherein the first amorphous layer contains hydrogen atoms and halogen atoms. 5. The photoconductive member according to claim 2, wherein the amount of hydrogen atoms contained in the first amorphous layer is 0.01 to 40 atomic%. 6. The photoconductive member according to claim 3, wherein the amount of halogen atoms contained in the first amorphous layer is 0.01 to 40 atomic%. 7. The photoconductive member according to claim 4, wherein the sum of the amounts of hydrogen atoms and halogen atoms contained in the first amorphous layer is 0.01 to 40 atomic%. 8. The photoconductive member according to claim 1, wherein the amount of germanium atoms contained in the first amorphous layer is 1 to 9.5×10 ⁵ atomic ppm. 9. The photoconductive member according to claim 1, wherein the first amorphous layer has a thickness of 1 to 100 μm. 10. The photoconductive member according to claim 3, wherein the halogen atom is selected from fluorine and chlorine. 11 The first amorphous layer further contains atoms selected from Group 1 or Group 3 of the periodic table, and has a thickness of 30 Å or more.
The photoconductive member according to claim 1, having a layer region having a layer thickness of 5 μm or less. 12. The photoconductive member according to claim 1, wherein the amount of carbon atoms contained in the second amorphous layer is 1×10 ⁻³ to 90 atomic %. 13. The photoconductive member according to claim 1, wherein the amount of hydrogen atoms contained in the second amorphous layer is 1 to 40 atomic %. 14. The photoconductive member according to claim 1, wherein the second amorphous layer contains halogen atoms in an amount of 1 to 20 atomic %. 15. The photoconductive member according to claim 1, wherein the second amorphous layer has a thickness of 0.003 to 30μ.