JPH0220104B2 - - 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.)
The present invention relates to photoconductive members for electrophotography that are 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 Ip/dark current Id], has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and is not harmful to the human body during use. On the other hand, solid-state imaging devices are required to have characteristics such as being non-polluting and being able to easily process afterimages within a predetermined time. Especially,
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/reading device is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there is a need to improve overall characteristics in terms of usage environment characteristics and stability over time, and there are areas that can be further improved. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, 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, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance 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. Furthermore, when the photoconductive layer is composed of a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, a problem may arise in the electrical or photoconductive properties or electrical withstand voltage 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" sometimes occurred. 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. On the other hand, in consideration of matching with a semiconductor laser, it has been proposed to provide an amorphous layer made of an amorphous material containing at least germanium atoms on a support. Adhesion with the crystalline layer and diffusion of impurities from the support into the amorphous layer may pose problems. 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 and applicability as a photoconductive member used in electrophotographic image forming members, a-
Si, especially a silicon atom as a host, and a hydrogen atom H
or an amorphous material containing at least one of the halogen atoms
SiH, It not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side. The present invention is not easily affected by the material of the support, has always stable electrical, optical, and photoconductive properties, and is applicable to all environments with almost no restrictions on the usage environment. The main object of the present invention is to provide a photoconductive member for electrophotography which has excellent photosensitivity characteristics, is extremely resistant to light fatigue, does not cause any deterioration phenomenon 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 for electrophotography 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 for electrophotography that has 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 for electrophotography having high signal-to-noise ratio characteristics. The electrophotographic photoconductive member of the present invention includes a support for an electrophotographic photoconductive member, and a 1 to 1×
A first layer region containing 10 ⁶ atomic ppm germanium atoms and having a layer thickness of 30 Å to 50 μ, which is at least partially crystallized, and silicon atoms with a thickness of 1 to 9.5×
a second layer region with a layer thickness of 30 Å to 50 μm containing an amorphous material containing 10 ⁵ atomic ppm of germanium atoms, and a third layer region with a layer thickness of 0.5 to 90 μm containing an amorphous material containing silicon atoms. layer area and 1×10 ^-3 ~
A photoreceptive layer for electrophotography, comprising a fourth layer region having a layer thickness of 0.003 to 30μ made of an amorphous material containing 90 atomic% of carbon atoms and silicon atoms, and a photoreceptive layer provided in order from the support side. A photoconductive member (hereinafter referred to as "photoconductive member"), in which at least one of the first layer region and the second layer region contains a substance controlling conductivity of 0.01 to 5×
It is characterized by containing 10 ⁴ atomic ppm. The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it is highly sensitive.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, 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 optical response. 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.
The photoreceptive layer 102 has a free surface 105 on one end surface. From the support 101 side, the light-receiving layer 102 is composed of only germanium atoms or germanium atoms and silicon atoms as a matrix, and contains either hydrogen atoms or halogen atoms as necessary, and at least a part thereof is crystalline. a-Si(H,X) containing germanium atoms (hereinafter referred to as "a-Si, −Si
The second layer region (G) 103 is composed of a-Si(H,X) and has photoconductivity (S )10
4 and an amorphous material containing at least a carbon atom and a silicon atom, and optionally a hydrogen atom or/and a halogen atom (hereinafter referred to as "a-(Si _x C _1-x ) _y
(H,X) _1-y ") are sequentially laminated. When the first layer region (C) 106 is composed of a material containing germanium atoms and silicon atoms, the germanium atoms and silicon atoms are
It is contained so as to be continuous and uniformly distributed in the layer thickness direction of the layer region (C) 106 and in the in-plane direction parallel to the surface of the support, or it is contained non-uniformly in the layer thickness direction. It is contained in such a way that it has a distribution state. The germanium atoms contained in the second layer region (G) 103 are continuous and uniform in the layer thickness direction of the second layer region (G) 103 and in the in-plane direction parallel to the surface of the support 101. It is contained in the second layer region (G) 103 in a distributed state, or it is contained in a non-uniform distribution state in the layer thickness direction. In the photoconductive member 100 of the present invention, the first layer region (C) 106 and the second layer region (G) 103
A substance (D) that controls conductive properties is contained in at least one of the second layer regions (G) 10.
Preferably, 3 contains a material that provides the desired conductive properties. In the present invention, the first layer region (C) 106
Alternatively, the substance (D) that controls the conductive properties contained in the second layer region (G) 103 is distributed throughout the entire layer region of the first layer region (C) 106 or the second layer region (G) 103. It may be contained evenly and uniformly, and the first
layer region (C) 106 or second layer region (G) 1
It may be contained so as to be unevenly distributed in some layer regions of 03. Substance (D) that controls conduction properties in the present invention
In the case where the substance (D) is contained in the second layer region (G) so as to be omnipresent in a part of the layer region (G), the layer region (D) containing the substance (D) PN) is preferably provided as an end layer region of the second layer region (G). Especially,
When the layer region (PN) is provided as the end layer region on the support side of the second layer region (G), the type of the substance (D) contained in the layer region (PN) and its By appropriately selecting the content as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the photoreceptive layer. In the photoconductive member of the present invention, the substance (D) capable of controlling conduction properties is incorporated into the second layer region (G) constituting a part of the photoreceptive layer as described above. It is contained evenly throughout the layer region (G) or unevenly distributed in the layer thickness direction,
Furthermore, a third layer provided on the second layer region (G)
The substance (D) may also be contained in the layer region (S). When the substance (D) is contained in the third layer region (S), the type, amount, and content of the substance (D) contained in the second layer region (G) are determined. Depending on the method, the type and amount of the substance (D) to be contained in the third layer region (S), and the manner in which it is contained are appropriately determined. In the present invention, when the substance (D) is contained in the third layer region (S), preferably the substance (D) is contained in the layer region including at least the contact interface with the second layer region (G). It is desirable to include substance (D). In the present invention, the substance (D) may be contained uniformly in the entire layer area of the third layer area (S), or may be contained uniformly in a part of the layer area. is also good. When both the second layer region (G) and the third layer region (S) contain a substance (D) that controls conduction characteristics, the substance (D) in the second layer region (G) It is desirable that the layer region containing the substance (D) and the layer region containing the substance (D) in the second layer region (S) be in contact with each other. Moreover, the first layer region (C) and the second layer region (G)
When the substance (D) is contained in the first layer area (C), the second layer area (G) and the third layer area (S), the substance (D) is contained in the first layer area (C), the second layer area (G) and the third layer area. (S)
They may be of the same type or different types,
Further, the content may be the same or different in each layer region. However, in the present invention, when the substance (D) contained in each layer region is the same in the three, the content in the second layer region (G) is It is preferable that the number of substances (D) be increased or that different types of substances (D) with different electrical characteristics be contained in each desired layer region. In the present invention, by containing the substance (D) that controls the conduction characteristics at least in the second layer region (G) constituting the photoreceptive layer, the layer containing the substance (D) can be improved. Region [Second layer region (G)
It is possible to arbitrarily control the conduction properties of the layer (which may be a part or all of the layer region) as desired, but such a material (D) is
The so-called impurities in the semiconductor field can be mentioned, and in the present invention, a-SiGe(H,X)
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), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. 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 (bismuth), etc.
Particularly preferably used are P and As. In the present invention, the content of the substance that controls the conduction properties in the layer region (PN) depends on the conduction properties required for the layer region (PN) or the layer region (PN) on the support. When 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, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also taken into consideration, and the material that controls the conduction characteristics is determined. The content is selected appropriately. In the present invention, the content of the substance (D) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1× 10 ⁴ atomic ppm, optimally 1
It is desirable that the amount is 5×10 ³ atomic ppm. In the present invention, the content of the substance (D) that controls conduction characteristics in the layer region (PN) containing the substance (D) is preferably 30 atomic ppm.
As described above, by setting the concentration to more preferably 50 atomic ppm or more, optimally 100 atomic ppm or more, for example, when the substance (D) to be contained is the above-mentioned P-type impurity, the free surface of the photoreceptive layer becomes polar. When subjected to a charging treatment, injection of electrons from the support side through at least the second layer region (G) into the third layer region (S) can be effectively prevented, and
When the substance (D) to be contained is the n-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the substance (D) to be contained may be charged from the support side through at least the second layer region (G). Injection of holes into the third layer region (S) can be effectively prevented. In the above case, as described above, the layer region (Z) excluding the layer region (PN) has the conductivity type of the substance that controls the conduction characteristics contained in the layer region (PN). The layer region (PN) may contain a substance that governs the conduction characteristics of a polarity different from the polarity of the layer region (PN), or a substance that governs the conduction characteristics of a conduction type of the same polarity as the polarity of the layer region (PN). It may be contained in an amount much smaller than the actual amount. 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 should be determined appropriately, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 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 (D) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, the photoreceptive layer contains a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by directly contacting the layer region containing the material. For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other, so-called P-n.
A junction can be formed to provide a depletion layer. In the present invention, germanium atoms are not contained in the third layer region (S) provided on the second layer region (G), and a light-receiving layer is not provided in such a layer structure. By forming such a photoconductive member, it is possible to obtain a photoconductive member that has excellent photosensitivity to light in the entire range of wavelengths from short wavelengths to relatively long wavelengths, including the relatively visible light region. In addition, the distribution state of germanium atoms in the first layer region (C) is such that germanium atoms are continuously distributed in the entire layer region, so that the distribution state of germanium atoms in the first layer region (C) and the second layer region is different. It has excellent affinity with the region (G), and when a semiconductor laser or the like is used, the first layer region (C) absorbs light on the longer wavelength side that cannot be completely absorbed by the second layer region (S). ), substantially complete absorption can be achieved, and interference due to reflection from the support surface can be prevented. Further, in the photoconductive member of the present invention, the materials constituting the first layer region (G) and the second layer region (S) each have common constituent elements of silicon atoms and germanium atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. In the present invention, the content of germanium atoms contained in the first layer region (C) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably is 1~1×
¹⁰⁶ atomic ppm, more preferably 100-1×
10 ⁶ atomic ppm, optimally 500 to 1×10 ⁶ atomic
Preferably in ppm. The content of germanium atoms contained in the second layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9.5×10 ⁵ atomic ppm, more preferably 100 to 8×10 ⁵ atomic ppm, optimally
It is desirable that the content be 500 to 7×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region (C) and the second layer region (G) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the photoconductive member formed has the desired properties. In the present invention, the layer thickness of the first layer region (C) is preferably 30 Å to 50 μ, more preferably 40 μ
It is desirable that the thickness be 50 Å to 30 μ, most preferably 50 Å to 30 μ. Further, the layer thickness T _B of the second layer region (G) is preferably 30 Å to 50 μ, more preferably 40 Å to 40 μ, and optimally 50 Å to 30 μ. Further, the layer thickness T of the third layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. The sum (T _B +T) of the layer thickness T _B of the second layer region (G) and the layer thickness T of the third layer region (S) is based on the characteristics required for both layer regions and the overall photoreceptive layer. It is appropriately determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the required properties. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
When satisfying the relationship T _B /T≦1, it is desirable to select appropriate numerical values for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness D be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (C) is 1×
In the case of 10 ⁵ atomic ppm or more, the layer thickness of the first layer region (C) is desirably made quite thin, preferably 30μ or less, more preferably 30μ or less.
It is desirable that the thickness be 25μ or less, optimally 20μ or less. In the present invention, the first layer region (C), the second layer region (G), the third layer region (S),
Specifically, the halogen atoms (X) contained in the fourth layer region (M) include fluorine, chlorine,
Examples include bromine and iodine, with fluorine and chlorine being particularly preferred. 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 layer region (C) composed of μc-Ge (Si, H, X). This is accomplished by a vacuum deposition method and a vacuum evaporation method. For example, μc-Ge (Si, H,
In order to form the first layer region (C) composed of A raw material gas for supplying Si, a raw material gas for introducing hydrogen atoms (H), and/or a raw material gas for introducing halogen atoms (X) is kept at a desired gas pressure in a deposition chamber whose interior can be reduced in pressure. A glow discharge may be generated in the deposition chamber to form a layer made of .mu.c-Ge (Si, H, In addition, when forming by sputtering method, Ge
using one target composed of Ge and a target composed of Si, or using two targets composed of this target and Ge, or
Using a mixed target of Si and Ge, Ge diluted with diluent gas such as He or Ar as necessary.
When necessary, a raw material gas for supply and a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) are introduced into a deposition chamber for sputtering to form a desired gas plasma atmosphere and to form a desired gas plasma atmosphere. All you have to do is spat it out. 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 resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and passed through a desired gas plasma atmosphere. Further, when forming the first layer region (C), it is necessary to raise the support temperature by 50° C. to 200° C. higher than the support temperature when forming the second layer region (G). In order to form the second layer region (G) composed of a-SiGe (H, It will be done. For example, by glow discharge method, a-SiGe
To form the second layer region (G) composed of (H, A raw material gas for supplying Ge, and a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as necessary, into a deposition chamber whose interior can be made to have a reduced pressure. It is sufficient to introduce the a-SiGe (H, In addition, when forming by sputtering method, for example, in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
One target made of Ge and a target made of Si, or
Using two targets composed of Ge,
Alternatively, using a mixed target of Si and Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He or Ar as necessary is converted into hydrogen atoms (H) or / and introducing a gas for introducing halogen atoms (X) into a deposition chamber for sputtering,
The target may be sputtered by forming a desired gas 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 deposition boat as evaporation sources, and the evaporation sources are heated using resistance heating method or electron beam method ( This can be carried out in the same manner as in the case of sputtering, except that the flying evaporates are heated and evaporated by EB method or the like and 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 Ge supply 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 , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. 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 ₂ ,
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 layer region (C) and the second layer region (G) containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating a first layer region (C) and a second layer region (G) containing halogen atoms according to the glow discharge method, basically silicon halide, which serves as a raw material gas for supplying Si, for example, is used. A first layer region (C) and a second layer region are prepared by mixing germanium hydride, which is a raw material gas for supplying Ge, and gases such as Ar, H ₂ , He, etc., at a predetermined mixing ratio and gas flow rate. (G) into a deposition chamber forming a first layer region (C) and a second layer region (C) on the desired support by creating a glow discharge and forming a plasma atmosphere of these gases. However, in order to make it easier to control the introduction ratio of hydrogen atoms, hydrogen gas or a silicon compound gas containing hydrogen atoms may be added to these gases. A layer may be formed by mixing desired amounts. 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. Further, when forming the first layer region (C), the support temperature must be 50 to 200° C. higher than the temperature of the support forming the second layer region (G). 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 +
Halogen-substituted silicon hydrides such as SiH ₂ 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 I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
A first layer region (C) and a second layer region (G) in which gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr _{2 and} GeI 2 are also effective. It can be mentioned as a starting material for the formation. Among these substances, halides containing hydrogen atoms are used to introduce electrically or photoelectrically the halogen atoms into the layers when forming the first layer region (C) and the second layer region (G). Since hydrogen atoms, which are extremely effective in controlling properties, are also introduced, they are used as a suitable raw material for introducing halogen in the present invention. In order to structurally introduce hydrogen atoms into the first layer region (C) and the second layer region (G), in addition to the above, H ₂ or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ etc. with germanium or a germanium compound for supplying Ge, or GeH ₄ ,
Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₀ , Ge ₆ H ₁₄ ,
This can also be done by causing a discharge by coexisting germanium hydride such as Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. . In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the first layer region (C) of the photoconductive member to be formed The sum (H+X) is preferably 0.0001 to 40 atomic%, more preferably
0.005-30atomic%, optimally 0.01-25atomic%
It is desirable that this is done. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer region (C), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled. In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the amount of hydrogen atoms and halogen atoms contained in the second layer region (G) of the photoconductive member to be formed The sum (H+X) is preferably 0.01 to 40 atomic%, more 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 second layer region (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. The amount of the starting material used to contain (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the third layer region (S) composed of a-Si(H,X), the starting material (I) for forming the second layer region (G) described above is used. The second layer region (G) is formed using the starting materials [starting materials for forming the third layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying Ge. It can be carried out according to the same method and conditions as in the case of forming. That is, 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 third layer region (S) composed of a-Si(H,X). It is made by a vacuum deposition method. For example, in order to form the third layer region (S) composed of a-Si (H, Along with the raw material gas for supplying Si, a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure. to generate a glow discharge, and a
A layer consisting of -Si(H,X) may be formed.
In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the third layer region (S) to be formed is preferably 1 to
It is desirable that the content be 40 atomic %, more preferably 5 to 30 atomic %, most preferably 5 to 25 atomic %. A substance (D) that controls conduction properties, for example, group group atoms or group atoms, is structurally introduced into the layer region constituting the photoreceptive layer to form a layer region containing the substance (D) (PN ), during layer formation, the starting material for introducing group atoms or the starting material for introducing group atoms is placed in a gaseous state in a deposition chamber, and another starting material for forming the photoreceptive layer is added. It is best to introduce it along with the substance. As a starting material for introducing such 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 ₄ H ₁₀ ,
Examples include boron hydrides such as B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . 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 a group atom 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 , SiH ₃ , SiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. The fourth layer region (M) in the present invention is an amorphous layer containing silicon atoms (Si), carbon atoms (C), and optionally hydrogen atoms (H) and/or halogen atoms (X). quality material ('a-(Si _x C _1-x ) _y (H,X) _1-
y '', where 0<x, y<1). The fourth composed of a-(Si _x C _1-x ) _y (H,X) _1-y
The layer region (M) is formed by a glow discharge method, a sputtering 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 a photoconductive member, it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the fourth layer region (M) to be manufactured, etc. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same equipment system to achieve the fourth
A layer region (M) may be formed. To form the fourth layer region (M) by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x ) _y (H, X) _1-y is diluted as necessary. The gas is mixed with a predetermined mixing ratio and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and the gas is already deposited on the support. What is necessary is to deposit a-(Si _x C _1-x ) _y (H,X) _1-y on the formed third layer region (S). In the present invention, a-(Si _x C _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Most gaseous substances or gasified substances containing at least one of carbon atoms (C), hydrogen atoms (H), and halogen atoms (X) as constituent atoms are used. obtain. 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, preferred halogen atoms (X) contained in the fourth layer region (M) are F,
Cl, Br, and I, with F and Cl being particularly desirable. In the present invention, raw material gases that can be effectively used to form the fourth layer region (M) include those in a gas state at normal temperature and normal pressure, or substances that can be easily gasified. can be mentioned. In the present invention, gases effectively used as raw material gases for forming the fourth layer region (M) include SiH 4 , Si 2 H 6 , Si 3 H 8 , and SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , _{Si4H10 _}
Silicon hydride gas such as silanes, C
and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogen, hydrogen halide, halogen intermediate compound,
Examples include silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), and n-butane (n-
C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ), 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 ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogens include fluorine,
Halogen gases such as chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, HBr, and 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 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 ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. be able to. 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,
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ , SF ₆ , Si
Alkyl silicides such as (CH ₃ ) ₄ , Si(C ₂ H ₅ ) ₄ , and SiCl
Silane derivatives such as halogen-containing alkyl silicides such as (CH ₃ ) ₂ , SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These fourth layer region (M) forming substances contain silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the fourth layer region (M) to be formed. is selected and used as desired when forming the fourth layer region (M) so that it contains. 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. _{A- _ _ _} (Si _x
C _1-x ) _y (H,X) Fourth layer region (M) consisting of _1-y
can be formed. To form the fourth layer region (M) by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements as necessary. For example, if a Si wafer is used as a target, raw material gases for introducing C, H and/or The Si wafer may be sputtered by forming plasma. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as necessary by using Si and C as separate targets or by using a mixed target of Si and C. This is done by sputtering inside.
The material used as the source gas for introducing C, H and can be used. In the present invention, so-called rare gases such as He, Ne, Ar, etc. are suitable as the diluting gas used when forming the fourth layer region (M) by the glow discharge method or the sputtering method. It can be mentioned as such. The fourth layer region (M) in the present invention is carefully formed so as to provide the required properties as desired. In other words, substances containing Si, C, and optionally H or/and In the present invention, a-(Si _x C1 _-x ) _y
In order to form (H,X) _1-y , the preparation conditions are strictly selected as desired. For example, to provide the fourth layer region (M) with the main purpose of improving voltage resistance, a-(Si _x C _1-x ) _y (H,X) _1-y is electrically insulating in the usage environment. Created as an amorphous material with pronounced sexual behavior. In addition, when the fourth layer region (M) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and it resists the irradiated light to a certain extent. As an amorphous material with a sensitivity of 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 third layer region (S)
A _fourth layer region (M) consisting of a-(Si _x C _1-x ) _y (H _, 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 during layer formation be strictly controlled so that C _1-x ) _y (H,X) _1-y can be formed as desired. In the present invention, an optimal range is appropriately selected in accordance with the method of forming the fourth layer region (M) in order to effectively achieve the desired purpose, and the fourth layer region (M)
formation is carried out, usually at 20-400℃,
The temperature is preferably 50 to 350°C, most preferably 100 to 300°C. Fourth layer area (M)
The glow discharge method and sputtering method are used to form the layer, 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. is advantageous, but when forming the fourth layer region (M) by these layer forming methods, the discharge power during layer forming is set at a-( Si _x C _1-x ) _y (H,X) This is one of the important factors that influences the characteristics of _1-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
It is desirable that the power be 50 to 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 above-mentioned values are listed as the preferable numerical ranges of the support temperature and discharge power for creating the fourth layer region (M), but these layer creation 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 formation factor be determined based on mutual organic relationship so that a fourth layer region (M) consisting of (H,X) _1-y is formed. Similar to the production conditions of the fourth layer region (M), the amount of carbon atoms contained in the fourth layer region (M) in the photoconductive member of the present invention is determined according to the desired amount to achieve the object of the present invention. This is an important factor in the formation of the fourth layer region (M) where the properties are obtained. The amount of carbon atoms contained in the fourth layer region (M) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the fourth layer region (M). It can be determined by That is, the general formula a-(Si _x C _1-x ) _y (H,X) _1-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ". However, 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 fourth layer region (M) is a-
When composed of Si _a C _1-a , the fourth layer region (M)
The amount of carbon atoms contained in is preferably 1×
10 ^-3 to 90 atomic%, more preferably 1 to 80 atomic%
%, preferably 10 to 75 atomic%. That is, if expressed as a in a-Si _a C _1-a above, a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25 to 0.9. In the present invention, the fourth layer region (M) is a-
(Si _b C _1-b ) _c H _1-c , the amount of carbon atoms contained in the fourth layer region (M) is preferably 1×10 ⁻³ to 90 atomic%, More preferably, it is 1 to 90 atomic %, most preferably 10 to 80 atomic %. The hydrogen atom content is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 35 atomic%.
It is desirable that the hydrogen content be 30 atomic %, and photoconductive members formed with a hydrogen content in this range can be satisfactorily applied in practice. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is preferably 0.1 to 0.99999, more preferably 0.1 to
0.99, optimally 0.15~0.9, C preferably 0.6~
0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. The fourth layer region (M) is a-(Si _d C _1-d ) _e (H,
X) When composed of _1-e , the content of carbon atoms contained in the fourth layer region (M) is as follows:
Preferably, it is 1×10 ⁻³ to 90 atomic %, preferably 1 to 90 atomic %, and optimally 10 to 80 atomic %. The content of halogen atoms is preferably 1 to 20 atomic%, and photoconductive members produced when the halogen atom content is within this range can be sufficiently applied to practical applications. It is. The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more 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 preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
It is desirable that it be between 0.82 and 0.99, most preferably between 0.85 and 0.98. The number range of the layer thickness of the fourth layer region (M) 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. Further, the layer thickness of the fourth layer region (M) is the same as that of the fourth layer region (M).
The relationship between the amount of carbon atoms contained therein and the layer thickness of the third layer region (S) is determined based on the organic relationship depending on the characteristics required for each layer region. It is necessary to decide accordingly. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The thickness of the fourth layer region (M) in the present invention is preferably 0.003 to 30μ, more preferably
It is desirable that the thickness be 0.004 to 20μ, most preferably 0.005 to 10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. 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. In the gas cylinders 202 to 206 in the figure, raw material gas for forming the photoconductive member of the present invention is sealed.
SiH ₄ gas diluted with He (purity 99.999% or less)
Abbreviated as SiH ₄ /He. ) cylinder, 203 is GeH ₄ gas diluted with He (purity 99.999%, hereinafter GeH ₄ /
Abbreviated as He. ) cylinder, 204 diluted with He
SiF ₄ gas (99.99% purity, hereinafter abbreviated as SiF ₄ /He)
cylinder, 205 is a B ₂ H ₆ gas diluted with He (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /He);
206 is a H ₂ gas (purity 99.999%) cylinder. In order to flow these gases into the reaction chamber 201, the valves 222 to 22 of the gas cylinders 202 to 206 are used.
6. Check that the leak valve 235 is closed, and also check the inflow valves 212 to 216, the outflow valves 217 to 221, and the auxiliary valves 232 and 233.
After confirming that the main valve 234 is opened, the reaction chamber 201 and each gas pipe are evacuated by opening the main valve 234. Next, the reading on the vacuum gauge 236 is approximately 5×
When the temperature reaches 10 ^-6 torr, the auxiliary valves 232 and 23
3. Close the outflow valves 217-221. Next, to give an example of forming the first layer region on the cylindrical base 237, the gas cylinder 2
SiH ₄ /He gas from 02, from gas cylinder 203
GeH ₄ /Ee gas, B ₂ H ₆ / from gas cylinder 205
Open He gas valves 222, 223, 225, respectively, adjust the pressure of outlet pressure gauges 227, 228, 230 to 1 Kg/cm ² , and inflow valves 212, 21
3 and 215 are gradually opened to flow into the mass flow controllers 207, 208, and 210, respectively. Subsequently, the outflow valves 217, 218, 22
0. Gradually open the auxiliary valve 232 to allow each gas to flow into the reaction chamber 201. At this time
SiH ₄ /He gas flow rate and GeH ₄ /He gas flow rate
Adjust the outflow valves 217, 218, 220 so that the ratio with the B ₂ H ₆ /He gas flow rate becomes the desired value,
Also, while checking the reading on the vacuum gauge 236, adjust the main valve 2 so that the pressure inside the reaction chamber 201 reaches the desired value.
Adjust the aperture of 34. After confirming that the temperature of the substrate 237 is set to a temperature in the range of 400°C to 600°C by the heating heater 238, the power source 240 is set to the desired power to generate glow discharge in the reaction chamber 201. In this way, a first layer region (C) is formed on the base body 237. At the time when the first layer region (C) is formed to a desired layer thickness, the temperature of the base body 237 is raised to 50 to 400°C by the heating heater 238.
A second layer is formed on the first layer region (C) by setting the glow discharge to A layer region (G) can be formed. Once the second layer region (G) has been formed to the desired layer thickness, similar conditions and procedures are followed except for completely closing the outflow valve 218 and changing the discharge conditions as necessary. By maintaining the glow discharge for a desired period of time, a third layer region (S) substantially free of germanium atoms can be formed on the second layer region (G). In order to contain the substance (D) that controls conductivity in the third layer region (S),
For example, a gas such as B ₂ H ₆ or PH ₃ may be added to other gases introduced into the deposition chamber 201 during the formation of the deposition chamber 201 . In order to form the fourth layer region (M) in the third layer region (S) formed to the desired layer thickness as described above, the same steps as in the case of forming the third layer region (S) are performed. This is accomplished by, for example, diluting each of SiH ₄ gas and C ₂ H ₄ gas with He or the like as necessary to generate glow discharge according to desired conditions by operating a valve. In order to contain halogen atoms in the fourth layer region (M), for example, SiF ₄ gas and C ₂ H ₄ gas, or
Add SiH ₄ gas to this and do the same as above to make a fourth
This is done by forming a layer region (M) of. 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 201. Valve 21
In order to avoid gas from remaining in the gas pipe leading from 7 to 221 into the reaction chamber 201, the outflow valve 21
7 to 221, open the auxiliary valves 232 and 233, and fully open the main valve 234 to temporarily evacuate the system to a high vacuum, as necessary. The amount of carbon atoms contained in the fourth layer region (M) can be determined, for example, by glow discharge, SiH ₄ gas,
The flow rate ratio of the C ₂ H ₄ gas introduced into the reaction chamber 201 can be changed as desired, or if the layer is formed by sputtering, the sputtering of the silicon wafer and graphite wafer can be used to form the target. It can be controlled as desired by changing the area ratio or by changing the mixing ratio of silicon powder and graphite powder and molding the target. The amount of halogen atoms (X) contained in the fourth layer region (M) is determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF ₄ gas, is introduced into the reaction chamber 201. It is accomplished by doing so. In this way, the light-receiving layer composed of the first layer region (C), the second layer region (G), the third layer region (S), and the fourth layer region (M) is formed on the substrate 237. formed on top. During layer formation, it is desirable that the base body 237 be rotated at a constant speed by a motor 239 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 Al substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member. 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 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 2 An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 1 using the manufacturing apparatus shown in FIG. 2, except that the conditions shown in Table 2 were used. 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, except that the charge polarity and the charge polarity of the developer were opposite to those in Example 1. The image was extremely clear. A good image quality was obtained. Example 3 Using the manufacturing apparatus shown in FIG. 2, layers were formed in the same manner as in Example 1 except that the conditions shown in Table 3 were used to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 In Example 1, GeH ₄ /He gas and SiH ₄ /
Electrophotographic image forming members were prepared in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of He gas. Created. Using the 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 4 were obtained. Example 5 Each electrophotographic image forming member was prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5. 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 5 were obtained. Example 6 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical Al substrate under the conditions shown in Table 6 to obtain an electrophotographic image forming member. 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 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 7 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical Al substrate under the conditions shown in Table 7 to obtain an electrophotographic image forming member. 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 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;
Transferred onto transfer paper with 0.5KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 8 Using the manufacturing apparatus shown in FIG. 2, layers were formed on a cylindrical Al substrate under the conditions shown in Table 8 to obtain an electrophotographic image forming member. 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 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;
Transferred onto transfer paper with 5.0KV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 9 Layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 9 were changed using the manufacturing apparatus shown in FIG. 2 to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 10 Layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 10 were changed using the manufacturing apparatus shown in FIG. 2 to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 11 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 12 An electrophotographic image forming member was produced according to the same conditions and procedures as in Examples 2 to 10, except that the conditions for creating the fourth layer region (M) were as shown in Table 11. (Sample No. 12-201 to 12-208, 12-301 to 12-
308,..., 72 samples from 12−1001 to 12−1009)
It was 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 12 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use. Example 13 When forming the fourth layer region (M), the target area ratio between the silicon wafer and graphite is changed to change the content ratio of carbon atoms to silicon atoms in the fourth layer region (M). Each of the image forming members was produced in exactly the same manner as in Example 1, except for the following steps. 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 13 were obtained. Example 14 When forming the layer of the fourth layer region (M), the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas was changed to increase the concentration of silicon atoms and carbon atoms in the fourth layer region (M). Each of the image forming members was prepared in exactly the same manner as in Example 1 except that the content ratio was changed. For each of the image forming members 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 14 were obtained. Example 15 When forming the fourth layer region (M), SiH ₄ gas,
Completely the same method as in Example 1 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 fourth layer region (M). Each of the imaging members was prepared by.
After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed.
The results shown in Table 15 were obtained. Example 16 Imaging and development were carried out as described in Example 1, in which each of the image forming members was prepared in exactly the same manner as in Example 1, except that the layer thickness of the fourth layer region (M) was changed. , the cleaning process was repeated to obtain the results shown in Table 16. Common layer forming conditions in the above embodiments of the present invention are shown below. Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

【table】

【table】

【table】

【table】

[Table] ◎: Excellent ○: Good

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

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes 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】 [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 an apparatus used for producing the photoconductive member of the present invention in Examples. FIG. 100...Photoconductive member, 101...Support, 1
02...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a layer thickness on the support containing 1 to 1×10 ⁶ atomic ppm of germanium atoms and at least partially crystallized.
A first layer region of 30 Å to 50 μ and silicon atoms and 1
A second layer with a layer thickness of 30 Å to 50 μ containing an amorphous material containing ∼9.5 × 10 ⁵ atomic ppm of germanium atoms
a third layer region with a layer thickness of 0.5 to 90μ containing an amorphous material containing silicon atoms, and a layer region of 1×10 ⁻³
An electrophotographic image comprising a photoreceptive layer having a layered structure in which a fourth layer region having a layer thickness of 0.003 to 30μ is formed from an amorphous material containing ~90 atomic% of carbon atoms and silicon atoms, and is provided in order from the support side. A photoconductive member for use, characterized in that at least one of the first layer region and the second layer region contains a substance that controls conductivity in an amount of 0.01 to 5×10 ⁴ atomic ppm. A photoconductive member for electrophotography. 2. Photoconductive material for electrophotography according to claim 1, wherein hydrogen atoms are contained in any of the first layer region, the second layer region, the third layer region, and the fourth layer region. Element. 3. The photoconductive material for electrophotography according to claim 1, wherein any of the first layer region, the second layer region, the third layer region, and the fourth layer region contains a halogen atom. Element. 4. The photoconductive member for electrophotography according to claim 1, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table. 5. The photoconductive member for electrophotography according to claim 1, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table.