JPH0423775B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (light here in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). As a photoconductive material for forming a photoconductive layer in a fixed imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. Fixed imaging devices are sometimes 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 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. There were many cases where spots appeared. 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, and in matching with semiconductor lasers currently in practical use. When 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 longer wavelength side. Separately, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the reflectance of the support itself to the light that passes through the photoconductive layer will decrease. When it 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 included 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 the properties of the photoconductive layer. In some cases, problems may arise in the electrical or photoconductive properties or voltage resistance of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, or ,
There may be image defects commonly called "white spots" on the image transferred to the transfer paper, which are thought to be caused by localized discharge destruction development, or, for example, when a blade is used for cleaning, there may be defects caused by rubbing. 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. 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. Still another object of the present invention is to provide high density images without any image defects or blurring during long-term use.
To provide a photoconductive member for electrophotography, which can easily produce high-quality images with clear halftones and high resolution. a support for a photoconductive member; a first amorphous layer exhibiting photoconductivity made of an amorphous material having silicon atoms and germanium atoms as a matrix; and a second amorphous layer made of an amorphous material having atoms as a matrix from the support side, and the first amorphous layer includes a material selected from Group 1 or Group 3 of the periodic table. It is characterized in that the layer region containing the atoms contained in the layer is unevenly distributed 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. 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 has a-SiGe (H,
A first amorphous layer (I) 102 having photoconductivity consisting of X) and a second amorphous layer () 103 provided on the amorphous layer (I) 102. . The germanium atoms contained in the first amorphous layer (I) 102 are continuously formed in the thickness direction of the amorphous layer (I) 102 and in the in-plane direction parallel to the surface of the support 101. It is contained in the amorphous layer (I) 102 so as to be uniformly distributed. In the photoconductive member of the present invention, the first amorphous layer (I) containing germanium atoms is provided with a layer region (PN) containing a substance controlling conductive properties on the support side. , the conduction properties of the layer region (PN) can be controlled arbitrarily as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-SiGe (H, On the other hand, a P-type impurity that provides P-type conduction characteristics and an n-type impurity that provides N-type conduction characteristics can be mentioned. Specifically, P-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), A (aluminum), Ga (gallium), In (indium), T (thallium), etc. Among them, particularly suitable ones are:
B. Ca. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bis-as), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance that controls the conduction properties contained in the layer region (PN) provided in the first amorphous layer (I) is determined by the conduction properties required for the layer region (PN). Alternatively, the layer region (PN) can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support provided in direct contact with the layer region (PN). In addition, the content of the substance that controls the conduction properties is determined by taking into consideration the characteristics of other layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the other layer regions. Selected appropriately. In the present invention, the content of the substance controlling conduction properties contained in the layer region (PN) is usually 0.01 to 5×10 ⁴ atomic ppm, preferably
0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5×10 ³
It is preferable to set it to atomic ppm. In the present invention, the content of the substance controlling the conduction characteristics in the layer region (PN) containing the substance is usually 30 atomic ppm or more, preferably
By adding 50 atomic ppm or more, optimally 100 atomic ppm or more, for example, when the substance to be contained is the P-type impurity, the free surface of the second amorphous layer () is subjected to polar charging treatment. When the substance to be contained is the n-type impurity, injection of electrons from the support side into the first amorphous layer (I) can be effectively prevented. To effectively prevent the injection of holes from the support side into the first amorphous layer (I) when the free surface of the second amorphous layer () is subjected to polar charging treatment. I can do it. 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 controlling the conduction characteristics contained in the layer region (Z) may be determined as desired depending on the polarity and content of the substance contained in the layer region (PN). Therefore, it is determined as appropriate, but in normal cases, it 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 that controls conductivity, the content in the layer region (Z) is preferably 30 atomic ppm or less. is desirable. In addition to the above-described case, in the present invention, the first amorphous layer (I) includes a layer region containing a substance controlling conductivity having one polarity, and a conductivity region having the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance controlling the properties. That is, for example, in the first amorphous layer (I), the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided so as to be in direct contact with each other. A depletion layer can be provided by forming an n-junction. In the present invention, the content of germanium atoms contained in the first amorphous layer (I) is appropriately determined as desired so as to effectively achieve the object of the present invention, but usually is 1 to 9.5×10 ₅ atomic
ppm, preferably 100 to 8.0×10 ₅ atomic ppm, optimally 500 to 7×10 ₅ atomic ppm. In the present invention, specific examples of the halogen atom (X) contained in the first amorphous layer (I) as necessary include fluorine, chlorine, bromine, and iodine. 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 (I) composed of a-SiGe (H, It is made by a vacuum deposition method. For example, to form the first amorphous layer (I) composed of a-SiGe (H, Raw material gas for Si supply, raw material gas for Ge supply obtained by supplying germanium atoms (Ge), and hydrogen atoms (H) as necessary.
Raw material gas or/and halogen atom (X) for introduction
A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber, which is then deposited onto the surface of a predetermined support that has been placed at a predetermined position. a-SiGe(H,X)
What is necessary is to form a layer consisting of. In addition, when forming by 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. If necessary, use He, Ar, or a mixed target of Si and Ge.
A raw material gas for supplying Ge diluted with a diluent gas such as The target may be sputtered by forming a plasma atmosphere. 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 evaporation boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam method ( It can be carried out in the same manner as in the case of spartaling, except that the evaporation is carried out by heating and evaporation by EB method, etc., and the flying evaporation is passed through the desired gas plasma atmosphere. Substances that can be used as the 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 ,
_{Ge4H10 , Ge5H12 , Ge6H14 , Ge7H16 , Ge8H18 ,}
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 , Ge2H6 , 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, CF, _CF3 ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₃ , IF ₇ , IC, and IBr. As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, silicon halides such as SiF ₄ , Si ₂ F ₆ , SiC ₄ , SiBr ₄ and the like are specifically preferred. 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 creating 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. Gases such as hydrogen germanium Ar, H ₂ , He, etc. are introduced into the deposited material forming the first amorphous layer at a predetermined mixing ratio and gas flow rate to generate a glow discharge. By forming a plasma atmosphere of these gases, the first amorphous layer () can be formed on the desired support, but the ratio of hydrogen atoms to be introduced can be more easily controlled. In order to obtain the desired result, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. 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 halogen compound or a silicon compound containing the halogen atoms is introduced into the deposition chamber. It is sufficient to form a gas plasma atmosphere. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a gaseous plasma atmosphere. 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, HC, HBr,
Hydrogen halides such as HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂
Halogen-substituted silicon hydrides such as C ₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ , GeH ₂ F ₂ ,
_GeH3F , _GeHC3 , _GeH2C2 , _{GeH3C ,
GeHBr3 , GeH2Br2} , _GeH3Br , _GeHI3 , _GeH2
germanium hydrogenated halides such as I ₂ , GeH ₃ I,
Halides containing hydrogen atoms as one of their constituent elements, such as _{GeE 4} , GeC 4 , GeBr ₄ , GeI ₄ , GeF ₂ , GeC
Germanium halides such as ₂ , GeBr ₂ , GeI ₂ , etc., gaseous or gasifiable substances may 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 (), 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 and germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge _Five
Germanium hydride such as H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc. and a silicon compound or a silicon compound for supplying Si are made to coexist in the deposition chamber to generate a discharge. It can also be done by causing it to occur. 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 amounts (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%. To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first amorphous layer (), for example, the support temperature and/or hydrogen atoms (H) or The amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge power, etc. may be controlled. In the layer region constituting the first amorphous layer (),
In order to structurally introduce a substance that controls conductivity, such as a group atom or a group atom, the starting material for introducing a group atom or a starting material for introducing a group atom is in a gaseous state during layer formation. It may then be introduced into the deposition chamber together with other starting materials for forming the first amorphous layer. As the starting material for introducing the group atom, it is desirable to use a material that is gaseous at room temperature and humidity, 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 and B ₄ for introducing boron atoms.
_{H10 , B5H9 , B5H11 , B6H10 , B6H12 , B6H14 ,}
and boron halides such as BF ₃ , BC ₃ , BBr ₃ and the like. In addition, AC ₃ ,
GaC ₃ , Ga(CH ₃ ) ₃ , InC ₃ , TC ₃ and the like may also be mentioned. Effective starting materials for the introduction of group atoms in the present invention include hydrogenated phosphorus such as PH ₃ and P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as PF ₅ , PC ₃ , PC ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, _AsH3 ,
AsF ₃ , AsC ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ ,
SbF ₅ , SbC ₃ , SbC ₅ , BiH ₃ , BiC ₃ , BiBr ₃
etc. can also be mentioned as effective starting materials for the introduction of group atoms. The layer thickness of the first amorphous layer (2) in the photoconductive member of the present invention is appropriately determined as desired so that the photocarrier generated in the first amorphous layer (2) is efficiently transported. determined, usually 1~
It is desirable that the thickness be 100μ, 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 thickness of the layer region and the layer region. It is determined as desired depending on the characteristics required for the other layer regions constituting the first amorphous layer formed above, but the lower limit is usually For this reason, it is desirable that the thickness be 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 photoconductive member 100 shown in FIG. It is provided in order to achieve the objectives of the present invention in terms of repeated use characteristics, pressure resistance, use environment characteristics, and durability. In addition, in the present invention, the first non-crystalline layer ()
102 and the second amorphous layer ( ) 103 each have a common constituent element of silicon atoms, so that sufficient chemical stability is ensured at the laminated layer interface. has been completed. The second amorphous layer () in the present invention is an amorphous material containing silicon atoms (Si), carbon atoms (C), and optionally hydrogen atoms (H) and/or halogen atoms (X). (Hereafter, “a−(SixC ₁ −x)y
( _H ,
Consists of. The formation of the second amorphous layer ( ) composed of a-(Si _X C ₁ - _X ) _y (H, This is done by the Teing method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having silicon atoms, and carbon atoms and halogen atoms can be easily introduced into the second amorphous layer (2) to be manufactured. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second amorphous layer () may be formed by using a glow discharge method and a sputtering method in the same apparatus system. To form the second amorphous layer () by the glow discharge method, a-(Si _X C ₁ − _X )y(H,X) ₁ −y
The raw material gas for formation is mixed with a diluent gas at a predetermined mixing ratio if necessary, and introduced into a deposition chamber for vacuum deposition where a support is installed, and the introduced gas is subjected to glow discharge. A-(Si _X C ₁ - _X ) y (H,
X) ₁ -y should be deposited. In the present invention, a-( _SiXC1 - _X )y( _H ,X) ₁
The raw material gas for -y formation is a gaseous substance or gas whose constituent atoms are at least one of silicon atoms (Si), carbon atoms (C), hydrogen atoms (H), and halogen atoms (X). Most gasified substances that can be evaporated can 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 C as a constituent atom, and as necessary, A raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom are mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom and a raw material gas containing C and H as constituent atoms are used. Either the raw material gas containing atoms and/or the raw material gas containing X constituent atoms are mixed at a desired mixing ratio, or the raw material gas containing Si and three of Si, C, and H are mixed at a desired mixing ratio. Raw material gas with constituent atoms or Si, C
and a raw material gas having three constituent atoms of X can be used in combination. 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 as constituent atoms. A mixture of raw material gases containing atoms may be used. In the present invention, F, C, Br, and I are preferable as the halogen atoms (X) contained in the second amorphous layer ( ), with F and C being particularly preferable. In the present invention, raw material gases that can be effectively used to form the second amorphous layer include gaseous substances or substances that can be easily gasified at room temperature and pressure. I can do it. In the present invention, Si and H are effectively used as the raw material gas 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 hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), 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, hydrochloric acid, bromine, and iodine, and hydrogen halides include FH, HI, HC, HBr,
Interhalogen compounds include BrF, CF, C
F ₃ , CF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , IC,
IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiC
₄ , _SiC3Br , _SiC2Br2 , _{SiCBr3 , SiC3}
I, SiBr ₄ , halogen-substituted silicon hydride,
SiH ₂ F ₂ , SiH ₂ C ₂ , SiHC ₃ , SiH ₃ C,
SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , silicon hydride such as SiH ₄ , Si ₂ H ₈ , Si ₄ H ₁₀ , etc.
You can list the types, etc. In addition to these, CF ₄ , CC ₄ , CBr ₄ , CHF ₃ ,
_CH2F2 , _CH3F , _CH3C , _CH3Br , _{CH3I ,}
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ C, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si
Alkyl silicides such as (CH ₃ ) ₄ , Si(C ₂ H ₅ ) ₄ and SiC
Silane derivatives such as halogen-containing alkyl silicides such as (CH ₃ ) ₃ , SiC ₂ (CH ₃ ) ₂ and SiC ₃ CH ₃ can also be mentioned as effective. These second amorphous layer () forming substances contain silicon atoms, carbon atoms, halogen atoms and optionally hydrogen atoms in a predetermined composition ratio in the second amorphous layer () to be formed. It is selected and used as desired when forming the second amorphous layer (2) so that it contains atoms. 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 SiHC ₃ and SiH can contain halogen atoms. _{2C 2} , SiC ₄
Alternatively, a-(Si _{X C 1} - A second amorphous layer () consisting of _X )y(C+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, Si and C may be used as separate targets, or by using a single mixed target of Si and C, if necessary, in a gas atmosphere containing hydrogen atoms and/or halogen atoms. This is done by sputtering.
As the raw material gas for introducing C, H and Can be used as a substance. In the present invention, so-called rare gases, such as He, Ne, Ar, etc., are suitable as the diluting gas used when forming the second amorphous layer () by a glow discharge method or a sputtering method. It can be mentioned as such. The second amorphous layer ( ) in the present invention is carefully formed so that its required properties are imparted as desired. In other words, substances containing Si, C, and optionally H or/and In the present invention, a that exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive.
-(Si _X C ₁ - _X ) _y (H, For example, to provide the second amorphous layer () with the main purpose of improving _voltage resistance, a-(Si _X C ₁ − _X ) y(H, It is produced as an amorphous material with remarkable kinetic behavior. In addition, if a second amorphous layer () is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned electrical insulation problem will be alleviated to some extent, and it will be more effective against the irradiated light. As an amorphous material with a certain degree of sensitivity, a-( _SiXC1 - _X ) _y
(H,X) ₁ -y is created. a-(Si _X C ₁ − _X ) on the surface of the first amorphous layer (I)
A second amorphous layer () consisting of y(H,X) ₁ -y
When forming a layer _, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer _. It is desirable that the temperature of the support at the time of layer formation be strictly controlled so that _-X ) _y (H, In the present invention, the formation of the second amorphous layer () is performed by appropriately selecting an optimal range in accordance with the method of forming the second amorphous layer () in order to effectively achieve the desired purpose. is executed, but normally 20~
400℃, preferably 50-350℃, optimally 100-300℃
It is desirable that this is the case. In order to form the second amorphous layer (2018), we use a glow method, as 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. This is one of the important factors that influences the characteristics _of a-( _SiXC1 - _X ) _yX1 -y, which generates the discharge power. The discharge power conditions _for effectively producing a-( _SiXC1 - _X ) _yX1 -y with good productivity are usually
10~300W, preferably 20~250W, optimally 50~
It is desirable that it be 200W. It is desirable that the gas pressure in the deposition chamber is usually about 0.01 to 1 Torr, preferably about 0.1 to 0.5 Torr. In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second amorphous layer () include the values in the ranges described above.
These layer creation factors are not determined independently and separately, but are based on the desired characteristics a-(Si _X C ₁ −
It is preferable that the optimum values of each layer forming factor be determined based on mutual organic relationships so that a second amorphous layer ( ) consisting of _X )y(H,X) ₁ -y is formed. The amount of carbon atoms contained in the second amorphous layer (2) in the photoconductive member of the present invention is determined as desired to achieve the object of the present invention, similar to the production conditions of the second amorphous layer (2). The second amorphous layer (2) is an important factor in forming the properties. The amount of carbon atoms contained in the second amorphous layer () in the present invention may be determined as desired depending on the type and characteristics of the amorphous material constituting the second amorphous layer (). It can be determined by That is, the general formula a-( _SiXC1 - _X )y( _H ,X) ₁
The amorphous material denoted by -y can be roughly divided into an amorphous material composed of silicon electrons and carbon atoms (hereinafter referred to as "a-SiaC ₁ -a". However, 0<a
<1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as “a-(SibC ₁ −
d) cH ₁ −c”. However, 0<b, c<1),
An amorphous material (hereinafter referred to as "a-[SibC ₁ -d)e(H,X) ₁ -e"] composed of silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary. However, it is classified as 0<d, e<1). In the present invention, the second amorphous layer () is a-
When SiaC ₁ −a<a, the amount of carbon atoms contained in the second amorphous layer () is usually 1×10 ³ to 90 atomic%, preferably 1 to 90 atomic%.
It is desirable that it be 80 atomic%, optimally 10 to 75 atomic%. That is, the previous a-SiaC ₁
- If you display a as a, a is usually 0.1~
0.99999, preferably 0.2-0.99, optimally 0.25-0.9
It is. In the present invention, the second amorphous layer () is a-
When composed of (SibC ₁ -b)cH ₁ -c, the amount of carbon atoms contained in the second amorphous layer () is usually 1 x 10 ^-3 to 90 atomic%, preferably 1 It is desirable that it be ~90 atomic%, optimally 10-80 atomic%. The content of hydrogen atoms is usually 1 to 40 atomic%, preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%.
It is desirable that the hydrogen content be within these ranges, and photoconductive members formed with hydrogen contents within these ranges can be sufficiently applied as excellent materials in practical applications. That is, if expressed as a-(SibC ₁ -b)cH ₁ -c, b is usually 0.1 to 0.99999, preferably 0.1 to 0.99999.
0.99, optimally 0.15-0.9c, usually 0.6-0.99, preferably 0.65-0.98, optimally 0.7-0.95. The second amorphous layer () is a-(SidC ₁ -d)
When composed of e ⁽ _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%, optimally 2 to 18 atomic%
It is preferable that the halogen atom content be 15 atomic %, and photoconductive members prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is usually 19 atomic% or less, preferably
It is desirable that the content be 13 atomic% or less. That is, the previous a-(SidC ₁ -d)e(H,X) ₁ -e
If you display d and e, d is usually 0.1~
0.99999, preferably 0.1-0.99, optimally 0.15-0.9,
It is desirable that e is usually 0.8 to 0.99, preferably 0.82 to 0.99, and optimally 0.85 to 0.98. The number range of the layer thickness of the second amorphous layer ( ) in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. In addition, the layer thickness of the second amorphous layer () is determined depending on the amount of carbon atoms contained in the layer () and the thickness of the first amorphous layer (). It needs to be appropriately determined according to the desired organic relationship depending on the properties required for the layer region. In addition, it is desirable to consider the economical aspects including 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 includes:
It may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, and alloys thereof. As the electrically insulating support, filters 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,
A, Cr, Mo, Au, 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, A ,Ag,Pb,Zn,
Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of a metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired.
If the photoconductive member 100 shown in the figure is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, from the viewpoint of manufacturing and handling of the support, functional strength, etc.
It is considered to be 10μ or more. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 2 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
GeH ₄ gas (purity 99.999%, hereinafter abbreviated as GeH ₄ /He) cylinder, 1104 is SiF ₄ gas (purity 99.999%, hereinafter abbreviated as SiF ₄ /He) diluted with He cylinder, 1105 is diluted with He B ₂ H ₆ gas (purity
99.999%, hereinafter abbreviated as B ₂ H ₆ /He. ) cylinder, 1
106 is a C ₂ H ₄ gas (purity 99.999%) 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.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the reinforcing valves 1132 and 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 11.
B ₂ H ₆ /He gas from valve 1122, 11 from 05
23, 1125, respectively and open the outlet pressure gauge 11.
Adjust the pressure of 27, 1128, 1130 to 1Kg/cm ² , and inflow valves 1112, 1113, 1115.
gradually open the mass flow controller 110.
7, 1108, and 1110, respectively. Subsequently, the outflow valves 1117, 1118, 112
0. Gradually open the auxiliary valve 1132 to allow each gas to flow into the reaction chamber 1101. At this time
SiH ₄ /He gas flow rate vs. GeH ₄ /He gas flow rate vs. B ₂
Adjust the outflow valves 1117, 1118, 1120 so that the ratio with the H ₆ /He gas flow rate becomes the desired value, and read the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 becomes the desired value. Adjust the opening of the main valve 1134 while watching. And basic 1
The temperature of 137 is raised to 50~ by heating heater 1138.
After confirming that the temperature is set in the range of 400°C, the power supply 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101 to deposit the amorphous layer () onto the substrate 1137. begins to form. When the thickness of the layer formed on the substrate 1137 reaches the desired thickness, the discharge is stopped and the outflow valve 112
0 completely closed. Thereafter, the discharge is started again to continue forming further layers. In this manner, a first amorphous layer ( ) having a desired layer thickness is formed on the substrate 1137 . When halogen atoms are contained in the first amorphous layer (), glow discharge may be generated by further adding, for example, SiF ₄ gas to the above gas. Moreover, when the first amorphous layer (2) contains halogen atoms instead of hydrogen atoms, instead of the SiH ₄ /H ₄ gas and GeH ₄ /He gas,
SiF ₄ /He gas and GeH ₄ /He gas may be used. In order to form a second amorphous layer () on the first amorphous layer () formed to 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, SiF ₄ gas and C ₂ H ₄ gas, or by adding SiH ₂ gas thereto, form the second amorphous layer in the same manner as above. This is done by forming (). 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 inside the reaction chamber 1101. Outflow 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. The amount of carbon atoms to be 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 in accordance with the desired flow rate in the case of glow discharge, for example. Alternatively, when forming a layer by sputtering, change the sputter area ratio of the silicon wafer and graphite wafer when forming the target, or change the mixing ratio of silicon powder and graphite powder to form the target. By molding, it can be controlled as desired. The amount of halogen atoms (X) to be contained in the second amorphous layer () is such that the raw material gas for introducing halogen atoms, for example SiF ₄ gas, is
This is done by adjusting the flow rate when introduced into the 01. 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. 2, layers were formed on a cylindrical substrate A under the conditions shown in Table 1 to obtain an electrophotographic image forming member. The image-forming member thus obtained was installed in a charging exposure experimental device, corona charged at 5.0KV for 0.3 seconds, and immediately exposed to a light image using a tungsten lamp light source, with a light intensity of 2ux・sec. 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;
Transferred onto transfer paper with 0.5KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 2 In Example 1, B ₂ H ₆ (SiH ₄ +
Each of the electrophotographic layer forming members was produced under the same conditions as in Example 1, except that the flow rate for GeH ₄ ) was changed as shown in Table 2. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 2 were obtained. Example 3 Each electrophotographic image was prepared in the same manner as in Example 1, except that the thickness of the first layer constituting the first amorphous layer () was changed as shown in Table 3. A forming member was created. 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 3 were obtained. Example 4 Same as Example 1 except that the first amorphous layer ( ) was formed on the cylindrical A substrate under the conditions shown in Table 4 using the manufacturing apparatus shown in FIG. An ancient electrophotographic imaging member was formed. The image-forming member thus obtained was installed in a charging exposure experimental device, corona charged at 0.5 KV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source, with a light intensity of 2ux·sec being transmitted through 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 5 Electrophotography was carried out under the same conditions as in Example 4, except that the flow rate of PH ₃ to (SiH ₄ +GeH ₄ ) was changed as shown in Table 5 when creating the first layer. Each of the imaging members was prepared. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained. Example 6 Each electrophotographic image was formed in the same manner as in Example 1, except that the layer thickness of the first layer constituting the first amorphous layer () in Example 1 was changed as shown in Table 6. Created the parts. An image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, and the results shown in Table 6 were obtained. Example 7 Same as Example 1 except that the first amorphous layer ( ) was formed on the cylindrical A substrate under the conditions shown in Table 7 using the manufacturing apparatus shown in FIG. An electrophotographic imaging member was formed. The image-forming member thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 KV for 0.3 seconds, and then a light image was irradiated using a tungsten lamp light source, transmitting a light intensity of 2ux・sec. It was irradiated through a molded stetochaat. 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 8 Same as Example 1 except that the first amorphous layer ( ) was formed on the cylindrical A substrate under the conditions shown in Table 8 using the manufacturing apparatus shown in FIG. An electrophotographic imaging member was formed. The image-forming member thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 KV for 0.3 seconds, and then a light image was irradiated using a tungsten lamp light source, transmitting a light intensity of 2ux・sec. It was irradiated through a mold 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 9 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 transfer image was evaluated for 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 10 Electrophotographic image formation was performed according to the same conditions and procedures as in Examples 4, 7, and 8, except that the conditions for creating the amorphous layer () were as shown in Table 9. Each member (sample No. 12-401 to 12-408, 12-701 to 12
-708, 12-801 to 12-808). Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine under the same conditions as described in each example. Then, for each of the electrophotographic forming members corresponding to each example, an overall image quality evaluation of the transferred image and an evaluation of durability after repeated and continuous use were conducted. Table 10 shows the results of the overall image quality evaluation of the transferred image of each sample and the durability evaluation after repeated and continuous use. Example 11 When forming an amorphous layer (), the same procedure was carried out except that the target area ratio of the silicon wafer and graphite was changed to change the content ratio of silicon atoms and carbon atoms in the amorphous layer (). Each of the imaging members was made in exactly the same manner as in Example 1. For each of the imaging members thus obtained, Example 1
After repeating the image forming, developing, and cleaning steps approximately 50,000 times, as described in
The results shown in Table 11 were obtained. Example 12 When forming the amorphous layer (), SiH ₄ gas and C ₂
Each of the image forming members was created in exactly the same manner as in Example 1, except that the flow rate ratio of H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the amorphous layer ( ). . For each of the image forming members thus obtained, the steps up to transfer were repeated about 50,000 times in the directions described in Example 1, and then image evaluation was performed, and the results shown in Table 12 were obtained. Example 13 When forming the amorphous layer (), SiH ₄ gas,
Images were obtained in the same manner as in Example 1, except that the content ratio of silicon atoms and carbon atoms in the amorphous layer () was changed by changing the flow rate ratio of SiF ₄ gas and C ₂ H ₄ gas. Each of the forming members was created. 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 13 were obtained. Example 14 Each of the image forming members was prepared in exactly the same manner as in Example 1, except that the layer thickness of the amorphous layer (2) was changed. Image formation, development, as described in Example 1
The cleaning process was repeated to obtain the results shown in Table 14.

【table】

[Table] ◎〓Excellent ○〓Good

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

【table】

[Table] ◎〓Excellent ○〓Good △〓Sufficient for practical use

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

【table】

【table】

【table】

【table】

【table】

[Table] Evaluation criteria: ◎…Excellent
○…Good

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur.

[Table] ◎: Very good ○: Good △: Sufficient for practical use ×: Image defects occur

【table】

[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) content: approx. 200℃ No germanium atom (Ge) content: approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIG. 2 is a schematic diagram of the apparatus used to create the photoconductive member of the present invention in Examples. This is an explanation. 100...Photoconductive member, 101...Support, 1
02...First amorphous layer (), 103...Amorphous layer ().

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member, and a first amorphous material exhibiting photoconductivity made of an amorphous material having silicon atoms and germanium atoms as a matrix on the support. layer, and a second amorphous layer made of an amorphous material having silicon atoms and carbon atoms as a matrix from the support side, and the first amorphous layer has a periodic table. A photoconductive member characterized in that a layer region containing atoms selected from Group 3 or Group 3 is unevenly distributed 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 first amorphous layer contains halogen hydrogen atoms. 4. The photoconductive member according to claim 1, wherein the first amorphous layer contains hydrogen atoms and halogen hydrogen atoms. 5. The photoconductive member according to claim 2, wherein the hydrogen atom content is 0.01 to 40 atomic%. 6 The content of the halogen atoms is 0.01 to 40 atomic
% of the photoconductive member according to claim 3. 7 The content of the hydrogen atoms and the halogen atoms is
The photoconductive member according to claim 4, wherein the content 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 is 1 to 9.5×10 ⁵ atomic ppm. 9 The atoms belonging to the group of the periodic table are B, Ga
The photoconductive member according to claim 1, which is selected from the following. 10 The atom belonging to Group 1 of the periodic table is P,
The photoconductive member according to claim 1, which is selected from Aa. 11. The photoconductive member according to claim 1, wherein the photoconductive member contains 0.01 to 5×10 ⁴ atoms ppm of atoms selected from Group 1 or Group 3 of the periodic table. 12. The photoconductive member according to claim 3 or 4, wherein the halogen atom is selected from fluorine and chlorine. 13. The photoconductive member according to claim 1, wherein the layer region containing atoms selected from Group 1 or Group 3 of the periodic table has a layer thickness of 30 Å to 5 μ. 14. The photoconductive member according to claim 1, wherein the amount of carbon atoms contained in the second amorphous layer is 1 x 10 ^-3 to 90 atomic %. 15. The photoconductive member according to claim 1, wherein the amount of hydrogen atoms contained in the second amorphous layer is 1 to 40 atomic %. 16. The photoconductive member according to claim 1, wherein the amount of halogen atoms contained in the second amorphous layer is 1 to 20 atomic %. 17. The photoconductive member according to claim 1, wherein the second amorphous layer has a thickness of 0.003 to 30 μm.