JPH0225171B2 - - 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 photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image formation in the image forming field, and document reading devices, it is highly sensitive and has a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)]. It has high absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, it has fast photoresponsiveness, it has the desired dark resistance value, it is non-polluting to the human body during use, and it is solid-state. Imaging devices are required to have characteristics such as 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 reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and stability over time, and it is necessary to improve overall characteristics. For example, when applied to an electrophotographic image forming member, if an attempt was made to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the response gradually decreases, etc. This often occurred. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when the commonly used halogen lamps and fluorescent lamps are used as light sources, there remains room for improvement in that they cannot effectively use light on the long wavelength side. In addition, if the 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 forming a photoconductive layer with an a-Si material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability 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, or halogen-containing hydrogen amorphous silicon [hereinafter referred to as "a- A photoconductive material is designed and created by specifying the structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity composed of "Si(H,X)" as described below. The parts not only exhibit outstanding properties in practical use, but also
Compared to conventional photoconductive materials, it is superior in all respects, especially as a photoconductive material for electrophotography, and has excellent absorption spectrum characteristics on the long wavelength side. It is based on what we have found to be excellent. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member 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 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 provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member for electrophotography having high properties. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties with sufficient performance and with almost no deterioration of the properties observed even in a humid atmosphere. 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,
An object of the present invention is to provide a photoconductive member for electrophotography that has high signal-to-noise ratio characteristics and good electrical contact with a support. The electrophotographic photoconductive member of the present invention (hereinafter simply referred to as photoconductive member) includes a support for the photoconductive member,
1×10×10 ⁵ atomic for the sum with silicon atoms
A first layer region with a layer thickness of 30 Å to 50 μ made of an amorphous material containing ppm of germanium atoms and a layer thickness of 0.5 to 90 μ made of an amorphous material containing silicon atoms (but not germanium atoms) a second layer region of the substrate, and a photoreceptive layer exhibiting photoconductivity and having a layer thickness of 1 to 100μ, which is provided in order from the support side, and the photoreceptor layer contains 0.001 to 50 atomic% of carbon. It is characterized by having a layer region (C) containing atoms. 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 characteristics are stable, and it is highly sensitive and has high
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, in the photoconductive member of the present invention, the photoreceptive layer formed on the support is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG.
The photoreceptive layer 102 has a free surface 105 on one end surface. The photoreceptive layer 102 includes germanium atoms and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms (X) from the support 101 side.
a-Ge (Si,
A first layer region (G) 103 composed of a-Si(H,X) and a second layer region (S) 104 composed of a-Si(H,X) and having photoconductivity. It has a layered structure laminated in sequence. When germanium atoms are contained together with other atoms in the first layer region (G) 103, germanium atoms are distributed in the layer thickness direction of the first layer region (G) 103 and parallel to the surface of the support 101. It is contained in the first layer region (G) 103 so as to be continuous and uniformly distributed in the in-plane direction. In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first 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 wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, so the distribution state of germanium atoms in the first layer region (G) and the second layer region is different. (S), and when a semiconductor laser or the like is used, the first layer region absorbs light on the long wavelength side that is almost completely absorbed by the second layer region (S). In (G), 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, when silicon atoms are contained in the first layer region (G),
Since each of the amorphous materials constituting the first layer region (G) and the second layer region (S) has a common constituent element of silicon atoms, chemical Stability is sufficiently ensured. In the present invention, the content of germanium atoms contained in the first layer region (G) may be appropriately determined as desired so as to effectively achieve the object of the present invention. preferably 1 to 10×10 ⁵ atomic ppm, more preferably 100 to 9.5×10 ⁵ atomic ppm, optimally 500
It is desirable that the content be 8×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer region (G) and the second layer region (S) 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 has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is preferably 30 Å to 50 μ, more preferably 40
It is desirable that the thickness be 50 Å to 30 μ, most preferably 50 Å to 30 μ. Further, the layer thickness T of the second layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. The sum of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) (T _B +T) is based on the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is appropriately determined as desired when designing the layers of the photoconductive member, based on the organic relationship between the characteristics and the characteristics to be used. 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 to 80μ, and optimally 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
It is desirable that appropriate numerical values be selected for each of them so as to satisfy the relationship T _B /T≦1. 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×
In the case of 10 ⁵ atomic ppm or more, the layer thickness T _B of the first layer region (G) is desirably made as thin as possible, preferably 30 μ or less, more preferably 25 μ or less, optimally 20 μ The following is desirable. In the photoconductive member of the present invention, carbon is contained in the photoreceptive layer for the purpose of increasing photosensitivity and dark resistance, as well as improving the adhesion between the support and the photoreceptive layer. Contains atoms. The carbon atoms contained in the photoreceptive layer may be uniformly contained in the entire layer region of the photoreceptive layer, or may be contained unevenly in only some layer regions of the photoreceptor layer. good. Further, the distribution state of carbon atoms may be such that the distribution concentration C (C) is uniform or non-uniform in the layer thickness direction of the photoreceptive layer. In the present invention, when the main purpose of the layer region (C) containing carbon atoms provided in the photoreceptive layer is to improve photosensitivity and dark resistance, the entire layer region of the photoreceptive layer is When the main purpose is to strengthen the adhesion between the support and the light-receiving layer, the light-receiving layer is provided so as to occupy the support-side end layer region of the light-receiving layer. In the former case, the content of carbon atoms contained in the layer region (C) is relatively low in order to maintain high photosensitivity, and in the latter case, to ensure enhanced adhesion with the support. It is desirable to have a relatively large amount for measurement purposes. In addition, in order to achieve both the former and the latter at the same time, it is necessary to distribute the concentration at a relatively high concentration on the support side and at a relatively low concentration on the free surface side of the photoreceptive layer, or In the surface layer region on the free surface side of the light-receiving layer, a distribution state of carbon atoms may be formed in the layer region (C) such that carbon atoms are not actively contained therein. In the present invention, the content of carbon atoms contained in the layer region (C) provided in the light-receiving layer depends on the characteristics required for the layer region (C) itself or when the layer region (C) is a 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, when another layer region is provided in direct contact with the layer region (C), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The carbon atom content is appropriately selected with consideration given to the carbon atom content. The amount of carbon atoms contained in the layer region (C) can be determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0.001 to 50 atomic%, more preferably 0.002 atomic%. ~
It is desirable that it be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region (C) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness of the photoreceptor layer is equal to the layer thickness T _O of the layer region (C). When the proportion of T is sufficiently large, the upper limit of the content of carbon atoms contained in the layer region (C) is
It is desirable that it be sufficiently smaller than the above value. In the case of the present invention, the ratio of the layer thickness T _O of the layer region (C) to the layer thickness T of the photoreceptive layer is two-fifths.
In such a case, the upper limit of the amount of carbon atoms contained in the layer region (C) is preferably
It is desirable that the content be 30 atomic % or less, more preferably 20 atomic % or less, and optimally 10 atomic % or less. FIGS. 2 to 10 show typical examples of the distribution state of carbon atoms contained in the layer region (C) of the photoconductive member of the present invention in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis shows the carbon atom distribution concentration C (C), the vertical axis shows the layer thickness of the layer region (C), and t _B is the layer region (C) on the support side. The position of the end surface, t _T , indicates the position of the end surface of the layer region (C) on the opposite side to the support side. That is, in the layer region (C) containing carbon 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 carbon atoms contained in the layer region (C) in the layer thickness direction. In the example shown in FIG. 2, from the interface position tB where the surface of the support where the layer region (C) containing carbon atoms is formed and the surface of the layer region (C) contact, to _the position _t1 . is contained in the layer region (C) where carbon atoms are formed while the distribution concentration C (C) of carbon atoms takes a constant value of C ₁ , and the concentration C 2 is lower than the concentration C ₂ at the interface position t _T than at the position t ₁ . has been gradually and continuously reduced. At the interface position _tT , the distribution concentration C (C) of carbon atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C (C) of the contained carbon atoms gradually and continuously decreases from the concentration _C4 from position _tB to position _tT , and at position _tT , A distribution state is formed such that the concentration is _C5 . In the case of Fig. 4, the distribution concentration C (C) of carbon atoms is assumed to be a constant value of concentration C ₆ from position t _B to position t ₂ , and gradually increases between position t ₂ and position t _T. Continuously decreased, at position t _T , the distribution concentration C(C)
is substantially zero (substantially zero here means less than the detection limit amount). In the case of Figure 5, the distribution concentration of carbon atoms C (C)
is gradually decreased continuously from the concentration C ₈ from the position t _B to the position t _T , and becomes substantially zero at the position t _T. In the example shown in FIG. 6, the distribution concentration C (C) of carbon atoms is a constant value of C ₉ between position t _B and position t ₃ , and the concentration C ₁₀ at position t _T.
It is said that Between the position t ₃ and the position t _T , the distribution concentration C (C) is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 7, the distribution concentration C
In (C), the concentration C ₁₁ is constant from position t _B to position t ₄ , and from position t ₄ to position t _T , the distribution state is such that the concentration decreases linearly from C ₁₂ to C ₁₃ . ing. In the example shown in FIG. 8, from position t _B to position t _T
The distribution concentration C (C) of carbon atoms is the concentration
From C ₁₄ , it decreases linearly to virtually zero. In FIG. 9, from position t _B to position t ₅ , the distribution concentration C (C) of carbon atoms decreases linearly from the concentration C ₁₅ to the concentration C ₁₆ , and from position t ₅ to position t _T An example is shown in which the concentration C ₁₆ is set to a constant value. In the example shown in FIG. 10, the distribution concentration C (C) of carbon atoms is a concentration C ₁₇ at position t _B , and initially decreases slowly from this concentration C ₁₇ until reaching position t ₆ . , t ₆ , the concentration decreases rapidly to a concentration C ₁₈ at position t ₆ . Between position t ₆ and position t ₇ , the concentration is decreased rapidly at first, then slowly and gradually decreased to reach C ₁₉ at position t ₇ , and then between position t ₇ and position t ₈ Then, it is gradually decreased very slowly and reaches the concentration C ₂₀ at position t ₈ . At 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 carbon atoms contained in the layer region (C) in the layer thickness direction, in the present invention, on the support side , a carbon atom distribution state in which a portion with a high distribution concentration C (C) of carbon atoms is provided, and a portion where the distribution concentration C (C) is considerably lower on the interface _t side than on the support side. is provided in the layer region (C). In the present invention, the layer region (C) containing carbon atoms constituting the photoreceptive layer is the localized region (B) containing carbon atoms at a relatively high concentration on the side of the support as described above. It is desirable that the support be provided as having the following properties, and in this case, the adhesion between the support and the light-receiving layer can be further improved. The above localized region (B) can be explained using the symbols shown in FIGS. 2 to 10, by 5μ from the interface position _tB .
It is desirable that it be established within In the present invention, the localized region (B) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. In the localized region (B), the maximum value Cmax of the distribution concentration of carbon atoms is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and most preferably 800 atomic ppm or more. It is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be achieved. That is, in the present invention, the layer region (C) containing carbon atoms has the maximum value Cmax of the distribution concentration C (C) within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B) . It is desirable that the structure be formed in such a way that it exists. In the present invention, the halogen atoms (X) optionally contained in the first layer region (G) and second layer region (S) constituting the photoreceptive layer include fluorine atoms. , chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, the first layer region (G) composed of a-Ge (SiH, It is done by a deposition method. For example, in order to form the first layer region (G) composed of a-Ge (Si, H, and, if necessary, a raw material gas for supplying Si that can supply silicon atoms (Si), a raw material gas for introducing hydrogen atoms (H), and/or a raw material gas for introducing halogen atoms (X). The gas may be introduced at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber to form a layer on the surface of a predetermined support that has been placed at a predetermined position. When germanium atoms are contained in the first layer region (G) with a uniform concentration distribution, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve.
It is sufficient to form a layer made of Ge (Si, H, X). In addition, when forming by sputtering method,
For example, by using a target composed of i in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or using two targets composed of the target and a target composed of Ge, or Si and
Using a mixed target of Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He or Ar as necessary is mixed with hydrogen atoms (H) and/or halogen atoms (X). This is accomplished by introducing a gas for introduction into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas.
At this time, by sputtering the target while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve, the distribution concentration of germanium atoms in the first layer region (G) can be arbitrarily controlled. I can do it. 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 vapor deposition board as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the above method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for 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 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) made of a-Ge containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) containing halogen atoms according to the glow discharge method, for example, silicon halide, which will be the raw material gas for supplying Si, germanium hydride, which will be the raw material gas for Ge supply, and Ar. ，
Gases such as H ₂ and He are introduced into the deposition chamber forming the first layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to generate plasma of these gases. The first layer region (G) can be formed on the desired support by forming an atmosphere, but in order to more easily control the ratio of hydrogen atoms introduced, A layer may be formed by further mixing hydrogen gas or a silicon compound gas containing hydrogen atoms in a desired amount. 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 ,
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 ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances may also be mentioned as useful starting materials for forming the first layer region (G). I can do it. Among these substances, halides containing hydrogen atoms are extremely effective hydrogen atoms for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer region (G). 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), in addition to the above, H ₂ or SiH ₄ ,
Silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compounds to supply Ge, or with GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H _Ten ,
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc. and silicon or silicon compound for supplying Si coexist in the deposition chamber and discharge is performed. This can also be done by causing . 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 (G) constituting the photoreceptive layer to be formed The sum of the 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), 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 power, etc. may be controlled. In the present invention, in order to form the second layer region (S) composed of a-Si (H, Accordingly, the first layer region (G) 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 Ge. It can be carried out according to the same method and conditions as in the case. 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 second layer region (S) composed of a-Si (H, It is made by a vacuum deposition method. For example, in order to form the second 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 / A gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the photoconductive member of the present invention, the second layer region (S) provided on the first layer region (G) containing germanium atoms and not containing germanium atoms has conductive properties. By including a controlling substance, the conductive properties of the layer region (S) can be controlled as desired. Such substances include so-called impurities in the semiconductor field, and in the present invention, a-Si(H,X) constituting the second layer region (S) to be formed. On the other hand, p-type impurities that give p-type conductivity characteristics and n-type impurities that give n-type conduction characteristics can be mentioned. Specifically, p-type impurities include atoms belonging to the group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). ), among which B and Ga are particularly preferably used. As n-type impurities, atoms belonging to Group 3 of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., are particularly preferably used. are P and As. In the present invention, the content of the substance controlling the conduction properties contained in the second layer region (S) is determined based on the conduction properties required for the layer region (S) or the content of the substance controlling the conduction properties contained in the second layer region (S). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layer regions provided in direct contact and the relationship with the characteristics at the contact interface with the other layer regions. In the present invention, the content of the substance controlling conduction properties contained in the second layer region (S) is preferably 0.001 to 1000 atomic ppm, more preferably
0.05-500atomic ppm, optimally 0.1-200atomic
Preferably in ppm. In order to structurally introduce a substance controlling the conduction properties into the second layer region (S), such as a group atom or a group atom, a starting material for introducing a group atom or The starting material for introducing group atoms may be introduced in gaseous form into the deposition chamber together with other starting materials for forming the second layer region. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ ,
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , EF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ . In addition, ACl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ ,
InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₃ , S ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. In the present invention, in order to provide the layer region (C) containing carbon atoms in the photoreceptive layer, when forming the photoreceptive layer, the starting material for introducing carbon atoms is added to the above-mentioned starting material for forming the photoreceptive layer. It may be used together with the starting material and contained in the formed layer while controlling its amount. When a glow discharge method is used to form the layer region (C), a starting material for introducing carbon atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for introducing carbon atoms, most of the gaseous substances containing at least carbon atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (C), and hydrogen atoms (H) or halogen atoms (X) as necessary. A raw material gas is used by mixing it at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are carbon atoms (C) and hydrogen atoms (H) are used. are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) are mixed. It can be used in combination with a raw material gas having two constituent atoms. Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing carbon atoms (C). Examples of those having C and H as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-butane (n _{- C4H10} ) _, pentane ( _C5H12 ), _ethylene hydrocarbons include ethylene ( _C2H4 ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Examples include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. In addition to these, alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ can be cited as raw material gases containing Si, C, and H as constituent atoms. In the present invention, the layer region (C) may contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effects obtained by carbon atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (C) include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), trinitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atom (O), and hydrogen atom (H) as constituent atoms, such as lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). I can do it. The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming the layer region (C) is one containing N as a constituent atom or containing N and H. Atoms such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. in gaseous or gaseous form Mention may be made of nitrogen, nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Mention may be made of halogenated nitrogen compounds. In order to form a layer region (C) containing carbon atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a C wafer, or a wafer containing a mixture of Si and C is used. This can be done by sputtering these as targets in various gas atmospheres. For example, if a Si wafer is used as a target, carbon atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to sputter the Si wafer. All you have to do is ring it. Alternatively, by using Si and C as separate targets or by using a single mixed target of Si and C, at least hydrogen atoms can be formed in an atmosphere of diluted gas as sputtering gas or at least hydrogen atoms. This is accomplished by sputtering in a gas atmosphere containing (H) or/and halogen atoms (X) as constituent atoms. As the raw material gas for carbon atom introduction, the raw material gas for carbon atom introduction in the raw material gas shown in the glow discharge example mentioned above is used.
It can also be used as an effective gas in sputtering. In the present invention, when a layer region (C) containing carbon atoms is provided when forming a photoreceptive layer, the distribution concentration C of carbon atoms contained in the layer region (C) is
Layer region (C) having a desired distribution state (depth profile) in the layer thickness direction by changing (C) in the layer thickness direction
In order to form, in the case of glow discharge, the distribution concentration C (C) is to be changed by using a gas as a starting material for introducing carbon atoms, while appropriately changing the gas flow rate according to a desired rate of change curve. This is done by introducing it into the deposition chamber. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (C) is formed by a sputtering method, the distribution concentration C of carbon atoms in the layer thickness direction
In order to change (C) in the layer thickness direction and form a desired distribution state (depth profile) of carbon atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, carbon atoms are introduced. This is accomplished by using a starting material in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, if a mixed target of Si and C is used as a target for sputtering, the mixing ratio of Si and C must be varied in advance in the layer thickness direction of the target. This is accomplished by letting it happen. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second layer region (S) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 1 to 40 atomic%, more preferably 5 to 40 atomic%.
It is desirable that it be 30 atomic %, most preferably 5 to 25 atomic %. 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,
Conductivity can be imparted by providing a thin film made of Pt, 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, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Conductivity is imparted to the surface by providing a thin film of a metal such as by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired.
If the photoconductive member 100 shown in the figure is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, the thickness is preferably 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. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is SiF ₄ gas diluted with He (99.99% purity, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is C ₂ H ₄ gas (purity
99.999%) cylinder, 1106 is _H2 gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, confirm that the leak valve 1135 is closed, and also check that the inflow valve 1112-1126 is closed.
Step 1116: After confirming that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ⁻⁶ torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical base 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, gas from gas cylinder 1105
C ₂ H ₄ gas through valves 1122, 1123, 112
5 and outlet pressure gauges 1127, 1128, 1
Adjust the pressure of 130 to 1Kg/cm ² and open the inflow valve 11.
12, 1113, 1115 gradually, and mass flow controllers 1107, 1108, 1110
Let the inflow into each of the areas. Subsequently, the outflow valve 11
17, 1118, 1120, auxiliary valve 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
Outflow valves 1117 and 111 are installed so that the ratio of GeH ₄ /He gas flow rate to C ₂ H ₄ gas flow rate becomes a desired value.
8 and 1120, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of approximately 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. and maintain the glow discharge for the desired time.
A first layer region (G) is formed on the base 1137 to a desired layer thickness. First layer region (G) to desired layer thickness
At the stage where the outflow valve 1118 is formed, the outflow valve 1118
A substantial amount of germanium atoms is formed on the first layer region (G) by maintaining the glow discharge for the desired time under the same conditions and procedures, except for completely closing the cell and changing the discharge conditions as necessary. It is possible to form a second layer region (S) that does not contain any of the above. In order to contain a substance that controls conductivity in the second layer region (S), a gas such as B ₂ H ₆ or PH ₃ is added to the deposition chamber when forming the second layer region (S). 11
It may be added to the gas introduced into 01. During layer formation, the base 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Using the manufacturing apparatus shown in FIG. 11, 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 installed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source, and a light intensity of 2 lux.sec was applied to the transmission type. It was irradiated through a test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0kV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 2 Using the manufacturing apparatus shown in FIG. 11, layers were formed in the same manner as in Example 1 except that the conditions shown in Table 2 were used to obtain an electrophotographic image forming member. An image was formed on a transfer paper using the thus obtained image forming member under the same conditions and procedures as in Example 1, except that the charge polarity and the charge polarity of the developer were each reversed from Example 1. Image quality was achieved. Example 3 Layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 3 were changed using the manufacturing apparatus shown in FIG. 11 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 Electrophotographic image forming members were 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. 11, 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 installed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and a light image was immediately irradiated using a tungsten lamp light source, transmitting a light amount of 2 lux.sec. It was irradiated through a mold test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0kV corona charging,
Clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 7 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner transfer image was evaluated 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.

【table】

【table】

【table】

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

[Table] ◎: Excellent ○: Good

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are illustrations for explaining the distribution state of germanium atoms in the photoreceptive layer, respectively. 11 are schematic illustrations of the apparatus used in the present invention. 100...Photoconductive member, 101...Support, 102
...Photoreceptor layer.

Claims (1)

[Claims] 1. 1×10×10 ⁵ atomic ppm based on the sum of the support for a photoconductive member for electrophotography and silicon atoms.
A first layer region with a layer thickness of 30 Å to 50 μ made of an amorphous material containing germanium atoms of The layer thickness of the layer structure in which the second layer region is provided in order from the support side
It consists of a photoreceptive layer that exhibits photoconductivity of ~100μ,
A photoconductive member for electrophotography, characterized in that the photoreceptive layer has a layer region (C) containing 0.001 to 50 atomic% of carbon atoms. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region and the second layer region contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein at least one of the first layer region and the second layer region contains a halogen atom.