JPH0210944B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
It must have a high signal-to-noise ratio [photocurrent (I _p )/dark current (I _d )], have absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have a desired dark resistance value. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body during use, and being able to easily dispose of afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image-forming member, DE 2933411 describes its application to a light guiding conversion and reading device. However, conventional photoconductive members having a photoconductive layer 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, which require a combined improvement in characteristics. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it was often observed that residual potential remained during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in 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 a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, 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 issues that need to be resolved in terms of stability over time. be. 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 comprehensive and intensive research on Si from the viewpoint of its applicability and applicability as a photoconductive member for electrophotography used in image forming members for electrophotography, we found that silicon atoms are used as a matrix and hydrogen Amorphous materials containing at least either an atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon,
Or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "a-Si (H,
The layer structure of the photoconductive member for electrophotography, which is composed of " Photoconductive members for electrophotography not only exhibit extremely excellent properties in practical use, but also surpass in every respect when compared with conventional photoconductive members for electrophotography. This is based on the discovery that it has extremely excellent properties as a carbon fiber and has excellent absorption spectrum properties on the long wavelength side. The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member 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 for electrophotography, which has sufficient performance and excellent electrophotographic properties 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,
Another 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 includes a support for the electrophotographic photoconductive member, and a layer having a thickness of 30 Å to 50 μm on the support and made of an amorphous material containing silicon atoms and germanium atoms. and a second layer region having a layer thickness of 0.5 μ to 90 μ and made of an amorphous material containing silicon atoms (but not containing germanium atoms) are provided in order from the support side. A photoconductive member for electrophotography, comprising an amorphous layer with a layer thickness of 1 μ to 100 μ, which exhibits photoconductivity in the layer structure,
The distribution state of germanium atoms in the first layer region is such that the distribution concentration C of germanium atoms is relative to silicon atoms on the support side.
The first part has a high portion of 1000 atomic ppm or more.
The distribution state is such that on the side opposite to the support side of the layer region, there is a portion where the distribution concentration C is considerably lower than on the support side, and the substance controlling conductivity is contained in the first layer region. and the amorphous layer contains oxygen atoms. The photoconductive member for electrophotography of the present invention (hereinafter referred to as "photoconductive member") designed to have the above-mentioned layer structure can solve all of the problems described above and has extremely excellent electrical properties. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, and its electrical properties are excellent. Stable physical characteristics, high sensitivity, and
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously used at high speed for a long time. Can be used repeatedly. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. A photoconductive member 100 shown in FIG. 1 has an amorphous layer 102 on a support 101 for photoconductive member.
The amorphous layer 102 has a free surface 105 on one end surface. The amorphous layer 102 is formed from a-Si(H,X) containing germanium atoms (hereinafter referred to as "a-
The first
Consisting of layer region (G) 103 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 germanium atoms contained in the first layer region (G) 103 are continuous in the layer thickness direction of the first layer region (G) 103 and on the side where the support 101 is provided. Contained in the first layer region (G) 103 so that it is more distributed on the support 101 side than on the opposite side (the surface 105 side of the amorphous layer 102). be done. In the photoconductive member 100 of the present invention, at least the first layer region (G) 103 contains a substance (C) that controls conduction characteristics, and the first layer region (G) 103
is given the desired conduction properties. In the present invention, the substance (C) that controls the conduction characteristics contained in the first layer region (G) 103 is uniformly distributed throughout the entire layer region of the first layer region (G) 103. It may be contained, or it may be contained so as to be unevenly distributed in a part of the layer region of the first layer region (G) 103. In the present invention, the first layer region (G) is made such that the substance (C) that controls the conduction characteristics is unevenly distributed in a part of the first layer region (G).
When the substance (C) is contained in the layer region (G) of
The layer region (PN) containing is the first layer region (G)
Preferably, it is provided as an end layer region. In particular, when the layer region (PN) is provided as the end layer region on the support side of the first layer region (G), the substance (C) contained in the layer region (PN) By appropriately selecting the type and content thereof as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the amorphous layer. In the photoconductive member of the present invention, the substance (C) capable of controlling conduction properties is added to the first layer region (G) constituting a part of the amorphous layer as described above. It is contained evenly throughout the layer region (G) or unevenly distributed in the layer thickness direction.
The substance (C) may also be contained in the second layer region (S) provided on the layer region (G). When the substance (C) is contained in the second layer region (S), the type, amount, and content of the substance (C) contained in the first layer region (G) are determined. Depending on the method, the substance contained in the second layer region (S)
The type of (C), its content, and the manner of its inclusion are determined as appropriate. In the present invention, when the substance (C) is contained in the second layer region (S), preferably the substance (C) is contained in the layer region including at least the contact interface with the first layer region (G). It is desirable to include a substance. In the present invention, the substance (C) may be evenly contained in the entire layer region of the second layer region (S),
Alternatively, it may be contained uniformly in a part of the layer region. When both the first layer region (G) and the second layer region (S) contain a substance (C) that controls conduction characteristics, the substance (C) in the first layer region (G) It is desirable that the layer region containing the substance (C) and the layer region containing the substance (C) in the second layer region (S) are provided so as to be in contact with each other. Also, the first layer region (G)
and the substance (C) contained in the second layer region (S).
may be the same or different types in the first layer region (G) and second layer region (S), and the content may be the same or different in each layer region. You can leave it there. However, in the present invention, when the substance (C) contained in each layer region is the same in both, the content in the first layer region (G) is sufficiently increased. or a type of substance (C) with different electrical properties,
It is preferable to contain each layer in each desired layer region. In the present invention, by containing the substance (C) that controls the conduction characteristics at least in the first layer region (G) constituting the amorphous layer, the content of the substance (C) can be improved. The conductive properties of the layer region [which may be part or all of the first layer region (G)] can be controlled as desired, and such materials include , so-called impurities in the semiconductor field, and in the present invention, a-SiGe constituting the amorphous layer to be formed.
For (H, Specifically, the P-type impurities include atoms belonging to Group 3 of the periodic table (Group atoms);
For example, there are B (boron), Al (aluminum), Ga (gallium), In (indium), 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., and particularly preferably used are P and As. In the present invention, the content in the layer region (PN) containing the substance controlling conduction properties is as follows:
The conductive properties required for the layer region (PN), or if the layer region (PN) is provided in direct contact with the support, the relationship with the characteristics at the contact interface with the support, etc. , can be selected as appropriate depending on the organic relationship. In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material controlling the conduction characteristics is determined. The content is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is as follows:
Usually 0.01 to 5×10 ⁴ atomic ppm, preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to
It is desirable that the content be 5×10 ³ atomic ppm. In the present invention, the content of the substance (C) that controls the conduction characteristics in the layer region (PN) containing the substance (C) is usually 30 atomic ppm or more, preferably
50atomic ppm or more, optimally 100atomic ppm
By doing the above, for example, when the substance (C) to be contained is the above-mentioned P-type impurity, when the free surface of the amorphous layer is subjected to polar charging treatment, the amorphous from the support side can be removed. In addition, when the substance (C) to be contained is the n-type impurity, the free surface of the amorphous layer is charged with polarity. When receiving the amorphous layer, injection of holes from the support side into the amorphous layer can be effectively prevented. In the above case, as described above, the layer region (Z) excluding the layer region (PN) contains a substance (C) that controls the conductive properties contained in the layer region (PN). It may contain a substance (C) that governs the conduction characteristics of a conduction type polarity different from that of the conduction type polarity, or a substance (C) that governs the conduction characteristics of a conduction type of the same polarity, It may be contained in an amount much smaller than the actual amount contained in the layer region (PN). In such a case, the content of the substance (C) that controls the conduction characteristics contained in the layer region (Z) depends on the polarity and content of the substance (C) contained in the layer region (PN). It is determined as desired depending on the amount, but usually 0.001 to 1000 atomic
ppm, preferably 0.05-500atomic ppm, optimally
It is desirable that the content be 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, the amorphous layer contains a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing the layer region in direct contact with the contact region. For example, the layer region containing the P-type impurity and the layer region containing the N-type impurity are provided in the amorphous layer so as to be in direct contact with each other to form a so-called P-n junction. A depletion layer can be provided. In the photoconductive member of the present invention, the first layer region
The distribution state of the germanium atoms contained in (G) is as described above in the layer thickness direction, and is uniformly distributed in the in-plane direction parallel to the surface of the support. is desirable. In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (G), and an amorphous layer is not included in such a layer structure. including the visible light region, by forming
The photoconductive member can be made to have excellent photosensitivity to light having wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths. 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, and the distribution concentration C of germanium atoms in the layer thickness direction is from the support side to the second layer region. Since a decreasing change toward the layer region (S) is given, the first
to have excellent affinity between the layer region (G) and the second layer region (S), and to extremely increase the distribution concentration C of germanium atoms at the support side edge as described later. Therefore, when a semiconductor laser or the like is used, light on the long wavelength side that can hardly be absorbed by the second layer region (S) is absorbed in the first layer region (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, 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. Therefore, chemical stability is sufficiently ensured at the laminated interface. 2 to 10 show typical examples of the distribution state of germanium atoms contained in the first layer region (G) of the photoconductive member of the present invention in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer region.
(G) indicates the layer thickness, and t _B is the first layer region (G) on the support side.
The position of the end face of t _T is the first position opposite to the support side.
The position of the end face of the layer region (G) is shown. That is, the first layer region (G) containing germanium atoms is from the t _B side.
t Layer formation occurs toward _{the T} side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer region (G) in the layer thickness direction. In the example shown in FIG. 2, from the interface position _tB where the surface where the first layer region (G) containing germanium atoms is formed and the surface of the first layer region (G) are in contact with each other,
Up to the position t ₁ , the distribution concentration C of germanium atoms
is contained in the first layer region (G) where germanium atoms are formed while taking a constant value of C ₁ , and the position t ₁
The concentration is gradually and continuously decreased from C ₂ to the interface position t _T . 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. reduced, and 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 is a constant value C ₉ , and at the position t _T the concentration C ₁₀
be done. Between position _t3 and position _tT , the distribution concentration C
is linearly decreased from position t ₃ to position t _T . In the example shown in FIG. 7, the distribution concentration C takes a constant value of concentration C ₁₁ from position t _B to position t ₄ ,
From position _t4 to position _tT , the distribution state is such that the concentration decreases linearly from _C12 to _C13 . In the example shown in FIG. 8, from position t _B to position t _T
Up to , the distribution concentration C of 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 to a concentration _C18 at 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) in the layer thickness direction, in the present invention, On the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface _tT side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. is provided in the layer region (G). The first layer region (G) constituting the amorphous 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 region (A). In the present invention, the localized region (A) can be explained using the symbols shown in FIGS. 2 to 10, and can be defined as the interface position.
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 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 (A) is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. The localized region (A) is a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of germanium atoms is usually 1000 atomic ppm or more, preferably more than 1000 atomic ppm relative to silicon atoms.
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the present invention, the amorphous layer containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (layer region with a thickness of 5μ from t _B ). In the present invention, the content of germanium atoms contained in the first layer region is appropriately determined as desired so as to effectively achieve the object of the present invention, but is usually 1 to 9.5× 10 ⁵ atomic ppm,
It is preferably 100 to 8×10 ⁵ atomic ppm, most preferably 500 to 7×10 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 formed has the desired properties. In the present invention, the layer thickness T _B of the first layer region (G) is
Usually 30Å~50μ, preferably 40Å~
It is desirable that the thickness be 40μ, optimally 50Å to 30μ. Further, the layer thickness T of the second layer region (S) is usually 0.5 to 90μ, preferably 1 to 80μ, and optimally 2
It is desirable that the thickness be ~50μ. Layer thickness T _B of the first layer region (G) and second layer region (S)
The sum of the layer thicknesses T (T _B +T) of the photoconductive member is determined based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire amorphous layer. It is determined as desired during layer design. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is usually 1 to 100μ,
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are usually T _B /
When satisfying the relationship 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 atomic
In the case of ppm or more, the layer thickness T _B of the first layer region (G)
It is desirable that the thickness be as thin as possible, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ or less. In the present invention, specifically, the halogen atoms (X) contained in the first layer region (G) and the second layer region (S) constituting the amorphous layer are Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, the first layer region (G) composed of a-SiGe (H, It is done by a deposition method. For example, in order to form the first layer region (G) composed of a-SiGe (H, A raw material gas for Ge supply that can supply germanium atoms (Ge), and a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as necessary. , the germanium atoms contained on the surface of a predetermined support, which has been placed at a predetermined position, are introduced at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber. While controlling the distribution concentration according to the desired rate of change curve, a-
A layer made of SiGe(H,X) may be formed.
In addition, when forming by sputtering method, for example, a target made of Si, or a target made of Si and Ge in an atmosphere of an inert gas such as Ar or He, or a mixed gas based on these gases. Using two targets, or with Si
Using a mixed target of Ge, the raw material gas for supplying Ge diluted with a diluent gas such as He or Ar is added as necessary to hydrogen atoms (H) or/and halogen atoms. (X) Introducing an introduction gas into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas, and controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. Then, sputtering the target described above is sufficient. In the case of the ion plating method, for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using resistance heating or electrobeam. This can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the EB method, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as the raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
_GeH4 , _{Ge2H6 , Ge3H8 , Ge4H10 , Ge5H12 ,}
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 which can be gasified are mentioned as those which can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ and Ge ₅ 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-SiGe 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, basically, for example, silicon halide, which is the raw material gas for supplying Si, and
Germanium hydride, which is the source gas for supplying Ge, and gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber forming the first layer region (G) at a predetermined mixing ratio and gas flow rate. The first layer region (G) on the desired support can be formed by generating a glow discharge and forming a plasma atmosphere of these gases, but the introduction ratio of hydrogen atoms is In order to further facilitate the control, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the 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 and HI, SiH ₅ 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 ,
_GeH2F2 , _GeH3F , _{GeHCl3 , GeH2Cl2 ,
GeH3Cl} , _GeHBr3 , _GeH2Br2 , _{GeH3Br ,}
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing a hydrogen atom 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 effective starting materials for forming the first layer region (G). I can do it. The halides containing hydrogen atoms in these substances introduce halogen atoms into the layer when forming the first layer region (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ and germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Generating a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in a deposition chamber. But it can be done by doing. In a preferred example of the present invention, hydrogen atoms contained in the first layer region (G) of the photoconductive member to be formed
The amount of (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is normal
0.01~40atomic%, preferably 0.05~30atomic%,
The optimum range is preferably 0.1 to 25 atomic%. Hydrogen atoms (H) contained in the first layer region (G)
or/and to control the amount of halogen atoms (X), for example by controlling the support temperature or/and hydrogen atoms (H) or the deposition system of the starting material used to contain the halogen atoms (X). What is necessary is to control the amount introduced into the cell, the discharge force, etc. In the present invention, in order to form the second layer region (S) composed of a-Si (H, Than,
When forming the first layer region (G) using the starting material [starting material for forming the second layer region (S) ()] excluding the starting material that becomes the raw material gas for G supply) It can be carried out according to similar methods and conditions. 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,X). 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. a-Si(H,
What is necessary is to form a layer consisting of X). In addition, when forming by sputtering method, for example, Ar, He
When sputtering a target composed of Si in an atmosphere of an inert gas such as or a mixed gas based on these gases, sputtering a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) It is sufficient to introduce it into the deposition chamber for use. In the present invention, hydrogen atoms (H) contained in the second layer region (S) constituting the amorphous layer to be formed
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%,
The optimum range is preferably 5 to 25 atomic%. A substance (C) that controls conduction properties, for example, group group atoms or group atoms, is structurally introduced into the layer region constituting the amorphous layer to create a layer region containing the substance (C) ( To form PN), during layer formation,
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 amorphous layer. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group atom include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ ,
Boron hydride _{such as B5H11} , _B6H10 , _{B6H12 , B6H14 ,} etc.
Examples include boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ ,
InCl ₃ , TlCl ₃ and the like can also be mentioned. In the present invention, starting materials for introducing group atoms that are effectively used include hydrogenated phosphorus such as PH ₃ and P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PIr ₅ and PI ₃ . 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 the introduction of group atoms. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the amorphous layer, contains an oxygen atom. The oxygen atoms contained in the amorphous layer may be uniformly contained in the entire layer region of the amorphous layer, or may be contained in only some layer regions of the amorphous layer so that they are unevenly distributed. You can let me. Furthermore, even if the distribution concentration C(O) of oxygen atoms is uniform in the thickness direction of the amorphous layer, the distribution state of germanium atoms as explained using FIGS. Similar to the state, the distribution concentration C(O)
may be non-uniform in the layer thickness direction. The distribution state of oxygen atoms when the distribution concentration C(O) of oxygen atoms is non-uniform in the layer thickness direction can be explained in the same way as the case of germanium atoms using FIGS. 2 to 10. In the present invention, when the main purpose is to improve photosensitivity and dark resistance, the layer region (O) containing oxygen atoms provided in the amorphous layer is the entire layer of the amorphous layer. When the main purpose is to strengthen the adhesion between the support and the amorphous layer, it is provided so as to occupy the end layer area of the amorphous layer on the support side. provided. In the former case, the content of oxygen atoms contained in the layer region (O) is kept 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 amorphous layer. Alternatively, in the surface layer region on the free surface side of the amorphous layer, a distribution state of oxygen atoms may be formed in the layer region (O) so as not to actively contain oxygen atoms. In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the amorphous layer depends on the characteristics required of the layer region (O) itself or the support of the layer region (O). When it is provided in direct contact with the body, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (O), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following. The amount of oxygen atoms contained in the layer region (O) is
It can be determined as desired depending on the characteristics required of the photoconductive member to be formed, but in normal cases,
0.001~50atomic%, preferably 0.002~
It is desirable that the content be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, whether the layer region (O) occupies the entire area of the amorphous layer or does not occupy the entire area of the amorphous layer, the layer thickness T _O of the layer region (O) If the proportion of the oxygen atoms in the layer thickness T is sufficiently large, the upper limit of the content of oxygen atoms in the layer region (O) 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 (O) to the layer thickness T of the amorphous layer is two-fifths.
In such cases, the upper limit of the amount of oxygen atoms contained in the layer region (O) is usually as follows:
30 atomic% or less, preferably 20 atomic% or less,
Optimally, it is desirable to set it to 10 atomic% or less. In the present invention, the layer region (O) containing oxygen atoms constituting the amorphous layer is the localized region (B) containing oxygen atoms at a relatively high concentration toward the support side as described above. ), and in this case, the adhesion between the support and the amorphous layer can be further improved. The localized region (B) is desirably provided within 5 μm from the interface position _tB , if explained using the symbols shown in FIGS. 2 to 10. In the present invention, the localized region (B) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the amorphous layer to be formed. The localized region (B) has a distribution state of oxygen atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of oxygen atoms is usually 500 atomic ppm or more, preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more.
It is desirable to form a layer in such a way that a distribution state of ppm or more can be obtained. That is, in the present invention, the layer region (O) containing oxygen atoms has the maximum distribution concentration within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the structure be formed so that Cmax exists. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the amorphous layer, the starting material for introducing oxygen atoms is added to the amorphous layer during the formation of the amorphous layer. It may be used together with the starting materials for formation and contained in the formed layer while controlling its amount. When a glow discharge method is used to form the layer region (O), a starting material for introducing oxygen atoms is selected as desired from among the starting materials for forming the amorphous layer described above. Added. As such a starting material for introducing oxygen atoms, most of the gaseous substances containing at least oxygen atoms or gasified substances that can be gasified can be used. For example, a raw material gas containing silicon atoms (Si), a raw material gas containing oxygen atoms (O), and hydrogen atoms (H) or halogen atoms (X) as necessary. Either a raw material gas is mixed 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 oxygen atoms (O) and hydrogen atoms (H) are used. , also in a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and three atoms of silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). It can be used in combination with a raw material gas having two constituent atoms. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
You may mix and use the raw material gas which has an oxygen atom (O) as a constituent atom with the raw material gas whose constituent atoms are . Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO) Nitric oxide (NO ₂ ), Nitric oxide (N ₂ O), Nitric oxide (N ₂ O ₃ ), Nitric oxide (N ₂ O ₄ ), Nitric oxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H), for example,
Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). To form the first amorphous layer () containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or SiO ₂ wafer, or a mixture of Si and SiO ₂ is used. This can be carried out by sputtering the contained wafer and target in various gas atmospheres. For example, if a Si wafer is used as a target, oxygen atoms and optionally hydrogen atoms or/
The raw material gas for introducing halogen atoms is diluted with a 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, Si and SiO ₂ may be used as separate targets or by using a single mixed target of Si and SiO ₂ in an atmosphere of diluent gas as a sputtering gas or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In the present invention, when a layer region (O) containing oxygen atoms is provided when forming an amorphous layer, the distribution concentration C of oxygen atoms contained in the layer region (O) is
A layer region (O) having a desired distribution state (depth profile) in the layer thickness direction by changing (O) in the layer thickness direction
In the case of glow discharge, the gas flow rate of the starting material for introducing oxygen atoms whose distribution concentration C(O) is to be changed is changed as appropriate according to the desired rate of change curve. This is accomplished by introducing the liquid 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 by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When the layer region (O) is formed by the sputtering method, the distribution concentration C of oxygen atoms in the layer thickness direction
In order to change (O) in the layer thickness direction to form a desired distribution state (depth profile) of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, a method for introducing oxygen atoms is required. This is accomplished by using a starting material in a gaseous state and appropriately varying the gas flow rate when introducing the gas into the deposition chamber as desired. Second, if a sputtering target is used, for example, a mixture of Si and SiO ₂ , the mixing ratio of Si and SiO ₂ should be
This is accomplished by changing the layer thickness of the target in advance. In the present invention, hydrogen atoms (H) contained in the second layer region (S) constituting the amorphous layer to be formed
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%,
The optimum range is 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, 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 support may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 shown 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 the desired photoconductive member is formed, but when flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained. FIG. 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 B ₂ H ₆ gas diluted with He (purity 99.999%, hereinafter referred to as B ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is No 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 an amorphous layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH 4 /He gas from gas cylinder 1103, GeH ₄ /He gas from gas cylinder 1104
B ₂ H ₆ /He gas, NO gas from the gas cylinder 1105, open the valves 1122 to 1125, adjust the pressure of the outlet pressure gauges 1127 to 1130 to 1 Kg/ ^cm2 , gradually open the inflow valves 1112 to 1115, and Flow controllers 1107 to 1110 each flow into the flow controllers 1107 to 1110. Subsequently, the outflow valve 111
7 to 1120, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valves 1117 to 11 are adjusted so that the ratio of the SiH ₄ /He gas flow rate, the GeH ₄ /He gas flow rate, the B ₂ H ₆ /He gas flow rate, and the NO gas flow rate becomes a desired value.
20, and 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. Then, the temperature of the base 1137 is increased by the heating heater 1138.
After confirming that the temperature is set in the range of 50 to 400°C, the power supply 1140 is set to the desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the rate of change curve is adjusted to a pre-designed rate of change curve. Therefore, the distribution concentration of germanium atoms contained in the layer to be formed is controlled by gradually changing the opening of the valve 1118 by manually controlling the flow rate of GeH ₄ /He gas or using an externally driven motor. do. In this way, boron atoms (B) are placed on the base 1137.
A layer region (B, O) composed of a-SiGe (H, Formed to desired layer thickness. At the stage when the layer regions (B, O) are formed to a desired layer thickness, the outflow valves 1118, 1119, 11
20 by maintaining the glow discharge for the desired time under similar conditions and procedures, except for completely closing each of the layers 20 and changing the discharge conditions as necessary. A layer region (S) composed of a-Si (H, The formation of is completed. During the formation of the amorphous layer described above, after the desired time has elapsed after the start of the layer formation, the deposition chamber is
By stopping the inflow of B ₂ H ₆ /He gas or NO gas, the thickness of each layer in the layer region containing boron atoms (B) and the layer region containing oxygen atoms (O) can be controlled arbitrarily. I can do it. Also, according to a desired rate of change curve, the deposition chamber 110
By controlling the flow rate of NO gas to the layer region (O), the distribution state of oxygen atoms contained in the layer region (O) can be formed as desired. 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, GeH ₄ /GeH 4 was deposited on a cylindrical Al substrate under the conditions shown in Table 1 and according to the rate of change curve of the gas flow rate ratio shown in FIG.
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of He gas and SiH ₄ /He gas with the elapsed time of layer formation. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 KV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. The toner image on the imaging member
When transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 2 The gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas was adjusted using the manufacturing apparatus shown in FIG. An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 1, with the other conditions being changed with the elapsed time of layer formation. 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 3 The gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas was adjusted using the manufacturing equipment shown in FIG. An electrophotographic image forming member was obtained by forming layers in the same manner as in Example 1, with the other conditions being changed with the elapsed time of layer formation. 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 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH 4 /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 15 under the conditions shown in Table _4. Layer formation was carried out in the same manner as in Example 1, except that the ratio was changed with the elapsed time of layer formation, and an electrophotographic image forming member was obtained. 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 5 The gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas was adjusted using the manufacturing apparatus shown in FIG. An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, while changing the layer formation time with the elapsed time. 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 6 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 17 under the conditions shown in Table 6. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 7 Using the manufacturing apparatus shown in FIG. 11, the gas flow rates of GeH ₄ /He gas and SiH ₄ /He gas were adjusted according to the rate of change curve of the gas flow rate ratio shown in FIG. 18 under the conditions shown in Table 7. Layers were formed under the same conditions as in Example 1 except that the ratio was changed with the elapsed time of layer formation 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 8 In Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that Si ₂ H ₆ /He gas was used and the conditions shown in Table 8 were used. 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 9 In Example 1, instead of SiH ₄ /He gas
An electrophotographic image forming member was obtained by forming layers under the same conditions as in Example 1, except that SiF ₄ /He gas was used and the conditions shown in Table 9 were used. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 10 Same conditions as in Example 1 except that (SiH ₄ /He + SiF ₄ /He) gas was used instead of SiH ₄ /He gas and the conditions shown in Table 10 were changed. Layer formation was carried out to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 11 Using the manufacturing apparatus shown in FIG. 11, on a cylindrical Al substrate, according to the rate of change curve of the gas flow rate ratio shown in FIG. 12 under the conditions shown in Table 11,
An electrophotographic image forming member was obtained by forming layers while changing the gas flow rate ratio of GeH ₄ /He gas and SiH ₄ /He gas with the elapsed layer formation time. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 KV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0KV corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 12 In Example 11, when creating the first layer,
The flow rate of B ₂ H ₆ to (SiH ₄ + GeH ₄ ) is
When creating the layer, the flow rate of B ₂ H ₆ to SiH ₄ is
12 Each electrophotographic image forming member was produced under the same conditions as in Example 11 except for the changes shown in Table 12. Examples of the image forming member thus obtained
When an image was formed on a transfer paper under the same conditions and procedures as in No. 11, the results shown in Table 12 were obtained. Example 13 In Examples 1 to 10, the conditions for creating the second layer were
Electrophotographic image forming members (Samples Nos. 1301 to 1301 and 1401 to 1410) were prepared in the same manner as in each Example except for the conditions shown in Tables 13 and 14. For each of the image forming members 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 15 were obtained. Example 14 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.

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[Table] ◎: Excellent ○: Good

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[Table] ◎: Excellent ○: Good

【table】

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are diagrams for explaining the distribution state of germanium atoms in the amorphous layer, respectively. The explanatory diagram, FIG. 11, is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS.
FIG. 8 is an explanatory diagram showing the rate of change curve of the gas flow rate ratio in each embodiment of the present invention. 100...Photoconductive member, 101...Support, 102
...Amorphous layer.

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a first layer having a thickness of 30 Å to 50 μ and made of an amorphous material containing silicon atoms and germanium atoms on the support.
layer area and a layer thickness of 0.5 μ made of an amorphous material containing silicon atoms (but not containing germanium atoms).
A second layer region of ~90 μm, and a layer thickness of 1 μm ~ exhibiting photoconductivity of the layer structure provided in order from the support side.
A photoconductive member for electrophotography consisting of an amorphous layer of 100 μm in thickness, wherein the distribution state of germanium atoms in the first layer region is such that the distribution concentration C of germanium atoms is relative to silicon atoms on the support side. 1000 atomic ppm or more and a portion where the distribution concentration C is considerably lower on the side opposite to the support side of the first layer region than on the support side, and 1. A photoconductive member for electrophotography, characterized in that one layer region contains a substance that controls conductivity, and the amorphous layer contains oxygen 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 claims 1 and 2, wherein at least one of the first layer region and the second layer region contains a halogen atom. 4. The photoconductive member for electrophotography according to claim 1, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table. 5. The photoconductive member for electrophotography according to claim 1, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table.