JPH0462071B2 - - 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,
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. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, chemical, 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 afterimages, or when used repeatedly at high speeds, responsiveness 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 the commonly used halogen lamps and fluorescent lamps are used as light sources, there remains room for improvement in that they cannot effectively use light on the long wavelength side. Additionally, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. 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, neighboring atoms, etc. are included for control purposes, or other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving properties. In this case, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is 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, we found that silicon atoms are used as a matrix and hydrogen atoms (H ) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon [hereinafter referred to as "a-Si(H,X)" as a general notation for these] A photoconductive member designed and produced with the layer structure of a photoconductive member composed of [used] and having a photoreceptive layer exhibiting photoconductivity as explained hereinafter is extremely superior in practical use. It not only shows excellent characteristics, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography, and has long wavelength characteristics. This is based on the discovery that the absorption spectrum characteristics of the side are excellent. The present invention has stable electrical, chemical, 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 for electrophotography that has a long lifespan, 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 part for electrophotography which 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 without image blur. It is to be. 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. A support for a photoconductive member for electrophotography (hereinafter simply referred to as "photoconductive member") of the present invention,
A layer thickness of an amorphous material containing 1 to 10×10 ⁵ atomic ppm of germanium atoms is provided on the support.
A layer in which a first layer region (G) with a thickness of 30 Å to 50 μ and a second layer region (S) with a thickness of 0.5 to 90 μ made of an amorphous material containing silicon atoms are provided in order from the support side. Layer thickness 1 to 100μ indicating the photoconductivity of the composition
The first layer of () and silicon atoms and 1×10 ^-3 ~
a second layer () with a layer thickness of 0.003 to 30μ made of an amorphous material containing 90 atomic% of carbon atoms;
A substance (C) for controlling conductivity is present in the second layer region (S) with a maximum distribution concentration in the layer thickness direction of 30 atomic ppm or more, and in the second layer region (S). is characterized in that it is contained in a state where it has the maximum value on the side of the support. The photoconductive member of the present invention designed to have the above-described 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 image forming member for electrophotography, it is possible to sufficiently prevent interference even when using coherent light, and there is no influence of residual potential on image formation, and the electrical It has stable optical characteristics, high sensitivity, and high signal-to-noise ratio, and has good resistance to light fatigue and repeated use, and has high density, clear halftones, and high resolution. Images can be stably and repeatedly obtained. 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 structural diagram schematically shown to explain the layer structure of the photoconductive member of the present invention. The photoconductive member 100 shown in FIG.
102 and a second layer () 105, the photoreceptive layer 107 comprises a free surface 1
06 on one end face. The first layer ( ) 102 is made of an amorphous material ( ) containing germanium atoms and, if necessary, at least one of silicon atoms (Si), hydrogen atoms (H), and halogen atoms (X), from the support 101 side. From now on, “a-Ge
(abbreviated as “Si, H, X)”) and a-Si (H, X),
It has a layer structure in which a second layer region (S) 104 having photoconductivity is laminated in order. The first layer ( ) 102 contains a substance C that controls the conduction properties, and the substance C controls the conduction properties of the first layer ( ) 1
In 02, the maximum value of the distribution concentration in the layer thickness direction is in the second layer region (S), and in the second layer region (S), the concentration is more distributed toward the support 101 side. It is contained in a state where The germanium atoms in the first layer region (G) are contained uniformly in the in-plane direction parallel to the surface of the support, but in the layer thickness direction,
It may be uniform or non-uniform. In addition, if the distribution state of germanium atoms in the first layer region (G) 103 is non-uniform in the layer thickness direction, the distribution concentration C in the layer thickness direction may be changed to the support side or the second layer region (G). It is desirable to change it gradually, stepwise, or linearly toward the layer region (S) 104 side. In particular, the distribution state of germanium atoms in the first layer region (G) 103 is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration of germanium atoms in the layer thickness direction C, (G) is given a change that decreases from the support side toward the second layer region (S) 104, the first layer region (G)
103 and the second layer region (S) 104, and by extremely increasing the distribution concentration C of germanium atoms at the support side end as described later, the semiconductor laser etc., the light on the longer wavelength side that is hardly absorbed by the second layer region (S) 104 is transferred to the first layer region (G).
103, it is possible to substantially completely absorb and prevent interference due to reflection from the support surface, as well as to prevent reflection at the interface between layer region (G) 103 and layer region (S) 104. can be held down sufficiently. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the first layer region (G) 103 of the photoconductive member in the present invention in the layer thickness direction. 2 to 10, the horizontal axis represents the distribution concentration (C) of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G) 103, and _tB represents the first layer region (G) on the support side. The position of the end face of the layer region (G) 103 is t _T
is the first layer region (G) 10 on the side opposite to the support side
The position of the end face of No. 3 is shown. That is, in the first layer region (G) 103 containing germanium atoms, layers are formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer region (G) 103 in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B where the surface where the first layer region (G) 103 containing germanium atoms is formed and the surface of the first layer region (G) 103 are in contact with each other. Up to the position t ₁ , the distribution concentration C of germanium atoms takes a constant value C ₁ and is contained in the first layer region (G) 103 where germanium atoms are formed, and from the position t ₁ the concentration C ₂ , it is gradually and continuously decreased up to the interface position _tT . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained is from the position t _B to the position t _T
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching C ₅ at position t _T . In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at a concentration _C6 from position t _B to position t ₂ , and gradually and continuously between position t ₂ and position t _T. At position t _T , the distribution concentration C
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased continuously from the concentration C ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
It is said to be C ₁₀ . Between position _t3 and position _tT , the distribution density C is linearly decreased from position _t3 to position _tT . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration C ₁₅
The concentration C is linearly decreased to ₁₆ , and the position t ₅
An example is shown in which the concentration C ₁₆ is kept at a constant value between and the position t _T . In the example shown in FIG. 10, the distribution concentration C of germanium atoms is a concentration C ₁₇ at the position t _B , and is gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly and reaches the concentration _C18 up to the position _t6 . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly to reach the concentration C ₂₀ at position t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of germanium atoms contained in the first layer region (G) 103 in the layer thickness direction, in the present invention, , on the support side,
The distribution state of germanium atoms is such that the _first layer region ( G)1
03. The first layer region (G) 103 constituting the photoreceptive layer constituting the photoconductive member in the present invention preferably contains germanium atoms at a relatively high concentration on the support side as described above. It is desirable to have a localized area A. In the present invention, the localized region A is defined as the interface position by using the symbols shown in FIGS. 2 to 10.
It is desirable that it be provided within 5μ from _tB . In the present invention, the localized region A may be the entire layer region L _T up to 5 μm thick from the interface position t _B , or may be a part of the layer region L _T. Whether the localized region (A) is a part or all of the layer region L _T is determined as appropriate depending on the characteristics required of the layer to be formed. The localized region A has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration C _nax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 1000 atomic ppm or more with respect to the sum of the germanium atoms and silicon atoms. is more than 5000 atomic ppm, optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be achieved. That is, in the present invention, the first layer region (G) 103 containing germanium atoms has the maximum distribution concentration Cmax within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ). It is preferable that it be formed so that there is. In the present invention, the content of germanium atoms contained in the first layer region (G) 103 is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1~10×
¹⁰⁵ atomie ppm more preferably 100-9.5× ¹⁰⁵
aoimic ppm, optimally 500 to 8×10 ⁵ atomic
Preferably in ppm. In the present invention, the layer thickness of the first layer region (G) 103 and the second layer region (S) 104 is one of the important factors for effectively achieving the object of the present invention. Therefore, great care must be taken in designing the photoconductive member so that the photoconductive member formed has sufficient desired properties. In the present invention, the layer thickness T _B of the first layer region (G) 103 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 second layer region (S) 104 is preferably 0.5 to 90μ, more preferably 1 to 80μ,
The optimum thickness is preferably 2 to 50μ. The sum (T _B +T) of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) 104 is:
Based on the mutual organic relationship between the characteristics required for both layer regions and the characteristics required for the entire first layer 102, it is determined as desired when designing the layers of the photoconductive member 100. be done. In the photoconductive member 100 of the present invention, the above numerical value range of (T _B +T) is preferably 1 to 1.
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 _B and layer thickness T are preferably as follows:
When satisfying the relationship T _B /T≦1, it is desirable that appropriate numerical values be selected 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 T 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 (G) is 1×10 ⁵
In the case of atomic ppm or more, the layer thickness T _B of the first layer region (G) 103 is desirably as thin as possible, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ. The following is desirable. In the present invention, the first layer region (G) 103 and/or the second layer region (S) constituting the photoreceptive layer
Specifically, the halogen atom (X) contained in 104 as necessary includes fluorine, chlorine, bromine,
Examples include iodine, and particularly preferred are fluorine and chlorine. In the present invention, in order to form the first layer region (G) 103 composed of a-Ge (Si, H, This is done by a vacuum deposition method that utilizes this phenomenon. For example, to form the first layer region (G) 103 made of a-Ge (Si, H, X) by glow discharge method, germanium atoms (Ge) are basically supplied. possible raw material gas for Ge supply and, if necessary,
A source gas for Si supply that can supply silicon atoms (Si) and a source gas for introducing hydrogen atoms (H) or/
and introducing a raw material gas for introducing halogen atoms (X) into the deposition chamber at a desired gas pressure to reduce the internal pressure, thereby generating a glow discharge within the deposition chamber;
The layer may be formed on the surface of a predetermined support that has been placed in advance at a predetermined position. In order to non-uniformly distribute germanium atoms, the distribution concentration C of the contained germanium atoms can be controlled according to a desired rate of change curve, and a layer made of a-Ge (Si, H, X) can be formed. good. In addition, when forming by sputtering method, for example, Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using a target composed of Ge, or two targets composed of this target and Ge,
Alternatively, using a mixed target of Si and Ge, if necessary, use a raw material gas for Ge supply or a raw material gas for Si supply diluted with a diluent gas such as He or Ar. , a gas for introducing hydrogen atoms (H) or/and halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and at the same time, a gas for introducing hydrogen atoms (H) or/and halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and at the same time The target may be sputtered while controlling the gas flow rate of the raw material gas for supply according to a desired rate of change curve. In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and these evaporation sources are heated using a resistance heating method or an electron beam heating method. It can be carried out in the same manner as in the sputtering method, except that heating and evaporation is performed by a beam method (EB method) or the like, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
_GeH4 , _{Ge2H6 , Ge3H8 , Ge4H10 , Ge5H12 , Ge6}
Germanium hydride in a gaseous state or which can be gasified, such as H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc., can be mentioned as one that can be effectively used, and in particular, it is easy to handle during layer formation work. In terms of Ge supply efficiency, etc.
Preferred examples include GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ . 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. in gaseous or gasified form. Preferred examples include the halogen compounds obtained. Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer region (G) 103 made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) 103 containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which serves as a raw material gas for supplying Si, and raw material gas, which supplies Ge. Germanium hydride and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form the first layer region (G).
A first layer region (G) 103 is formed on the desired support by introducing the gas into a deposition chamber in which a gas is formed and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the ratio of hydrogen atoms introduced, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is further mixed with these gases to form a layer. Also good. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂
Halogen-substituted silicon hydrides such as I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ , GeH ₂ F ₂ ,
GeH ₃ F ₁ , GeHCl ₃ , GeH ₂ Cl ₂ , GeH ₃ Cl,
GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂
Germanium hydrogenated halides such as I ₂ , GeH ₃ I,
Halides containing hydrogen atoms as one of their constituent elements, such as GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ ,
Germanium halides such as Gecl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as useful starting materials for forming the first layer region (G) 103 . Halides containing hydrogen atoms in these substances are hydrogen atoms that are extremely effective for controlling electrical or photoelectric characteristics at the same time as introducing halogen atoms into the layer when forming the first layer region (G) 103. 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 layer region (G) 103, in addition to the above, H ₂ or SiH ₄ ,
Germanium or a germanium compound for supplying hydrogen silicon Ge such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ ,
Or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅
Germanium hydride such as H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₂ H ₂₀ , etc. and silicon or a silicon compound for supplying Si are made to coexist in a 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 layer region (G) 103 of the photoconductive member to be formed, or the amount of hydrogen atoms and halogen atoms Sum of quantities (H+
X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 30 atomic%, optimally 0.1 to 25 atomic%
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 (G) 103, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. What is necessary is to control the amount of the starting material used to incorporate the atoms (X) into the deposition system and the discharge power. In the photoconductive member 100 of the present invention, the second layer region (S) 1 which does not contain germanium atoms
04. If necessary, the first layer region (G) 103 containing germanium atoms may contain a substance C that controls conductivity, thereby improving the second layer region (S) 104 and the layer. The conduction properties of region (G) 104 can be controlled as desired. At this time, the substance C contained in the second layer region (S) 104 may be contained in the entire region or a part of the first layer region (G) 104, but in either case, It needs to be contained in a state where it is distributed more toward the support side. That is, the layer region (SPN) containing the substance C provided in the second layer region (S) 104 is provided as the entire layer region of the second layer region (S) 104, or is provided in the second layer region (S) 104. It is provided as a support side end layer region (SE) as a part of the region (S) 104.
In the former case where it is provided as a full-layer region, it is provided so that its distribution concentration C _s increases linearly, stepwise, or curved toward the support side. When the distribution concentration C _s increases in a curved manner, it is desirable to provide the substance C that controls the conductivity in the second layer region (S) 104 so that it monotonically increases toward the support side. . layer region (SPN) to second layer region (S) 104
When provided as a part of the support, the distribution state of the substance C in the layer region (SPN) is uniform in the in-plane direction parallel to the surface of the support, but in the layer thickness direction. It does not matter if it is uniform or non-uniform. In this case, in the layer region (SPN),
In order to provide the substance C so as to be distributed non-uniformly in the layer thickness direction, it is desirable to provide the substance C so as to form a distribution concentration line similar to that in the case where the substance C is provided in the entire layer region of the first layer region (G). Even when the first layer region (G) 103 contains a substance C that controls conductivity to provide a layer region (GPN) containing the substance C, the second layer region (S) 10
This can be done in the same way as when providing a layer region (SPN) in 4. In the present invention, the first layer region (G) 104
When both of the second layer region (S) 104 contain a substance C that controls conduction characteristics, the substances C contained in both layer regions may be the same type or different types. However, when both layer regions contain the same kind of substance C that controls conductivity, the maximum distribution concentration of the substance C in the layer thickness direction is equal to 10 in the second layer region (S).
4, that is, inside the second layer region (S) 104 or at the interface with the first layer region (G) 103. In particular, it is desirable that the maximum distribution concentration is provided at or near the contact interface with the first layer region (G) 103. In the present invention, as described above, the first layer ()
Preferably, a layer region (PN) containing a substance C that controls conduction properties is contained in the second layer region (S) 102 and occupies at least a part of the layer region of the second layer region (S) 104. , second layer region (S) 1
It is provided as the support side end layer region (SE) of 04. The layer region (PN) is the first layer region (G) and the second layer region (G).
When the material C is provided so as to straddle both the layer regions (S), the maximum distributed concentration C _G max in the layer region (GPN) of the substance C controlling the conduction characteristics and the Between the maximum distribution concentration C _S max is
The substance C is contained in the first layer ( ) 102 so that the relational expression C _G max<C _S max holds true. As the substance C that controls conductivity contained in the layer region (PN), so-called impurities in the semiconductor field can be mentioned, and in the present invention, Si
Alternatively, for Ge, p-type impurities that give p-type conductivity characteristics and n-type impurities that give n-type conductivity 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). , etc., and 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.
In particular, P and As are preferably used. In the present invention, the content of the substance C that controls the conduction properties contained in the layer region (PN) provided in the first () 102 is determined by the conduction properties required for the layer region (PN) or The layer region (PN) can be appropriately selected depending on the organic relationship, such as the relationship with the support provided in direct contact with the support or the characteristics at the contact interface with other layer regions. In addition, the content of the substance C that controls the conduction characteristics 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. is selected as appropriate. In the present invention, the content of the substance C that controls conduction properties contained in the layer region (PN) is as follows:
Preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5×
It is desirable to set it to 10 ³ atomic ppm. In the present invention, the layer region (PN) containing the substance C that controls conduction properties is referred to as the first layer region (G).
and the second layer region (S), or a part of the layer region (PN) occupies at least a part of the first layer region (G), and in the layer region (PN) The content of the substance C is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more.
ppm or more, optimally 100 atomic ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the support side It is possible to effectively prevent the movement of electrons injected into the second layer region (S) from When subjected to polar charging treatment, the movement of holes injected from the support side into the second layer region (S) can be effectively prevented. In the above case, under the above-mentioned basic structure of the present invention, the layer region (Z) excluding the layer region (PN) has a layer region (Z) that controls the conductive properties contained in the layer region (PN). It is also possible to contain a substance that controls conduction properties of a polarity different from that of the substance to be used, or a substance that controls conduction properties of the same polarity may be contained in a smaller amount than the actual amount contained in the layer region (PN). It may also be contained in a much smaller 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 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 layer ( ) 102 includes a layer region containing a substance that controls conductivity having one polarity, and a layer region that controls conductivity having the other polarity. It is also possible to provide a layer region containing a substance in direct contact with a layer region, and to provide a so-called depletion layer in this contact region. That is, for example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the first layer ( ) 102 so as to be in direct contact with each other to form a so-called p-n junction. Thus, a depletion layer can be provided. 11 to 24, the first layer () 1
A typical example of the distribution state of the substance C contained in 02 in the layer thickness direction that controls the conduction properties is shown. In these figures, the horizontal axis is the distribution concentration _CPN of the substance (G) in the layer thickness direction, and the vertical axis is the first layer ()1
The layer thickness t from the support side of 02 is shown. t _B is the position of the resistant surface on the support side of the first layer region (G), t _T
represents the position of the end surface of the second layer region (S) opposite to the support side, and t _O represents the position of the contact interface between the layer region (G) and the layer region (S), respectively. FIG. 11 shows a first typical example of the distribution state of the substance (C) that controls the conduction properties contained in the photoreceptive layer in the layer thickness direction. In the example shown in FIG. 11, the substance (C) is not contained in the first layer region (G) 103,
It is contained only in the second layer region (S) 104 at a constant distribution concentration of _C1 . That is, in the second layer region (S) 104, the substance (C) is contained in the end layer region between t ₀ and t ₁ at a constant distributed concentration of C ₁ . In the example of FIG. 12, the first layer region (G) 103
Although the substance (C) is evenly contained in the second layer region (S) 104, the substance (C) is not contained in the second layer region (S) 104. The substance (C) is contained in the layer region between t ₀ and t ₂ at a constant distribution concentration of C ₂ , and between t ₂ and t _T
In the layer region between them, _C3 is contained at a constant concentration, which is much lower than _C2 ! By containing the substance C in the layer region (S) constituting the photoreceptive layer at such a distributed concentration C _(PN) , the second layer region (S) 104 from the first layer region (G) 103
It is possible to effectively prevent charges injected into the surface from moving toward the surface, and at the same time, it is possible to improve photosensitivity and dark resistance. In the example of FIG. 13, the first layer region (G) 103
The distribution concentration C _{(PN) is such that the concentration C (PN)} monotonically decreases toward the upper surface from the concentration C ₄ at t ₀ and reaches 0 at t _T. Substance (C) is contained in a changed state. The first layer region (G) 103 does not contain the substance (C). In the examples shown in FIGS. 14 and 15, the substance (C) is unevenly contained in the lower end layer region of the second layer region (S) 104. That is,
In the case of the examples shown in FIGS. 14 and 15, the second layer region (S) 104 has a layer region containing the substance (C) and a layer region not containing the substance (C). , has a layered structure in which the layers are stacked in this order from the support side. The difference between the examples in Figures 14 and 15 is that in the case of Figure 14, the distribution concentration C _(PN) is greater than the concentration C ₅ at position t ₀ between t ₀ and t ₃ . While the concentration decreases monotonically to 0 at the position of t ₃ , the concentration at the first
In the case of FIG. 5, between t ₀ and t ₄ , the concentration decreases linearly and continuously from the concentration C ₆ at the t ₀ position to the concentration 0 at the t ₄ position. Figure 14 and 1
In the case of the example shown in FIG. 5 as well, the first layer region (G) 103 does not contain the substance (C). In the examples shown in FIGS. 17 to 24, the first layer region (G) 103 and the second layer region (S) 10
A case is shown in which both of No. 4 contain a substance (C) that controls conductivity. In the case of the examples shown in FIGS. 17 to 22, the second layer region (S) 104 is supported by a layer region containing the substance (C) and a layer region not containing the substance (C). They commonly have a two-layer structure in which the layers are stacked in this order from the body side. In the examples shown in FIGS. 17 to 21, the distribution state of the substance (C) in the first layer region (G) 103 is different from that in the second layer region (S) 104. The distribution concentration C _(PN) decreases from the interface position t ₀ toward the support. In the examples shown in FIGS. 23 and 24, the substance (C) is evenly contained in the layer thickness direction over the entire layer region of the first layer ( ) 102. In addition, in the case of FIG. 23, the first layer region (G)
103, the concentration increases linearly from t _B to t ₀ from C ₂₃ at t _B to C ₂₂ at t ₀ , and in the second layer region (S) 104. is from the concentration C ₂₂ at t ₀ to the concentration 0 at t _T from t ₀ to t _T
It decreases monotonically and continuously towards . In the case of Fig. 24, the layer region between t _B and t ₁₃ contains the substance (C) at a constant distribution concentration of C ₂₄ , and the layer region between t ₁₃ and t _T contains the substance (C). The concentration
It decreases linearly from C ₂₅ and reaches 0 at t _T. In the above, in FIGS. 11 to 24, typical cases of changes in the distribution concentration C _(PN) of the substance (C) that controls conductivity in the first layer ( ) 102 have been explained. Similarly, in each example, the maximum distribution concentration of the substance (C) is in the second layer region (S) 10
4, substance C is contained in the first layer () 102. In the present invention, in order to form the second layer region (S) 104 composed of a-Si (H, The first layer region (G) 103 is formed using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that becomes the raw material gas for supplying G from inside. It can be carried out according to the same method and conditions as in the case of forming. That is, in the present invention, to form the second layer region (S) 104 made of a-Si(H,X), a discharge method such as a glow discharge method, a sputtering method, or an ion plating method is used. It is made by a vacuum deposition method that takes advantage of this phenomenon. For example, in order to form the second layer region (S) 104 made of a-Si (H,
Along with the raw material gas for supply, a raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure, and What is necessary is to generate a glow discharge and form a layer made of a-Si (H, 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 first layer () 1 to be formed
The amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the second layer region (S) 104 constituting 02 is preferably, 1 to 40 atomic%, more preferably 5 to 30 atomic%, optimally 5 to 30 atomic%
It is desirable to set it to 25 atomic%. In the layer region constituting the first layer () 102,
In order to form a layer region (PN) containing the substance (C) by structurally introducing a substance (C) that controls conduction properties, for example, a group group atom or a group group atom, during layer formation. First, the starting material for introducing the group atom or the starting material for introducing the group atom may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the first layer ( ) 102 . 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 ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as _BBr3 . Other examples include AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ and TlCl ₃ . In the present invention, starting materials for introducing group atoms that are effectively used include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PIr ₅ and PI ₃ . In addition, _As H ₃ , _As F ₃ , _As
Cl3 , _AsF5 , _SbH3 , _{SbF3 , SbF5} , _SbCl3 ,
SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. In the photoconductive member 100 shown in FIG. 1, the second layer ( ) 105 formed on the first layer ( ) 102 has a free surface and mainly has moisture resistance, continuous repeated use characteristics, and electrical resistance. This is provided in order to achieve the objectives of the present invention in terms of pressure resistance, usage environment characteristics, and durability. Further, in the present invention, the first layer ( ) 102
Since each of the amorphous materials constituting the first layer and the second layer ( ) 105 has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. The second layer ( ) 105 in the present invention is an amorphous material ( Hereafter, “a−(Si _x C _1-x )y
(H,X) _1-y '', written as 0<x, y<1)
Consists of. The formation of the second layer ( ) composed of a-(Si _x C _1-x )y(H,X) _{1-y can} be performed by glow discharge method, sputtering method, ion plantation method, ion plating method, This is done by 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, and it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer ( ) 105 to be manufactured. Due to their advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second layer ( ) 105 may be formed by using a glow discharge method and a sputtering method in the same apparatus system. To form the second layer ( ) 105 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 mixture is mixed with gas at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition where a support is installed, and the introduced gas is
A glow discharge is generated to turn the gas into plasma, and a-(Si _x C _1-x )y(H,X) _1-y is applied onto the first layer ( ) 102 already formed on the support. All you have to do is deposit it. In the present invention, a-(Si _x C _1-x )y(H,X) _1-
The raw material gas for forming _y is a gaseous substance or a gasified substance having at least one constituent atom among silicon atoms (Si), carbon atoms (C), hydrogen atoms (H), and halogen atoms (X). Most of the gasified materials available 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 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 X as constituent atoms are also mixed at a desired mixing ratio, or the raw material gas containing Si and/or X as constituent atoms are mixed, or the raw material gas containing Si and/or
A raw material gas containing three constituent atoms of C and H, or
It is possible to use a mixture of a raw material gas containing the three constituent atoms of Si, C, and X. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. Raw material gases serving as constituent atoms may be mixed and used. In the present invention, F, Cl, Br, and I are preferable as the halogen atoms (X) contained in the second layer ( ) 105, and F and Cl are particularly preferable. In the present invention, raw material gases that can be effectively used to form the second layer ( ) 105 include gaseous substances or substances that can be easily gasified at normal temperature and normal pressure. . In the present invention, gases that are effectively used as raw material gases for forming the second layer ( ) 105 include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ whose constituent atoms are Si and H.
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 ), 1-butene (C ₄ H ₈ ), 2-butene (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylenic hydrocarbons. ,
Acetylene (C ₂ H ₂ ), Methylacetylene (C ₃
H ₄ ), butyne (C ₄ H ₆ ), and halogen alone:
Halogen gases such as fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH, HI, HCl, HBr,
Interhalogen compounds include BrF, ClF, ClF ₃ ,
ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃
Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH _2
Cl2 , _SiHCl3 , _SiH3Cl , _SiH3Br , _{SiH2Br2 ,}
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₈ ,
Silanes such as Si ₄ H ₁₀ , etc. can be mentioned. In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
_CH2F2 , _CH3F , _CH3Cl , _CH3Br , _{CH3I , C2}
Halogen-substituted paraffinic hydrocarbons such as H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ ,
Alkyl silicides such as Si(C ₂ H ₅ ) ₄ and SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These second layer ( ) 105 forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second layer ( ) 105 to be formed. They are selected and used as desired when forming the second layer ( ) 105, as shown in FIG. 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}
The second layer consisting of C _1-x )y(Cl+H) _1-y ()1
05 can be formed. Second layer ()1 by sputtering method
To form 05, target a single crystal or polycrystalline Si wafer or 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. Separately, by using Si and C as separate targets, or by using a single mixed target of Si and C, a gas containing hydrogen atoms and/or halogen atoms can be prepared as necessary. This is done by sputtering in an atmosphere.
As a material serving as a raw material gas for introducing C, H, and can be done. In the present invention, so-called rare gases such as He, Ne, Ar, etc. are preferably used as the diluting gas when forming the second layer ( ) 105 by the glow discharge method or the sputtering method. I can list them. The second layer ( ) 105 in the present invention is carefully formed to provide the desired properties. In other words, substances containing Si, C, and optionally H or/and In the present invention, a- (Si _x C _1-x )y(H,X) _1-y is formed,
The preparation conditions are strictly selected according to the desired conditions. For example, in order to provide the second layer ( ) 105 with the main purpose of improving electrical withstand voltage, a-(Si _x
C _1-x ) _y (H, In addition, when the second layer ( ) 105 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation described above is relaxed to a certain extent, and it has a certain degree of resistance to the irradiated light. As an amorphous material with sensitivity, a-(Si _x C _1-x )y
(H,X) _1-y is created. a-(Si _x C _1-x ) on the surface of the first layer ( ) 102
When forming the second layer ( ) 105 consisting of y _(H , In the present invention, the temperature of the desired body at the time of layer creation is strictly controlled so that a-(Si _x C _1-x )y(H,X) _1-y having the desired properties can be created as desired. It is desirable that In the present invention, an optimal range is selected as appropriate in accordance with the method of forming the second layer (205) in order to effectively achieve the desired purpose, and the second layer (105) is formed.
5 formations are carried out, but preferably 20 to 400
°C, more preferably 50-350 °C, optimally 100-300
It is preferable to set the temperature to ℃. The glow discharge method is used to form the second layer ( ) 105 because it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. However, when forming the second layer ( ) 105 using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, is advantageous. Created a−(Si _x C _1-x )yX _1-y
It is one of the important factors that influences the characteristics of The discharge power conditions for effectively producing a-(Si _x C _1-x )yX _1-y with the characteristics for achieving the purpose of the present invention with good productivity are preferably 10 to 300 W; More preferably 20-250W, optimally
It is desirable that the power be 50 to 200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr. In the present invention, the values of the support temperature and discharge power for forming the second layer ( ) 105 are preferably in the ranges described above, but these layer forming factors are determined independently and separately. a−(Si _x C _1-x )y of desired characteristics rather than fixed ones
It is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the second layer ( ) 105 consisting of (H,X) _1-y is formed. Second layer () 1 in the photoconductive member of the present invention
The amount of carbon atoms contained in 05 is the same as that of the second layer 1
Similar to the conditions for forming 05, this is an important factor in forming the second layer ( ) 105 that provides the desired properties to achieve the object of the present invention. The amount of carbon atoms contained in the second layer () 105 in the present invention is:
It can be determined as desired depending on the type of amorphous material constituting the second layer ( ) 105 and its characteristics. That is, the general formula a-(Si _x C _1-x )y(H,X) _1-
The amorphous material indicated by _y can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-SiaC _1-a ", where 0<a<1). ,
An 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 ")
It is written as However, 0<b, c<1), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary (hereinafter referred to as "a-(Si _d
C _1-d ) _e (H,X) _1-e '', where 0<d, e<
It is classified as 1). In the present invention, the second layer ( ) 105 is a-
When composed of Si _a C _1-a , the amount of carbon atoms contained in the second layer 105 is preferably 1×10 ⁻³
~90 atomic%, more preferably 1-80 atomic%,
Optimally, it is desirable to set it to 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 second layer ( ) 105 is a-
When composed of (Si _b C _1-b )cH _1-c , the amount of carbon atoms contained in the second layer () 105 is preferably 1×10 ⁻³ to 90 atomic%, more preferably is 1 to 90 atomic%, optimally 10 to 80 atomic%
% is preferable. The content of hydrogen atoms is preferably 1 to 40 atomic%,
More preferably 2 to 35 atomic%, 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 are excellent in practical applications and can be sufficiently applied. That is, if expressed as a-(Si _b C _1-b ) _e H _1-c above, b is preferably 0.1 to 0.99999, more preferably 0.1 to
0.99, optimal 0.15-0.9, c preferably 0.6-0.99,
It is more preferably 0.65 to 0.98, most preferably 0.7 to 0.95. The second layer 105 has a-(Si _d C _1-d )e(H,
X) When composed of _1-e , the second layer 105
The content of carbon atoms contained therein is preferably 1×10 _-3 to 90 atomic%, more preferably 1
It is desirable that it be ~90 atomic%, optimally 10-80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%, and optimally 2 to 20 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, which may be included as necessary, is preferably 19 atomic % or less, more preferably 13 atomic % or less. 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 second layer ( ) 105 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 second layer ( ) 105 depends on the amount of carbon atoms contained in the layer and the first layer ( ) 10
The relationship with layer thickness No. 2 also needs to be determined as desired based on the organic relationship depending on the characteristics required for each layer region. In addition, it is desirable to consider the economical aspects including productivity and mass production. The layer thickness of the second layer ( ) 105 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, 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 set to 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. 25 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.
_SiH4 gas diluted with He (purity 99.999% or less)
Abbreviated as SiH ₄ /He. ) cylinder, 203 is GeH ₄ gas diluted with He (99.999% purity, 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 to 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 a light-receiving layer on the cylindrical substrate 237, the gas cylinder 202
From SiH ₄ /He gas, gas cylinder 203
Open the valves 222, 223 and increase the pressure of the outlet pressure gauges 227 _, 228 to 1 kg/He gas.
cm ² and gradually open the inflow valves 212 and 213 to flow into the mass flow controllers 207 and 208, respectively. Subsequently, the outflow valve 21
7, 218, the auxiliary valve 232 is gradually opened to allow each gas to flow into the reaction chamber 201. At this time, _the outflow valve 217 _,
218 and the opening of the main valve 234 while checking the reading on the vacuum gauge 236 so that the pressure inside the reaction chamber 201 reaches the desired value. Then, the temperature of the base 237 is raised to 50°C by the heating heater 238.
After confirming that the temperature is set in the range of ~400°C, the power source 240 is set to the desired power to generate glow discharge in the reaction chamber 201 and the substrate 2 is heated.
A first layer region (G) 103 is formed on the layer 37.
At the time when the first layer region (G) 103 is formed to a desired layer thickness, the outflow valve 218 is completely closed and the B ₂ H ₆ /He gas is mixed with the SiH ₄ /He gas from the gas cylinder 205. Following the same conditions and procedures, except for controlling the mass flow controller 210 according to the desired doping curve by guiding the material into the reaction chamber 201 by the same valve operation, and changing the discharge conditions as necessary. By maintaining the glow discharge for a desired period of time, a second layer region (S) 104 substantially free of germanium atoms can be formed on the first layer region (G) 103. In this way, the first layer ( ) 102 composed of the first layer region (G) 103 and the second layer region (S) 104 is formed on the base body 237. To form the second layer ( ) 105 on the first layer ( ) 102 formed to the desired thickness as described above, the same valve operation as in the formation of the first layer ( ) 102 is performed. 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 layer ( ) 105, for example, SiF ₄ gas and C ₂ H ₄ gas, or by adding SiH ₂ gas thereto, form the second layer ( ) 105 in the same manner as above. It is done by forming. Needless to say, all the 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 out of the reaction chamber 201. valve 21
In order to avoid gas remaining in the gas piping 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 second layer ( ) 105 is determined by, for example, adjusting the flow rate ratio of DiH ₄ gas and C ₂ H ₄ gas introduced into the reaction chamber 201 in the case of glow discharge. 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) contained in the second layer ( ) 105 is determined by the amount of halogen atoms (X) contained in the reaction chamber 20 when the raw material gas for introducing halogen atoms, for example SiF ₄ gas
This is done by adjusting the flow rate when introduced into the 1. Further, 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. 25, each sample as an electrophotographic image forming member was formed on a cylindrical Al substrate under the conditions shown in Table 1 (see Table 2). When forming the second layer region (S), by changing the flow rate ratio of B ₂ H ₆ gas and PH ₃ gas according to a pre-designed change rate line, the distributed concentration shown in FIG. were formed for each sample.

[Table] Each sample thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 kV for 0.3 seconds.
A light image was immediately irradiated. 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 photoreceptive layer surface by cascading a charged developer (including toner and carrier) over the photoreceptive layer surface of each sample. When the toner image on the photoreceptive layer was transferred onto transfer paper by corona charging at 5.0 kV, each sample had excellent resolution and a clear, high-density image with good gradation reproduction was obtained. In the above, the light source is an 810nm GaAs semiconductor laser (10mW) instead of a tungsten lamp.
The image quality of the toner-transferred image was evaluated for each sample in the same manner as above, except that the electrostatic image was formed using Good, clear, high-quality images were obtained. Example 2 Using the manufacturing apparatus shown in FIG. 25, each sample as an electrophotographic image forming member was formed on a cylindrical Al substrate under the conditions shown in Table 3 (see Table 4). By changing the flow rate ratio of B ₂ H ₆ gas and PH ₃ gas according to a pre-designed rate of change line when forming the first layer region (G) and the second layer region (S). Then, the distribution concentration shown in FIG. 27 was formed for each sample. When each of these samples was subjected to image evaluation tests similar to those in Example 1, all samples gave high-quality toner-transfer images. When tested 200,000 times in a %RH environment, no deterioration in image quality was observed for any of the samples.

[Table] Example 3 Samples (sample Nos. 31-1 to 37-
12) respectively (Table 6). The concentration distribution of germanium atoms in each sample is shown in FIG. 28, and the distribution concentration of impurity atoms in each sample is shown in FIGS. 26 and 27. When each of these samples was subjected to image evaluation tests similar to those in Example 1, all samples provided high quality toner-transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples. Example 4 Sample No. 1- of Example 1 except that the conditions for creating the second layer ( ) 105 were as shown in Table 7.
Each of the electrophotographic imaging members shown in Table 8 (sample
No.1-1-1 to 1-1-8, 2-1-1 to 2-1
-8, 24 samples from 3-1-1 to 3-1-8) were created. Each of the electrophotographic image forming members thus obtained was individually installed in a copying machine, and the electrophotographic image forming members corresponding to each example were prepared under the same conditions as described in each example. For each, the overall image quality of the transferred image was evaluated and the durability was evaluated through repeated and continuous use. Table 8 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 5 When forming the second layer ( ) 105, the target area ratio of silicon wafer and graphite was changed,
Example 2 except that the content ratio of silicon atoms and carbon atoms in the second layer ( ) 105 was changed.
Each of the image forming members was prepared in exactly the same manner as Sample No. 2-1. After repeating the steps of image formation, development, and cleaning approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 9 were obtained. Ta. Example 6 When forming the second layer () 105, the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas was changed to form the second layer () 105.
Each of the image forming members was prepared in exactly the same manner as Sample No. 2-1 of Example 2, except that the content ratio of silicon atoms to carbon atoms in Sample No. 105 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 10 were obtained. Example 7 When forming the second layer ( ) 105, the flow rate ratio of SiH ₄ gas, SiF ₄ gas, and C ₂ H ₄ gas was changed to increase the concentration of silicon atoms and carbon atoms in the second layer ( ) 105. Each of the image forming members was prepared in exactly the same manner as Sample No. 31-1 of Example 3, except that the content ratio was changed. 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 11 were obtained. Example 8 Except for changing the layer thickness of the second layer ( ) 105,
Each of the image forming members was prepared in exactly the same manner as Sample No. 31-1 of Example 3. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 12.

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

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【table】

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

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of germanium atoms in the layer region (G), respectively. FIGS. 11 to 24 are explanatory diagrams for explaining the distribution state of impurity atoms in the first layer (), and FIG. 25 is a schematic diagram of the device used in the present invention. FIGS. 26 to 28 are explanatory diagrams each showing the distribution state of each atom in the embodiment of the present invention. 100...Photoconductive member, 101...Support, 1
02...First layer (), 105...Second layer (), 107...Photoreceptive layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a layer having a thickness of 30 mm on the support, comprising an amorphous material containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm. ~
A layer structure in which a first layer region (G) with a thickness of 50μ and a second layer region (S) with a layer thickness of 0.5 to 90μ made of an amorphous material containing silicon atoms are provided in order from the support side. A first layer () exhibiting photoconductivity with a thickness of 1 to 100μ, silicon atoms and 1×10 ^-3 to
a second layer () with a layer thickness of 0.003 to 30μ made of an amorphous material containing 90 atomic% of carbon atoms;
A substance (C) for controlling conductivity is present in the second layer region (S) with a maximum distribution concentration in the layer thickness direction of 30 atomic ppm or more, and in the second layer region (S). A photoconductive member for electrophotography, characterized in that the above-described maximum value is contained on the side of the support. 2. The photoconductive member for electrophotography according to claim 1, wherein the first layer region (G) contains silicon atoms. 3. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform in the layer thickness direction. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is uniform in the layer thickness direction. 5 First layer region (G) and second layer region (S)
The photoconductive member for electrophotography according to claim 1, wherein at least one of the above contains a hydrogen atom. 6 First layer region (G) and second layer region (S)
The photoconductive member for electrophotography according to claims 1 and 5, wherein at least one of the halogen atoms contains a halogen atom. 7. The photoconductive member for electrophotography according to claim 2, wherein the distribution state of germanium atoms in the first layer region (G) is such that more germanium atoms are distributed toward the support side. 8. The photoconductive member for electrophotography according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group 3 of the periodic table. 9. The photoconductive member for electrophotography according to claim 1, wherein the substance (C) that controls conductivity is an atom belonging to Group 3 of the periodic table.