JPH0225178B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. In some cases, solid-state imaging devices are required to have characteristics such as being harmless to the human body and being able to easily process afterimages within a predetermined time. In particular, 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 harmlessness 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. Application to photographic image forming members and application to photoelectric conversion/reading devices are 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, in order to improve the combined 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 due to repeated use accumulates, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speed, the response gradually decreases, etc. There were many cases where problems 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, there is still room for improvement in that when a commonly used halogen lamp or fluorescent lamp is used as a light source, it is not possible to effectively use light on the longer wavelength side. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases, the reflectance of the support itself to the light transmitted through the photoconductive layer may decrease. When the value 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. 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 extensive research and study on Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we have discovered that Si is an amorphous material whose matrix is silicon atoms. , in particular, an amorphous material having a silicon atom as its base material and containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous material. A photoconductive member composed of a-Si (hereinafter referred to as "a-Si (H, The photoconductive member specifically designed and produced as explained below not only exhibits extremely superior properties in practical use, but also surpasses conventional photoconductive members in every respect. This is based on the discovery that it has extremely excellent properties as a photoconductive member for electrophotography, and that it 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 which has high photosensitivity in the entire visible light range, has excellent matching with a photoconductor laser, and has a fast photoresponse. Another object of the present invention is to have charge retention properties during charging processing for electrostatic image formation to such an extent that ordinary electrophotography methods can be applied very effectively when used as an image forming member for electrophotography. An object of the present invention is to provide a photoconductive member for electrophotography which has sufficient properties. 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 to provide a photoconductive member for electrophotography having high photosensitivity and high signal-to-noise ratio characteristics. The electrophotographic photoconductive member of the present invention (hereinafter simply referred to as photoconductive member) includes a support for the photoconductive member,
1 to 10 for the sum of silicon atoms on the support.
A layer region (G) with a thickness of 30 Å to 50 μ made of an amorphous material containing x10 ⁵ atomic ppm germanium atoms and a layer made of an amorphous material containing silicon atoms (but not germanium atoms) Thickness 0.5~
A first layer exhibiting photoconductivity with a layer thickness of 1 to 100 μ and a layer region (S) of 90 μ in thickness provided in order from the support side, silicon atoms and 1×10 −3 to 1×10 ⁻³
and a second layer with a layer thickness of 0.003 to 30μ made of an amorphous material containing 90 atomic% carbon atoms, and the first layer is made of silicon atoms, germanium atoms, and oxygen atoms. 0.001 for the sum of atoms
Contains ~50 atomic% oxygen atoms, has a smooth concentration distribution, and has a maximum concentration distribution of 500 atomic ppm or more within a layer thickness of 5μ from the support side of the layer or the interface side with the second layer. . The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics. In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has high sensitivity.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG.
102 and a second layer ( ) 103, the photoreceptive layer has a free surface 106 on one end face. The first layer ( ) 102 is a layer region (G) composed of a-Ge (Si, H, X) from the support 101 side.
104 and a layer region (S) 105 made of a-Si(H,X) and having photoconductivity are laminated in this order. The germanium atoms contained in the layer region (G) 104 may be evenly distributed throughout the layer region (G) 104, or may be evenly contained in the layer thickness direction. However, the distribution density may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is important to have a uniform distribution and even distribution in order to make the properties uniform in the in-plane direction. is also necessary. In particular, it is contained evenly in the layer thickness direction of the first layer ( ) 102 and on the side opposite to the side where the support 101 is provided (the free surface 106 side of the photoreceptive layer).
It is contained in the layer region (G) 104 so that it is distributed in a larger amount on the support body 101 side than on the support body 101 side, or so that the distribution state is the opposite. In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the layer region (G) is as described above in the layer thickness direction, and the distribution state is as described above, and the distribution state of germanium atoms contained in the layer region (G) is as described above. It is desirable that the distribution be uniform in parallel in-plane directions. In the present invention, germanium atoms are not contained in the layer region (S) provided on the layer region (G), and the layer region (S) provided on the layer region (G) does not contain germanium atoms.
By forming this, it is possible to obtain a photoconductive member that has excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. Further, in one of the preferred embodiments, the distribution state of the germanium atoms in the layer region (G) is such that the germanium atoms are continuously and evenly distributed in the entire layer region, and the layer thickness of the germanium atoms is Since the distribution concentration C in the direction decreases from the support side toward the layer region (S), the affinity between the layer region (G) and the layer region (S) is excellent, and As will be described later, by extremely increasing the distribution concentration C of germanium atoms at the edge of the support side, when a semiconductor laser or the like is used, long wavelengths that can hardly be absorbed by the layer region (S) can be obtained. The side light can be substantially completely absorbed in the layer region (G), and interference due to reflection from the support surface can be prevented. FIGS. 2 to 10 show typical examples in which the distribution state of germanium contained in the layer region (G) of the photoconductive member of the present invention in the layer thickness direction is non-uniform. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the layer region (G).
, t _B indicates the position of the end surface of the layer region (G) on the side of the support, and t _T indicates the position of the end surface of the layer region (G) on the side opposite to the support. That is, in the layer region (G) containing germanium atoms, the layer is formed from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the layer region (G) 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 (G) containing germanium atoms is formed and the surface of the layer region (G) contact, to the position _t1 . , the distribution concentration C of germanium atoms takes a constant value C ₁ and is contained in the layer region (G) where germanium atoms are formed, 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 a constant value of 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 Ca is a constant value, and at the position t _T the concentration
It is said to be C ₁₀ . Between the position t ₃ and the position t _T , the distribution concentration 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 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 decreased linearly up 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 .} 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 until it reaches 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 layer region (G) in the layer thickness direction,
In the present invention, the support side has a portion with a high distribution concentration C of germanium atoms, and the interface t _T
On the side, the distribution state of germanium atoms having a portion where the distribution concentration C is considerably lower than on the support side is provided in the layer region (G), as one preferable example. . The layer region (G) constituting the first layer () constituting the photoconductive member in the present invention is preferably on the support side as described above, or on the contrary, on the free surface of the photoreceptive layer. It is desirable to have a localized region (A) in which germanium atoms are contained at a relatively high concentration on the side. For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, the localized region ( _A) is
It is desirable that the distance be within 5μ. 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 appropriately determined according to the characteristics required of the first layer ( ) to be formed. In the localized region (A), the distribution state of germanium atoms contained therein in the layer thickness direction has a maximum distribution concentration C _nax of germanium atoms of preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, The layer is formed so as to achieve a distribution state that is more preferably 5000 atomic ppm or more, and optimally 1×10 ⁴ atomic ppm or more. That is, in the present invention, in the layer region (G) containing germanium atoms, the maximum value C _nax of the distribution concentration exists within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B) . It is preferable that it be formed in a similar manner. In the present invention, the content of germanium atoms contained in the layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but it is preferably 1 to 10×10 ⁵ atomic ppm, preferably 100 to 9.5×
10 ⁵ atomic ppm, optimally 500 to 8×10 ⁵ atomic
Defined as ppm. In the present invention, the layer thickness of the layer region (G) and the 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 desired properties are adequately provided. In the present invention, the layer thickness T _B of the layer region (G) is
Preferably 30 Å to 50 μ, more preferably 40 Å to
40μ, optimally 50Å to 30μ. Further, the layer thickness T of the layer region (S) is preferably 0.5
~90μ, more preferably 1~80μ, optimally 2~
It is said to be 50μ. The sum (T _B +T) of the layer thickness T _B of the layer region (G) and the layer thickness T of the layer region (S) is the characteristic required for both layer regions and the characteristic required for the entire first layer (). It is determined as desired when designing the layers of the photoconductive member based on the organic relationship between the two. 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 T _B /T
It is desirable that appropriate numerical values be selected for each so as to satisfy the relationship ≦1. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, the layer thicknesses should be selected so that the relationship T _B /≦0.9 is more preferably satisfied, and optimally, the relationship T _B /T≦0.8 is satisfied. The values of T _B and layer thickness T are determined. In the present invention, the content of germanium atoms contained in the layer region (G) is 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the layer region (G) is
It is desirable to make it fairly thin, preferably 30μ
Hereinafter, it is more preferably 25μ or less, optimally 20μ or less. In the present invention, the halogen atoms (X) contained in the layer region (G) and layer region (S) constituting the first layer as necessary include fluorine, chlorine, bromine, Examples include iodine, and particularly preferred are fluorine and chlorine. In the photoconductive member of the present invention, the first layer (
A layer region (O) containing oxygen atoms is provided therein. The oxygen atoms contained in the first layer () may be contained evenly in the entire layer area of the first layer (), or may be contained in a part of the layer area of the first layer (). It is also possible to make it ubiquitous by only containing it. In the present invention, the distribution state of oxygen atoms in the layer region (O) is such that even if the distribution concentration C(O) is uniform in the in-plane direction parallel to the surface of the support, It is non-uniform in the thickness direction. In the example shown in FIG. 11, from position t _B to position t ₉
In the layer region up to, the distribution concentration of oxygen atoms C
The concentration of (O) is _C21 , and in the layer region from position _t9 to position _t10 , it increases sharply from _t9 to _t10 ,
At t ₁₀ , the distribution concentration of oxygen atoms reaches a peak value C ₂₂ .
In the layer region from position t ₁₀ to position t ₁₁ , the distribution concentration C(O) of oxygen atoms decreases, and at position _{t T} the concentration C ₂₁
becomes. In the example shown in FIG. 12, from position t _B to position t ₁₂
In the layer region from t12 to t13, the distribution concentration of oxygen atoms C(O) increases _rapidly from _t12 to _t13 , and at position _t13 , the oxygen atom distribution concentration C( _O ) is _C23 . The distribution concentration of atoms C(O) takes the peak value _C24 ,
In the layer region from position _t13 to position _tT , the distribution concentration C(O) of oxygen atoms decreases to almost zero. In the example shown in FIG. 13, from position t _B to position t ₁₄
In the layer region up to, the distribution concentration C(O) of oxygen atoms is
The distribution concentration C(O) of oxygen atoms increases gradually from C ₂₅ to C ₂₆ and reaches a peak value C ₂₆ at position t ₁₄ .
In the layer region from position t ₁₄ to position t _T , the distribution concentration C(O) of oxygen atoms decreases rapidly, and at position _{t T} the concentration C ₂₅
becomes. In the example shown in FIG. 14, the distribution concentration C(O) of oxygen atoms at position t _B is concentration C ₂₇ , and the distribution concentration C (O) decreases until position t ₁₅ , and at t ₁₅ , the concentration C (O) becomes C ₂₈ . Become.
In the layer region from position _t15 to position _t16 , the distribution concentration C(O) of oxygen atoms is constant at a concentration _C28 . position
In the layer region from t ₁₆ to position t ₁₇ , the distribution concentration C(O) of oxygen atoms increases, and the distribution concentration C at position t ₁₇ increases.
(O) takes the peak value _C29 . In the layer region from position _t17 to position _tT , the distribution concentration of oxygen atoms C(O)
decreases to a concentration C ₂₈ at position _tT . In the present invention, when the main purpose of the layer region (O) containing oxygen atoms provided in the first layer ( ) is to improve photosensitivity and dark resistance,
It is provided so as to occupy the entire layer area of the first layer (2), and in order to prevent charge injection from the free surface of the photoreceptive layer, it is provided near the free surface side and is provided between the support and the photoreceptive layer. When the main purpose is to strengthen the adhesion between layers, the layer is provided so as to occupy the support side end layer region (E) of the first layer (). In the first case above, the content of oxygen atoms contained in the layer region (O) is made relatively low in order to maintain high photosensitivity, and in the second case, the content of oxygen atoms contained in the layer region (O) is kept relatively low in order to maintain high photosensitivity; In the third case, it is desirable to use a relatively large amount in order to prevent the injection of the liquid, and in the third case, to ensure that the adhesion to the support is strengthened. In addition, for the purpose of achieving the above three at the same time,
Oxygen is distributed at a relatively high concentration on the support side, and at a relatively low concentration at the center of the first layer (), and in the interfacial layer region on the free surface side of the first layer (). It is sufficient to form a distribution state of oxygen atoms in the layer region (O) such that the number of atoms is increased. In the present invention, the content of oxygen atoms contained in the layer region (O) provided in the first layer () is as follows:
The characteristics required for the layer region (O) itself, or when the layer region (O) is provided in direct contact with the support, the relationship with the characteristics at the contact interface with the support, etc. Depending on the organic relationship, it can be selected as appropriate. 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 preferably
0.001~50atomic%, more preferably 0.002~
40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, the layer region (O) occupies the entire area of the first layer (), or the layer region (O) occupies the entire first layer ().
Even if the layer area (O) does not occupy the entire area, the layer thickness T _O
When the proportion of the first layer () in the layer thickness T is sufficiently large, it is desirable that the upper limit of the content of oxygen atoms contained in the layer region (O) is sufficiently smaller than the above value. . In the present invention, the ratio of the layer thickness T _O of the layer region (O) to the layer thickness T of the first layer ( ) is two-fifths.
In such a case, the upper limit of the amount of oxygen atoms contained in the layer region (O) is preferably 30 atomic% or less, more preferably 20 atomic%.
% or less, optimally 10 atomic or less. In the present invention, the layer region (O) containing oxygen atoms constituting the first layer () has a relatively high concentration of oxygen atoms near the support side and the free surface side, as described above. It is preferable to provide the localized region (B) containing the localized region (B). You can improve your performance. The localized region (B) is desirably provided within 5 μm from the interface position t _B or t _T , if explained using the symbols shown in FIGS. 11 to 14. In the present invention, the localized region (B) is the entire layer region (L _T ) up to 5μ thick from the interface position t _B or t _T
In some cases, it may be considered as a part of the layer region (L _T ). 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 first layer () to be formed. In the localized region (B), the distribution state of the oxygen atoms contained therein in the layer thickness direction is such that the maximum value C _nax of the distribution concentration of oxygen atoms is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more, and optimally is formed in a layer such that it can have a distribution state of 1000 atomic ppm or more. That is, in the present invention, the layer region (O) containing oxygen atoms is distributed within 5 μm in layer thickness from the interface on the support side or free surface side (layer region 5 μ thick from t _B or t _T ). It is desirable that the formation be such that a maximum concentration C _nax exists. In the present invention, to form the layer region (G) composed of a-Ge (Si, H, and For example, by glow discharge method,
Layer region (G) composed of a-Ge (Si, H, X)
In order to form the
A raw material gas for supply, a raw material gas for introducing hydrogen atoms (H), and/or a raw material gas for introducing halogen atoms (X) are introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure. A glow discharge may be generated in a deposition chamber to form a layer made of a-Ge (Si, H, Furthermore, in order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-Ge (Si, H, X) must be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. Good. In addition, when forming by sputtering method, for example, a target composed of Si or a target composed of Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using two targets composed of Ge,
Or using a mixed target of Si and Ge,
If necessary, raw material gas for Ge supply diluted with diluting gas such as He or Ar, and gas for introducing hydrogen atoms (H) or/and halogen atoms (X) as necessary for sputtering. This is accomplished by introducing the desired gas into a deposition chamber and creating a plasma atmosphere of the desired gas. In order to make the distribution of germanium atoms non-uniform, for example, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve. 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. A layer region (G) consisting of a-SiGe containing halogen atoms can be formed on the desired support without using silicon hydride gas.
can be formed. When creating a layer region (G) containing halogen atoms according to the glow discharge method, basically, for example,
Silicon halide and Ge, which are the raw material gas for Si supply
germanium hydride, which is the raw material gas for supply;
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber for forming the layer region (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to create a plasma atmosphere of these gases. The layer region (G) can be formed on the desired support by forming a layer region (G), but in order to more easily control the ratio of introducing hydrogen atoms, it is possible to form a layer region (G) on the desired support. Furthermore, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed 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. a-SiGe by ion plating method
To form a layer region (G) consisting of (H,X),
For example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition port as evaporation sources, respectively, and these evaporation sources are heated using a resistance heating method or an electron beam method (EB method).
This can be carried out by heating and evaporating the flying evaporated material using a method such as the above method and passing the flying evaporated material through a desired gas plasma atmosphere. At this time, 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 introduce the gas 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 Hl, SiH ₂ F ₂ , SiH ₂ I ₂ ,
Halogen-substituted silicon hydrides such as 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 ,
Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides such as GeH ₂ I ₂ and GeH ₃ I, GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ ,
Gaseous or gasifiable substances such as germanium halides such as GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for forming the layer region (G). In the halides containing hydrogen atoms in these substances, when forming the layer region (G), hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced at the same time as halogen atoms are introduced into the layer. 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 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 with 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. In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or hydrogen atoms and halogen atoms contained in the layer region (G) constituting the first 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 said that In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the layer region (G), for example, the support temperature or/and the hydrogen atoms (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the layer region (S) composed of a-Si (H, According to the same method and conditions as when forming the layer region (G) using the starting material [starting material for forming the layer region (S) ()] excluding the starting material that becomes the raw material gas of I can do it. That is, in the present invention, in order to form the layer region (S) composed of a-Si (H, It is done by law. For example, a layer region (S) composed of a-Si (H,
Basically, in order to form the above-mentioned silicon atoms (Si), in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), if necessary, a gas for introducing hydrogen atoms (H) or/and
Then, a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber, so that the material gas is introduced onto the surface of a predetermined support that has been installed at a predetermined position in advance. a-Si(H,X)
What is necessary is to form a layer consisting of. In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the layer region (S) constituting the first 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 set at 30 atomic%, optimally from 5 to 25 atomic%. In the present invention, in order to provide the layer region (O) containing oxygen atoms in the first layer (), the above-mentioned starting material for introducing oxygen atoms is added during the formation of the first layer (). It may be used together with the starting material for forming the first layer () 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 added to a material selected as desired from among the starting materials for forming the first layer (O) described above. Substances are 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. 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 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. 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 oxygen atoms (O) as constituent atoms. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ ),
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). Examples include lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). To form the layer region (O) containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or a SiO ₂ wafer, or a Si and
This can be carried out by sputtering a wafer containing a mixture of SiO ₂ 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 diluting 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. Good. 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 the first layer (), the distribution concentration C( In order to form a layer region (O) having a desired depth profile in the layer thickness direction by changing O) in the layer thickness direction, in the case of glow discharge, the distribution concentration C(O) must be changed. This is accomplished by introducing a gas of the starting material for introduction of oxygen atoms to be changed into the deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve. 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, for example, a microcomputer or the like may be used to control the flow rate according to a pre-designed change rate curve to obtain a desired content rate curve. When the layer region (O) is formed by a sputtering method, the distribution concentration of oxygen atoms in the layer thickness direction C(O)
In order to change the depth profile of oxygen atoms in the layer thickness direction, firstly, as in the case of the glow discharge method, the starting point for introducing oxygen atoms is This is accomplished by using the substance in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a target containing a mixture of Si and SiO ₂ is used, this can be achieved by changing the mixing ratio of Si and SiO ₂ in advance in the direction of the layer thickness of the target. In the photoconductive member of the present invention, the layer region (G) containing germanium atoms and/or the layer region (S) not containing germanium atoms contains a substance (C) that controls conduction properties. By this, the layer region (G) or/and the layer region (S)
The conduction properties of can be arbitrarily controlled as desired. In the present invention, the layer region (PN) containing the substance (C) that controls conduction characteristics may be provided in a part or the entire layer region of the first layer (). Alternatively, the layer region (PN) may be provided in a part or all of the layer region (G) or the layer region (S). Examples of the substance (C) that controls conduction characteristics include so-called impurities in the semiconductor field, and in the present invention, for (SiGe), p
Examples include a p-type impurity that provides type conduction characteristics, and an n-type impurity that provides n-type conduction characteristics. Specifically, P-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance (C) that controls conduction properties contained in the first layer () is determined by the conduction properties required for the first layer () or the content of the substance (C) that controls the conduction properties contained in the first layer (). ), in terms of organic relationships, such as the characteristics of other layers or supports provided in direct contact with the layer or the relationship with the characteristics at the contact interface with the other layers or supports,
It can be selected as appropriate. In addition, when the substance controlling the conduction properties is contained locally in the first layer () in a desired layer region of the first layer (), it is particularly preferable that Support side end layer area (E) of the first layer ()
When containing in the layer region (E), the characteristics of other layer regions provided in direct contact with the layer region (E) and the relationship with the characteristics at the contact interface with the other layer regions are also taken into consideration. The content of the substance controlling the conduction properties is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1× 10 ⁴ atomic ppm, optimally 1
~5×10 ³ atomic ppm. In the present invention, the content of the substance (C) in the layer region (PN) containing the substance (C) that controls conduction characteristics is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more, optimally
In the case of 100 atomic ppm or more, the substance (C)
is preferably contained locally in a part of the layer region of the first layer (), and is particularly contained ubiquitously in the support side end layer region (E) of the first layer (). is desirable. Among the above, by containing the substance (C) that controls the conductive characteristics in the support side end layer region (E) of the first layer (2) in a content that is greater than or equal to the above value. For example, when the substance (C) to be contained is the above p-type impurity, the movement of electrons injected from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is subjected to polar charging treatment. In addition, when the substance to be contained is the above-mentioned n-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the photoreceptor layer is removed from the support side. It is possible to effectively prevent the movement of holes injected therein. In this way, when the end layer region (E) contains a substance that controls conduction characteristics of one polarity, the remaining layer region of the first layer (E), that is, the end layer region (E) The layer region (Z) of the portion other than E) may contain a substance that controls the conduction characteristics of the other polarity, or a substance that controls the conduction characteristics of the same polarity may be added to the end layer region. It may be contained in an amount much smaller than the actual amount contained in (E). 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 contained in the end layer region (E). It is determined as appropriate depending on the desire, but preferably from 0.001 to
1000atomic ppm, more preferably 0.05~
500atomic ppm, optimally 0.1-200atomic ppm
It is said that In the present invention, when the end layer region (E) and the layer region (Z) contain the same type of substance governing conductivity, the content in the layer region (Z) is as follows:
It is desirable to set it to 30 atomic ppm or less. In addition to the above-described case, the present invention includes a layer region containing a substance controlling conductivity having one polarity in the first layer () and a layer region containing a substance controlling conductivity having one polarity. It is also possible to provide a so-called empty layer in direct contact with a layer region containing a controlling substance, so that a so-called empty layer is provided in the contact region. For example, in the first layer (2), the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in direct contact to form a so-called p-n junction. Then, an empty layer can be provided. In order to structurally introduce a substance (C) that controls the conduction properties into the first layer (2), such as a group atom or a group atom, a starting material for introducing a group atom or a group atom is added during layer formation. The starting material for introducing group atoms may be introduced into the deposition chamber in a gaseous state together with other starting materials for forming the second layer region.
As a starting material for introducing such a group atom, 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 , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₃ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as BBr ₃ . Other examples include AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ and TlCl ³ . In the present invention, effective starting materials for introducing group atoms include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₅ , 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 photoconductive member 100 shown in FIG. 1, the second layer ( ) 103 formed on the first layer ( ) 102 has a free surface and mainly has moisture resistance, continuous repeated use characteristics, and electrical resistance. This is provided in order to achieve the objectives of the present invention in terms of pressure resistance, usage environment characteristics, and durability. The second layer () in the present invention is an amorphous material (hereinafter referred to as , “a−(Si _x N _1-x ) _y (H,X)
_1-y '', where 0<x, y<1). The formation of the second layer () composed of a-(Si _x N _1-x ) _y ( _H , This is done by an electron beam method or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Advantages include that it is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member that has silicon atoms, and that it is easy to introduce nitrogen atoms and halogen atoms together with silicon atoms into the second layer () to be manufactured. Therefore, a glow discharge method or a sputtering method is preferably employed. Furthermore, in the present invention, the second layer () may be formed by using both the glow discharge method and the sputtering method within the same apparatus system. In order to form the second layer ( ) by the glow discharge method, the raw material gas for forming a-(Si _x N _1-x ) _y (H,X) _1-y is diluted as necessary. The gas is mixed at a predetermined mixing ratio and introduced into a deposition chamber for vacuum deposition in which a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and is then deposited on the support. What is necessary is to deposit a-(Si _x N _1-x ) _y (H,X) _1-y on the first layer ( ) which has already been formed. In the present invention, a-(Si _x N _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Most gaseous substances or gasified substances containing at least one of nitrogen atoms (N), hydrogen atoms (H), and halogen atoms (X) are used. obtain. When using a raw material gas containing Si as one of Si, N, H, and X, for example, a raw material gas containing Si and a raw material gas containing N, as necessary. Depending on the situation, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si and N and H may be used. The raw material gas having constituent atoms and/or the raw material gas having X as constituent atoms are also mixed at a desired mixing ratio, or the raw material gas having Si as constituent atoms and the raw material gas having Si,
A raw material gas containing three constituent atoms, N and H, or
It is possible to use a mixture of a raw material gas whose constituent atoms are Si, N, and X. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing N as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with N. You may mix and use raw material gas used as a constituent atom. In the present invention, preferred halogen atoms (X) contained in the second layer () include F, Cl,
Br and I, with F and Cl being particularly desirable. In the present invention, raw material gases that can be effectively used to form the second layer (2) include gaseous materials or substances that can be easily gasified at normal temperature and normal pressure. In the present invention, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ containing Si and H as constituent atoms are effectively used as the raw material gas for forming the second layer (). Silicon hydride gases such as silanes, etc., nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ) whose constituent atoms are N or N and H, etc. Gaseous or gasifiable nitrogen, such as hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc., nitrogen compounds such as nitrides and azides can be mentioned. In addition to this, nitrogen trifluoride (F ₃ N),
Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F ₄ N ₂ ). Effective starting materials that serve as raw material gas for introducing halogen atoms (X) include, for example, fluorine, chlorine,
Bromine, iodine halogen gas, BrF, ClF,
Examples include interhalogen compounds such as ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr, and hydrogen halides such as HF, HCl, HBr, and HI. These second layer () forming substances contain silicon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second layer () to be formed. Similarly, they are selected and used as desired when forming the second layer (2). For example, by introducing a raw material gas for introducing silicon atoms and nitrogen atoms, and, if necessary, a raw material gas for introducing hydrogen atoms and/or halogen atoms into a deposition chamber, and causing a glow discharge. −
Second layer consisting of (Si _x N _1-x ) _y (H,X) _1-y ( )
can be formed. To form the second layer () by the sputtering method, target a single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer containing a mixture of Si and Si ₃ N ₄ . ,
These may be performed by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary. For example, if a Si wafer is used as a target, the raw material gas for introducing Si ₃ N ₄ and H or/and X is diluted with diluting gas as necessary.
The Si wafer may be sputtered by introducing the gas into a deposition chamber for sputtering and forming a gas plasma of these gases. Alternatively, by using Si and Si ₃ N ₄ as separate targets or by using a single mixed target of Si and Si ₃ N ₄ , hydrogen atoms and/or halogens can be added as needed. This is done by sputtering in a gas atmosphere containing atoms. As the material gas for introducing N, H, and X, the material for forming the second layer () shown in the glow discharge example described above can also be used as an effective material in the case of the sputtering method. In the present invention, the diluent gas used when forming the second layer () by a glow discharge method or a sputtering method is a so-called rare gas, such as He,
Preferable examples include Ne and Ar. The second layer () in the present invention is carefully formed to provide its required properties as desired. In other words, substances whose constituent atoms are Si, N, and H or/and In the present invention, a that exhibits properties ranging from semiconducting to insulating, and properties ranging from photoconductive to non-photoconductive.
-(Si _x N _1-x ) _y ( _H , For example, to provide the second layer () with the main purpose of improving electrical withstand voltage, a-(Si _x N _1-x ) _y
( _H , In addition, if a second layer () is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the degree of electrical insulation described above will be relaxed to a certain extent, and the sensitivity to the irradiated light will be increased to a certain degree. As an amorphous material having a-(Si _x N _1-x ) _y (H,X) _1
-y is created. On the surface of the first layer () a-(Si _x N _1-x ) _y (H,
When forming the _second layer ( ) consisting of a-(Si _x N _1-x ) _y that has the desired characteristics
It is desirable that the temperature of the support during layer formation be strictly controlled so that (H,X) _1-y can be formed as desired. In the present invention, the formation of the second layer () is carried out by selecting an appropriate optimum range in accordance with the method of forming the second layer () in order to effectively achieve the desired purpose. The temperature is preferably 20 to 400°C, more preferably 50 to 350°C, and optimally 100 to 300°C. To form the second layer (), glow discharge method and Adoption of sputtering method is advantageous, but when forming the second layer () by these layer forming methods, the discharge power during layer formation is created in the same way as the support temperature described above. −(Si _x N _1-x ) _y This is one of the important factors that influences the characteristics of X _1-y . The discharge power conditions for effectively producing a-(Si _x N _{1-x ) y}
10-300W, more preferably 20-250W, optimally 50
~200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr. In the present invention, the above-mentioned values are listed as the preferable numerical ranges for the support temperature and discharge power for creating the second layer (), but these layer creation factors are determined independently and separately. a-(Si _x N _1-x ) _y (H,
X) It is desirable that the optimum value of each layer formation factor be determined based on mutual organic relationship so that the second layer ( ) consisting of _1-y is formed. The amount of nitrogen atoms contained in the second layer () in the photoconductive member of the present invention is the same as the production conditions of the second layer (), and the amount of nitrogen atoms contained in the second layer () is determined such that the desired characteristics that achieve the object of the present invention are obtained. This is an important factor in the formation of the layer (). The amount of nitrogen atoms contained in the second layer (2) in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (2). . That is, the general formula a-(Si _x N _1-x ) _y (H,X) _1-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and nitrogen atoms (hereinafter referred to as "a-Si _a N _1-a ". However, 0<a< 1),
Amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b N _1-b ) _c H _1-c ". However, 0<b, c<1) , an amorphous material (hereinafter referred to as "a-(Si _d
N _1-d ) _e (H,X) _1-e ”. However, 0<d, e<
It is classified as 1). In the present invention, the second layer () is a-Si _a
When composed of N _1-a , the amount of nitrogen atoms contained in the second layer ( ) is preferably 1 × 10 ^-3 ~
90 atomic%, more preferably 1 to 80 atomic%, optimally 10 to 75 atomic%. That is, the previous a
-Si _a N If a is expressed as _1-a , a is preferably
0.1 to 0.99999, more preferably 0.2 to 0.99, optimally
It is 0.25-0.9. In the present invention, the second layer () is a-(Si _b
When composed of N _1-b ) _c H _1-c , the second layer ()
The amount of nitrogen atoms contained in is preferably 1×
10 ^-3 to 90 atomic%, more preferably 1 to 90 atomic%
It is said to be 90 atomic%, optimally 10 to 80 atomic%.
The content of hydrogen atoms is preferably 1-
40 atomic%, more preferably 2 to 35 atomic%,
The optimal value is 5 to 30 atomic%. Photoconductive members formed with hydrogen contents within these ranges are well suited for practical applications. That is, if expressed as a-(Si _b N _1-b ) _c H _1-c above, b is preferably 0.1 to 0.99999, more preferably 0.1 to
0.99, optimally 0.15~0.9, c preferably 0.6~
0.99, more preferably 0.65~0.98, optimally 0.7~
It is 0.95. The second layer () is a-(Si _d N _1-d ) _e (H,X) _1
-e , the content of nitrogen atoms contained in the second layer () is preferably 1×
10 ^-3 to 90 atomic%, more preferably 1 to 90 atomic%
%, optimally 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%,
More preferably 1 to 18 atomic%, optimally 2 to 18 atomic%
It is assumed to be 15 atomic%. Photoconductive members prepared with a halogen atom content within these ranges can be satisfactorily applied in practice. The content of hydrogen atoms contained as necessary is preferably
It is preferably 19 atomic % or less, more preferably 13 atomic % or less. That is, d in the previous a-(Si _d N _1-d ) _e (H,X) _1-e ,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
0.82-0.99, optimally 0.85-0.98. The number range of the layer thickness of the second layer () in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. In addition, the layer thickness of the second layer () is determined based on the amount of nitrogen atoms contained in the layer () and the thickness of the first layer () required for each layer area. It needs to be appropriately determined as desired based on organic relationships depending on the characteristics. In addition, it is desirable to consider the economical aspects including productivity and mass production. The layer thickness of the second layer ( ) in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 20μ, and optimally 0.005 to 10μ. Further, in the present invention, in order to further enhance the effect obtained by nitrogen atoms, carbon atoms may be included together with nitrogen atoms in the second layer (2). As a raw material gas for introducing carbon atoms into the second layer (2), for example, saturated hydrocarbons having 1 to 5 carbon atoms and 2 to 5 carbon atoms, which have C and H as constituent atoms. Ethylene hydrocarbon, carbon number 2-4
Examples include acetylene hydrocarbons. 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. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr,
Examples include metals such as 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. Ru. These electrically insulating supports preferably have at least one surface conductively treated, and another layer is provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 of FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. 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 from the viewpoint 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. 15 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 a NO gas (purity 99.99%) cylinder, 1105 is a He gas (purity 99.999%) cylinder, and 1106 is a H ₂ 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 substrate 1137, the gas cylinder 11
SiH ₄ /He gas from 02, GeH ₄ /He gas from gas cylinder 1103, NO from gas cylinder 1104
Open the gas valves 1122, 1123, 1124 and check the outlet pressure gauges 1127, 1128, 1129.
Adjust the pressure to 1Kg/cm ² and open the inflow valve 1112,
1113 and 1114 are gradually opened to allow the flow into mass flow controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valve 111
7, 1118, 1119, the auxiliary valve 1132 is 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 NO gas flow rate becomes a desired value.
8 and 1119, 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 50 to 400°C by the heating heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the openings of the valves 1118 and 1120 are gradually changed according to a pre-designed rate of change curve by controlling the flow rates of GeH ₄ /He gas and NO gas manually or using an externally driven motor. By controlling this, the distribution concentration of germanium atoms and oxygen atoms contained in the formed layer is controlled. In the manner described above, the glow discharge is maintained for a desired time to form a layer region (G) on the substrate 1137 to a desired layer thickness.
form. At the stage where the layer region (G) has been formed to the desired layer thickness, the glow is carried out for the desired time according to the same conditions and procedures, except for completely closing the outflow valve 1118 and changing the discharge conditions as necessary. By maintaining the discharge, a layer region (S) substantially free of germanium atoms can be formed on the layer region (G). In order to contain the substance (C) that controls conductivity in the layer region (G) and the layer region (S), for example, when forming the layer region (G) and the layer region (S),
Gases such as B ₂ H ₆ and PH ₃ may be added to the gas introduced into the deposition chamber 1101. To form the second layer () on the first layer () formed to the desired thickness as described above, use the same valve operation as when forming the first layer (). , for example, by diluting each of SiH ₄ gas and C ₂ H ₄ gas with a diluent gas such as He as necessary to generate glow discharge according to desired conditions. To contain halogen atoms in the second layer (), for example, use SiF ₄ gas and C ₂ H ₄ gas, or add SiH ₂ gas to this and form the second layer () in the same manner as above. It is accomplished by Needless to say, all outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 1101. Valve 1
In order to avoid gas remaining in the gas piping leading from 117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1120 are closed, and the auxiliary valve 11
32, 1133 and fully open the main valve 1134 to temporarily evacuate the system to high vacuum, as necessary. The amount of nitrogen atoms contained in the second layer () is, for example, SiH ₄ gas in the case of glow discharge,
The flow rate ratio of NH ₃ gas introduced into the reaction chamber 1101 can be changed as desired, or when forming a layer by sputtering, the sputtering area of the silicon wafer and the Si ₃ N ₄ wafer can be changed when forming the target. Change the ratio or use silicone powder
It can be controlled as desired by changing the mixing ratio of Si ₃ N ₄ powder and molding the target. The amount of halogen atoms (X) contained in the second layer () can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF ₄ gas, is introduced into the reaction chamber 1101. It will be done. Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 Samples (sample Nos. 11-1 to 17-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 15 under the conditions shown in Table 1.
(Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen atoms in each sample is shown in FIG. Each sample thus obtained was placed in a charging exposure experimental device and corona charged at 5.0 kV for 0.3 seconds.
A light image was immediately irradiated. A tungsten lamp light source was used as the 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 chargeable developer (including toner and carrier) onto the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using 5.0 kV corona charging, all samples had excellent resolution, and clear, high-density images with good gradation reproducibility were obtained. In the above, the toner image forming conditions were the same as above, except that an 810 nm GaAs semiconductor laser (10 mW) was used as the light source instead of a tungsten lamp, and an electrostatic image was formed. When the image quality of the toner-transferred images was evaluated, all samples had excellent resolution, and clear, high-quality images with good gradation reproducibility were obtained. Example 2 Samples (sample Nos. 21-1 to 27-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate using the manufacturing apparatus shown in FIG. 15 under the conditions shown in Table 3.
were created respectively. (Table 4) The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of oxygen atoms in each sample is shown in FIG. When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. Furthermore, when each sample was tested for repeated use 200,000 times in an environment of 38°C and 80% RH, no deterioration in image quality was observed in any of the samples. Example 3 Samples Nos. 11-1 and 12- of Example 1 were used, except that the conditions for creating the second layer () were as shown in Table 5.
Each of the electrophotographic image forming members (sample No. 11-1-
1~11-1-8, 12-1-1~12-1-8, 13-
24 samples (Nos. 1-1 to 13-1-8) were created. The electrophotographic image forming members corresponding to each example were individually installed in a copying machine and subjected to the same conditions as described in each example. For each, we evaluated the overall image quality of the transferred image and evaluated the durability through repeated and continuous use. Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use. Example 4 When forming the second layer (), the target area ratio of the silicon wafer and Si ₃ N ₄ was changed to form the layer ().
Each of the image forming members was prepared in exactly the same manner as in Sample No. 11-1 of Example 1, except that the content ratio of silicon atoms to nitrogen atoms was changed. For each of the imaging members thus obtained,
After repeating the steps of image formation, development, and cleaning as described in Example 1 about 50,000 times, image evaluation was performed, and the results shown in Table 7 were obtained. Example 5 When forming the second layer (), SiH ₄ gas and
An image forming member was prepared in exactly the same manner as Sample No. 12-1 of Example 1 except that the content ratio of silicon atoms and nitrogen atoms in the layer () was changed by changing the flow rate ratio of NH ₃ gas. created each. For each image forming member thus obtained, the steps up to transfer were repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 8 were obtained. Example 6 When forming the second layer (), SiH ₄ gas,
By changing the flow rate ratio of SiF ₄ gas and NH ₃ gas, the layer ()
Each of the image forming members was prepared in exactly the same manner as in Sample No. 13-1 of Example 1, except that the content ratio of silicon atoms to nitrogen atoms was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed and the results shown in Table 9 were obtained. Example 7 Each of the image forming members was prepared in exactly the same manner as in Sample No. 14-1 of Example 1, except that the layer thickness of the second layer (2) was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 10.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

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

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

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 are for explaining the distribution state of germanium atoms in the layer region (G), respectively. , FIGS. 11 to 14 are explanatory diagrams for explaining the distribution state of oxygen atoms in the first layer ( ), and FIG. 15 is a schematic illustration of the apparatus used in the present invention. In the figure, Figure 16,
FIG. 7 is a distribution state diagram showing the content distribution state of each atom in each example of the present invention. 100...Photoconductive member, 101...Support, 1
02...First layer (), 103...Second layer (), 107...Photoreceptive layer.

Claims (1)

[Claims] 1. 1 to 10× with respect to the sum of the support for a photoconductive member for electrophotography and the silicon atoms on the support.
A layer region (G) with a layer thickness of 30 Å to 50 μ made of an amorphous material containing 10 ⁵ atomic ppm of germanium atoms and a layer region (G) made of an amorphous material containing silicon atoms (but not containing germanium atoms) 0.5～
A first layer exhibiting photoconductivity with a layer thickness of 1 to 100 μ and a layer region (S) of 90 μ in thickness provided in order from the support side, silicon atoms and 1×10 −3 to 1×10 ⁻³
and a second layer with a layer thickness of 0.003 to 30μ made of an amorphous material containing 90 atomic% carbon atoms, and the first layer is made of silicon atoms, germanium atoms, and oxygen atoms. 0.001 for the sum of atoms
Contains ~50 atomic% oxygen atoms, has a smooth concentration distribution, and has a maximum concentration distribution of 500 atomic ppm or more within a layer thickness of 5μ from the support side of the layer or the interface side with the second layer. Photoconductive member for electrophotography. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the layer region (G) and the layer region (S) contains hydrogen atoms. 3. The photoconductive member for electrophotography according to claim 1 or 2, wherein at least one of the layer region (G) and the layer region (S) contains a halogen atom. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the layer region (G) is non-uniform. 5. The photoconductive member for electrophotography according to claim 1, wherein the germanium atoms are uniformly distributed in the layer region (G). 6. The photoconductive member for electrophotography according to claim 1, wherein the first layer contains a substance that controls conductivity. 7. The photoconductive member for electrophotography according to claim 6, wherein the substance governing conductivity is an atom belonging to Group 3 of the periodic table. 8. The photoconductive member for electrophotography according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group 3 of the periodic table.