JPH0215867B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, gamma rays, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. At times, solid-state imaging devices are required to have characteristics such as being non-polluting to the human body and being able to easily process afterimages within a predetermined time.
Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point. Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having a photoconductive layer composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance. The reality is that there is a need to improve overall characteristics in terms of usage environment characteristics and stability over time, and there are areas that can be further improved. For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, resulting in the so-called ghost phenomenon that causes an afterimage, or when used repeatedly at high speeds, the responsiveness gradually decreases. There were many cases where spots appeared. Furthermore, a-Si has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively. In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light that reaches the support increases, the support itself will absorb the light that passes through the photoconductive layer. When the reflectance is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties. In this case, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in dark areas, etc. This often occurs. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive material used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms (Si) and a germanium atom (Ge) as a matrix, and an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium , or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to generically as "a-
SiGe (H, The conductive material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side. The present invention 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 that is durable, does not cause deterioration 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 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 with high quality. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member having excellent electrophotographic properties with sufficient performance and with almost no deterioration of the properties observed even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support. The photoconductive member for electrophotography of the present invention comprises a support for the photoconductive member for electrophotography, and an amorphous material containing germanium atoms in an amount of 1 to 9.5×10 ⁵ atomic ppm based on the sum of silicon atoms and silicon atoms. a first layer exhibiting photoconductivity, consisting of a material, and a second layer having a thickness of 0.003 to 30μ and consisting of an amorphous material containing silicon atoms and 1×10 ⁻³ to 90 atomic percent carbon atoms; and a photoconductive member for electrophotography, the photoreceptive layer containing nitrogen atoms and having a distribution concentration of nitrogen atoms in the layer thickness direction, respectively. , C(1), C(3), C(2) layer thickness
First layer area (1) of 0.003-100μ, layer thickness 0.003-80μ
and a second layer region (2) with a layer thickness of 0.003 to 100μ in this order from the support side, and the distribution concentration C(3) is composed of silicon atoms, germanium atoms, and nitrogen atoms. 10 atomic ppm to 67 atomic for the sum of atoms
%, and is characterized in that C(3)>C(2), C(1), and at least one of C(1) and C(2) is not 0. 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. The photoconductive member for electrophotography of the present invention has no influence of residual potential on image formation, has stable electrical characteristics, high sensitivity, and a high signal-to-noise ratio, and is resistant to light fatigue and repeated use. It has excellent usage characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Furthermore, in the photoconductive member of the present invention, the photoreceptive layer formed on the support is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. can be used. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 is made of a-SiGe (H, It has a first layer () 102 and a second layer () 103. The germanium atoms contained in the first layer ( ) 102 may be uniformly distributed in the first layer ( ) 102, or may be uniformly distributed in the layer thickness direction. The distribution concentration may be non-uniform, although the content may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly contained in order to make the properties uniform in the in-plane direction. is also necessary. In particular, it is uniformly contained 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 107 side of the photoreceptive layer). against the support side 101
The first layer ( ) 102 may be distributed more toward the side of the interface between the light-receiving layer and the support 101, or vice versa.
contained within. In the photoconductive member of the present invention, as described above, the distribution state of the germanium atoms contained in the first layer ( ) is as described above in the layer thickness direction, and It is desirable to have a uniform distribution state in the in-plane direction parallel to . The first layer ( ) 102 of the photoconductive member 100 shown in FIG. 1 has a first layer region (1 )
104, second layer region (2) having a value of C(2) 10
5, and a third layer region (3) 106 having a value of C(3). In the present invention, each of the first, second, and third layer regions described above does not necessarily need to contain nitrogen atoms in any of these three layer regions; C(3) is the distribution concentration C(1), C(2)
, and the distribution concentration C(1), C
At least one of (2) must not be 0, or the distribution concentrations C(1) and C(2) must not be equal. When either the distribution concentration C(1) or C(2) is 0, the first layer ( ) 102 is the first layer region (1) 104 as a layer region that does not contain nitrogen atoms.
Alternatively, it has a second layer region (2) 105 and a third layer region (3) having a higher distribution concentration C(3). In this case, if nitrogen atoms are contained in a relatively high concentration to prevent charge injection from the free surface side into the first layer (102), the first layer region (1) It is necessary to design the first layer ( ) 102 with 104 as a layer region that does not contain nitrogen atoms, and conversely, to prevent charge injection from the support 101 side into the first layer ( ) 102 and to support it. body 1
If the aim is to improve the adhesion between 01 and the first layer () 102, the second layer region (2) 105 should be set as a layer region that does not contain nitrogen atoms and the first layer ()
102 needs to be designed. In the present invention, the third layer region (3) 106 having the largest distribution concentration C(3) among the three layers has good photosensitivity characteristics and is superior to the first layer (2) 102. In order to improve the dark resistance of the layer, it is desirable to set the value of the distribution concentration C(3) to a relatively low value, and to set the layer thickness to a sufficient thickness within the necessary range. In addition, if the third layer region (3) 106 is expected to mainly have a charge injection prevention effect by setting the value of the distribution concentration C(3) to a relatively high value, the third layer region (3) 106 (3) The thickness of the layer 106 should be as thin as possible within the range where the effect of blocking charge injection is sufficiently obtained, and the free surface 107 of the first layer ( ) 102 should be made as thin as possible.
It is desirable to provide the third layer region (3) 106 on the side or as close as possible to the support 101 side. In this case, when the third layer region (3) 106 is provided closer to the support 101 side, the first layer region (1) 104 has a layer thickness within a necessary range. The layer is made sufficiently thin and is provided mainly to improve the adhesion between the support 101 and the first layer (102). When the third layer region (3) 106 is provided closer to the free surface 107 side, the second layer region (2) 105 is more likely to be exposed to the humid atmosphere than the third layer region (3) 106. It is mainly provided for the purpose of preventing In the present invention, the layer thicknesses of the first layer region (1) and the second layer region (2) can be adjusted as desired in relation to the distribution concentrations C(1) and C(2). It is determined by
It is desirable that the thickness be 80μ, optimally 0.005 to 50μ. Further, the layer thickness of the third layer region (3) is appropriately determined in relation to the distribution concentration C(3), but is preferably
It is desirable that the thickness be 0.003 to 80μ, more preferably 0.004 to 50μ, and optimally 0.005 to 40μ. When the third layer region (3) mainly functions as a charge injection blocking layer, it should be provided close to the support side or the free surface side of the first layer (2), and the layer thickness should be adjusted preferably. is less than 30μ, preferably 20μ
Hereinafter, it is optimally desirable to set it to 10μ or less. In this case, the layer thickness of the first layer region (1) on the support side where the third layer region (3) is provided or the second layer region (2) on the free surface side is the same as that of the third layer region (3). It is determined as appropriate from the viewpoint of the value of the distribution concentration C(3) of nitrogen atoms contained in the layer region (3) and the productive efficiency, but preferably
It is desirable that the thickness be 5 μ or less, more preferably 3 μ or less, and optimally 1 μ or less. In the present invention, the nitrogen atom content distribution concentration C(3)
The maximum value of is preferably 67 atomic%, more preferably 50 atomic%, and optimally 40 atomic% with respect to the sum of silicon atoms, germanium atoms, and nitrogen atoms (hereinafter referred to as "T (SiGeN)"). is desirable. Further, it is desirable that the minimum value of the distributed concentration C(3) is preferably 10 atomic ppm, more preferably 15 atomic ppm, and optimally 20 atomic ppm for T (SiGeN). When the distribution concentrations C(1) and C(2) are not 0, the minimum value is preferably 1 atomic ppm, more preferably 3 atomic ppm, relative to T (SiGeN).
The optimum level is preferably 5 atomic ppm. 2 to 10 show typical examples in which the distribution state of germanium atoms contained in the first layer ( ) of the photoconductive member in the present invention is non-uniform in the layer thickness direction. In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer exhibiting photoconductivity, and t _B represents the thickness of the first layer on the support side. _t indicates the position of the surface of the first layer () on the side opposite to the support side. That is, the first layer ( ) containing germanium atoms 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 first layer ( ) in the layer thickness direction. In the example shown in FIG. 2, from the interface position t _B to the position t ₁ between the surface on which the first layer containing germanium atoms ( ) is formed and the surface of the first layer ( ), The distribution concentration C of germanium atoms is C ₁
Germanium atoms are contained in the first layer () formed, and the distribution concentration _C2 is gradually and continuously decreased from the position _t1 to the interface position _tT , while taking a constant value. There is. 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). In the case of Fig. 5, the distribution concentration C of germanium atoms is gradually decreased continuously from the concentration C ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 6, the distribution concentration C of germanium atoms between position t _B and position t ₃ is as follows:
The concentration C is a constant value of ₉ , and at the position t _T the concentration
C ₁₀ will be done. 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 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 ₁₁ 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 ( ) 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
One preferred example is when the photoreceptive layer is provided with a germanium atom distribution state in which the distribution concentration C is considerably lower on the support side than on the support side. The first layer () constituting the photoconductive member of the present invention preferably has a relatively high concentration of germanium atoms on the support side as described above or, conversely, on the free surface side. It is desirable to have a localized region (A) contained therein. 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. The localized region (A) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or
It may also be part of the layer region (L _T ). 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. The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, more preferably. It is desirable that the layer be formed in such a manner that a distribution state of 5000 atomic ppm or more, optimally 1×10 ⁴ atomic ppm or more can be achieved. That is, in the present invention, in the first layer containing germanium atoms (), the maximum value Cmax 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 the following manner. In the present invention, the content of germanium atoms contained in the first layer (2) may be appropriately determined as desired so as to effectively achieve the object of the present invention, but the , preferably 1 to 9.5×10 ⁵ atomic ppm, more preferably 100 to 8×10 ⁵ atomic ppm, optimally 500
It is desirable that the content be 7×10 ⁵ atomic ppm. The distribution state of germanium atoms in the first layer ( ) 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 increases from the support side to the first layer ( ). is given a decreasing change towards the free surface of
Alternatively, if the opposite change is given, the first layer () having the required characteristics can be obtained by arbitrarily designing the rate of change curve of the distribution concentration C as desired. It can be realized just like that. For example, the distribution concentration C of germanium in the first layer () should be sufficiently high on the support side, and as low as possible on the free surface side of the first layer (). By giving a change in C to the distribution concentration curve of germanium atoms, it is possible to achieve photosensitivity to light of wavelengths in the entire range from relatively short wavelengths to relatively long wavelengths, including the visible light region. At the same time, it is possible to effectively prevent interference with coherent light such as laser light. Furthermore, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer ( ) on the side of the support, when a semiconductor laser is used, the laser of the photoreceptive layer can be reduced. Light on the long wavelength side that is not fully absorbed on the irradiated surface side can be substantially completely absorbed in the support side end layer region of the photoreceptive layer, eliminating interference due to reflection from the support surface. It can be effectively prevented. In the photoconductive member of the present invention, in order to increase photosensitivity and dark resistance, and furthermore to prevent charge injection from the free surface of the photoreceptive layer, contains a nitrogen atom. The nitrogen atoms contained in the first layer () may be evenly contained in the entire layer area of the first layer () satisfying the above conditions, or may be contained evenly in the entire layer area of the first layer (). It may be contained only in a part of the layer region and may be distributed ubiquitously. In the present invention, the distribution state of nitrogen atoms is non-uniform in the layer thickness direction in the entire first layer () as described above, but in each of the first, second and third layer regions. is uniform in the layer thickness direction. FIGS. 11 to 14 show typical examples of the distribution of nitrogen atoms in the entire first layer (). Symbols used throughout the description of these figures have the same meanings as used in FIGS. 2 through 10. In the example shown in FIG. 11, from position t _B to position t ₉
The distribution concentration of nitrogen atoms is C(N) C ₂₁ from position t ₉ to position t ₁₁ .
is _C22 , and the distribution concentration C(N) of nitrogen atoms from position _t11 to position _tT is _C21 . In the example shown in FIG. 12, from position t _B to position t ₁₂
The distribution concentration C(N) of nitrogen atoms is C ₂₃ from position t ₁₂ to position t ₁₃ .
(N) is increased stepwise to C ₂₄ from position t ₁₃ to position t _T
Up to this point, the distribution concentration C(N) of nitrogen atoms was reduced to _C25 . In the example of FIG. 13, the distribution concentration C(N) of nitrogen atoms from position t _B to position t ₁₄ is C ₂₆ , and the distribution concentration C (N) of nitrogen atoms from position t ₁₄ to position t ₁₅ is C ₂₇ . The distribution concentration C(N) of nitrogen atoms is increased stepwise from the position t ₁₅ to the position t _T to a concentration C ₂₈ that is lower than the initial concentration. In the example shown in FIG. 14, from position t _B to position t ₁₆
The distribution concentration C(N) of nitrogen atoms is C ₂₉ from position t ₁₆ to position t ₁₇ .
(N) is decreased to C ₃₀ , and from position t ₁₇ to position t ₁₈ , the distribution concentration of nitrogen atoms C(N) increases stepwise to C ₃₁ , and from position t ₁₈ to position t _B , the concentration of nitrogen atoms is The distribution concentration C(N) is reduced to _C30 . In the present invention, a nitrogen atom-containing layer region (N) provided in the first layer () (consisting of at least two layer regions of the above-mentioned first, second, and third layer regions) When the main purpose is to improve photosensitivity and dark resistance, the first layer () is provided to occupy the entire layer area of the first layer () to prevent charge injection from the free surface of the photoreceptive layer. In order to do this, it is provided near the interface on the free surface side, and if the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, the end of the first layer () on the support side It is provided so as to occupy the sublayer area. In the first case, the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain high photosensitivity, and in the second case to prevent charge injection from the free surface of the photoreceptor layer. In the latter case, it is desirable to use a relatively large amount to ensure strong adhesion to the support. In addition, in order to achieve the three simultaneously, it is distributed at a relatively high concentration on the support side, and at a relatively low concentration at the center of the first layer (2).
In the interfacial layer region on the free surface side of the first layer (),
It is sufficient to form a distribution state of nitrogen atoms in the layer region (N) such that the number of nitrogen atoms is increased. In order to prevent charge injection from the free surface, it is desirable to form a layer region (N) in which the distribution concentration C(N) of nitrogen atoms is increased on the free surface side. In the present invention, the content of nitrogen atoms contained in the layer region (N) provided in the first layer () is as follows:
The characteristics required for the layer region (N) itself, or when the layer region (N) 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 (N), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region The nitrogen atom content is appropriately selected with consideration given to the following. The amount of nitrogen atoms contained in the layer region (N) is
Although it can be determined as desired depending on the characteristics required of the photoconductive member to be formed, it is preferably 0.001 to 50 atomic%, more preferably 0.002 to 40 atomic%, and optimally 0.003 atomic% based on T (SiGeN). ~
It is desirable to set it to 30 atomic%. In the present invention, the layer region (N) occupies the entire area of the first layer (), or the layer region (N) occupies the entire area of the first layer ().
Even if the layer area (N) does not occupy the entire area, the layer thickness T ₀
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 nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value. . In the case of the present invention, the ratio of the layer thickness T ₀ of the layer region (N) to the layer thickness T of the first layer ( ) is 5
In such a case, the upper limit of the amount of nitrogen atoms contained in the layer region (N) is T
(SiGcN), preferably 30 atomic% or less, more preferably 20 atomic% or less, optimally
It is desirable that it be 10 atomic% or less. In the present invention, the layer region (N) containing nitrogen atoms constituting the first layer () has a relatively high concentration of nitrogen atoms near the interface on the support side and the free surface side, as described above. In the former case, it is desirable to further improve the adhesion between the support and the photoreceptive layer and to improve the receptive potential. can be measured. 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 maximum value Cmax of the distribution concentration C(N) of nitrogen atoms is preferably 500 atomic as the distribution state of the nitrogen atoms contained therein in the layer thickness direction.
ppm or more, more preferably 800 atomic ppm or more,
Optimally, it is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be obtained. That is, in the present invention, the layer region (N) containing nitrogen atoms has a distributed concentration within 5 μm in layer thickness from the support side or free surface side interface (layer region 5 μ thick from t _B or t _T ). It is desirable that the maximum value Cmax exists. In the present invention, if necessary, the first layer ()
Specific examples of the halogen atom (X) contained therein include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the photoconductive member of the present invention, the conductive properties of the first layer (2) can be controlled as desired by containing a substance that controls the conductive properties in the first layer (2). You can. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-
For SiGe (H, Specifically, p-type impurities include atoms belonging to Group 3 of the periodic table (Group atoms), such as 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.
In particular, P and As are preferably used. In the present invention, the content of the substance that controls the conduction characteristics contained in the first layer () is determined by the conduction characteristics required for the first layer () or It can be selected as appropriate based on the organic relationship, such as the relationship with the properties of the contact interface with the support provided in direct contact with the support. 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 to When it is contained in the support side end layer region of one layer (), the characteristics of the other layer region provided in direct contact with the layer region and the contact interface with the other layer region The content of the substance that controls the conduction properties is appropriately selected, taking into consideration the relationship with the properties. In the present invention, the content of the substance controlling conduction properties contained in the first layer () is preferably 0.01 to 5×10 atomic ppm, more preferably 0.5 to 1×10 ⁴ atomic ppm. ppm, optimally 1~
It is desirable that the content be 5×10 ³ atomic ppm. In the present invention, the content of the substance controlling conduction characteristics in the layer region containing the substance is preferably 30 atomic ppm or more, more preferably
50atomic ppm or more, optimally 100atomic ppm
In the above case, it is preferable that the substance be locally contained in a part of the layer region of the first layer (I), and particularly unevenly distributed in the end layer region of the first layer (I) on the side of the support. It is desirable to do so. Among the above, for example, by containing a substance that controls the conductive properties 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-mentioned value. When the substance to be contained is the above-mentioned p-type impurity, injection of electrons from the support side into the photoreceptive layer can be effectively prevented when the free surface of the photoreceptive layer is subjected to polar charging treatment. is possible,
In addition, when the substance to be contained is the n-type impurity described above, when the free surface of the photoreceptive layer is subjected to polar charging treatment, it is possible to effectively prevent holes from being injected from the support side into the photoreceptor layer. can be prevented. In this way, when the end layer region (E) contains a substance that controls conductivity of one polarity, the remaining layer region of the photoreceptive layer, that is, the end layer region (E) The removed layer region (Z) 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 (E). It may be contained in an amount much smaller than the actual amount contained in the. In such a case, the content of the substance controlling 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 appropriately according to desire, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the 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 preferably , preferably 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 layer region containing a dominating substance in direct contact with a so-called depletion layer in this 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 first 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 by forming a depletion layer. In the present invention, in order to form the first layer () composed of a-SiGe (H, It is done by law. For example, in order to form the first layer ( ) composed of a-SiGe (H, A source gas for Ge supply that can supply source gas and germanium atoms (Ge), and a source gas for introducing hydrogen atoms (H) and/or a source gas for introducing halogen atoms (X) as necessary, are a-SiGe (H, It is sufficient to form a layer consisting of. Furthermore, in order to contain germanium atoms in a non-uniform distribution state, a layer consisting of a-SiGe(H,X) may be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. . 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,
Alternatively, a raw material gas for supplying Ge diluted with a diluent gas such as He or Ar may be diluted with a diluent gas such as He or Ar by using a mixed gas of Si and Ge.
This is accomplished by introducing a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) into a sputtering deposition chamber to form a plasma atmosphere of the desired gas. In order to make the distribution of germanium atoms uniform, 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. 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 board as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
The process 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 a method of heating and evaporated, and the flying evaporated material is passed through a desired gas plasma atmosphere. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SIF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer () made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When manufacturing the first layer () containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which is the raw material gas for supplying Si, and
Hydrogenated germanium, which is the raw material gas for Ge supply, and
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber for forming the first layer () at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to generate plasma of these gases. The first layer () can be formed on the desired support by forming an atmosphere, but in order to make it easier to control the ratio of hydrogen atoms introduced, A desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with the gas 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, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Gaseous or gasifiable substances such as germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for the formation of the first layer. Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the first layer (), 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 (), 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), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms contained in the first layer () of the photoconductive member to be formed (H+X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. Hydrogen atoms (H) contained in the first layer ()
Or/and to control the amount of halogen atoms (X), for example, the support temperature or/and 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 provide the layer region (N) containing nitrogen atoms in the first layer (), the above-mentioned starting material for introducing nitrogen 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 (N), a starting material for introducing nitrogen atoms is added to a material selected as desired from among the starting materials for forming the first layer (N) described above. Substances are added. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen 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 nitrogen atoms (N), 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 nitrogen atoms (N) 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), nitrogen atoms (N), and hydrogen atoms (H). It is possible to use a mixture of raw material gases having two constituent atoms. Alternatively, a raw material gas containing nitrogen atoms (N) may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H). The starting material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming the layer region (N) is one containing N as a constituent atom or containing N and H. Atomic or gaseous or gasifiable substances such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. Mention may be made of nitrogen, nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Mention may be made of halogenated nitrogen compounds. In the present invention, the layer region (N) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms. Examples of raw material gases for introducing oxygen atoms into the layer region (N) include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), Nitrogen monoxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), trinitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atom (O), and hydrogen atom (H) as constituent atoms, such as lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). I can do it. To form the layer region (N) by the sputtering method, when forming the first layer (), a single crystal or polycrystalline Si wafer or a Si ₃ N ₄ wafer, or a mixture of Si and Si ₃ N ₄ is used. This can be carried out by sputtering the wafers contained in the wafer in various gas atmospheres. For example, if a Si wafer is used as a target, nitrogen atoms and optionally hydrogen atoms or/and
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, by using Si and Si ₃ N ₄ as separate targets, or by using a mixed target of Si and Si ₃ N ₄ , a dilution gas atmosphere can be created as a sputtering gas. This is accomplished by sputtering in a gas atmosphere containing at least 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 nitrogen 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 (N) containing nitrogen atoms is provided when forming the first layer (), the distribution concentration C ( N) in a stepwise manner in the layer thickness direction,
In order to form a layer region (N) with a desired depth profile, in the case of a glow discharge, the starting material for nitrogen atom introduction whose distribution concentration C(N) should be varied is This is accomplished by introducing a gas into the deposition chamber while appropriately varying 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 passage system may be appropriately changed by any commonly used method such as manually or by using an externally driven motor. When the layer region (N) is formed by sputtering, the distribution concentration of nitrogen atoms in the layer thickness direction C(N)
In order to change stepwise in the layer thickness direction and form a desired distribution state (depth profile) of nitrogen atoms in the layer thickness direction, first, as in the case of the glow discharge method, nitrogen atoms are introduced. This is accomplished by using a starting material in a gaseous state and appropriately varying the gas flow rate at which the gas is introduced into the deposition chamber as desired. Second, the target for sputtering,
For example, if a mixed target of Si and Si ₃ N ₄ is used, the mixing ratio of Si and Si ₃ N ₄ can be changed in advance in the layer thickness direction of the target. will be accomplished. In order to structurally introduce a substance that controls the conduction properties into the first layer (2), for example, a group atom or a group atom, a starting material for introducing a group atom or a group atom must be 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 first 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 group atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ ,
Boron hydride such as B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , etc., BF ₃ ,
Examples include boron halides such as BCl ₃ and BBr ₃ .
In addition, AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ ,
TlCl ₃ etc. can also be mentioned. 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 ₃ , SBF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. In the present invention, the layer thickness of the layer region constituting the first layer () and containing a substance that controls conduction properties and provided unevenly on the support side is defined as the thickness of the layer region and the layer region above the layer region. The lower limit is preferably 30 Å or more, and more preferably 30 Å or more. Preferably 40
It is desirable that the thickness be at least Å, most preferably at least 50 Å. Further, when the content of the substance controlling the conduction properties contained in the layer region is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region is preferably 10 μ or less, more preferably 8μ or less, optimally
It is desirable that the thickness be 5μ or less. 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. Further, in the present invention, the first layer ( ) 102
Since each of the amorphous materials constituting the second layer ( ) 103 has a common constituent element of silicon atoms, chemical stability is sufficiently ensured at the laminated interface. The second layer () in the present invention is an amorphous material (hereinafter referred to as , “a-(Si _x C _1-x ) _y (H,X) _1
-y '', where 0<x, y<1). The formation of the second layer () composed of a-(Si _x C _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 carbon 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 in the same apparatus system. To form the second layer () by the glow discharge method, a-(Si _x C _{1-x ) y} (H, 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 C _1-x ) _y (H,X) _1-y on the first layer ( ) which has already been formed. In the present invention, a-(Si _x C _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Most gaseous substances or gasified substances containing at least one of carbon atoms (C), hydrogen atoms (H), and halogen atoms (X) are used. obtain. When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as necessary. Depending on the situation, a raw material gas containing H as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si and C and H may be used. The raw material gas containing constituent atoms and/or the raw material gas containing X as constituent atoms are also mixed at a desired mixing ratio, or the raw material gas containing Si and/or X as constituent atoms are mixed, or the raw material gas containing Si and/or
A raw material gas containing three constituent atoms of C and H, or
It is possible to use a mixture of a raw material gas containing the three constituent atoms of Si, C, and X. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. Raw material gases serving as constituent atoms may be mixed and used. In the present invention, preferred halogen atoms (X) contained in the second layer () are F, Cl,
Br and I, with F and Cl being particularly preferred. 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 gas such as silanes, C and H
For example, a saturated hydrocarbon having 1 to 4 carbon atoms, an ethylene hydrocarbon having 2 to 4 carbon atoms,
Examples include acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n
-Butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ),
Propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylenic hydrocarbons ,
Acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl,
HBr, interhalogen compounds include BrF, ClF,
ClF ₃ , ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ , ICl, IBr,
Silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ ,
SiCl ₃ Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I, SiBr ₄ ,
Examples of halogen-substituted silicon hydride include SiH ₂ F ₂ ,
SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ ,
SiHBr ₃ , as silicon hydride, SiH ₄ , Si ₂ H ₈ ,
Silanes such as Si ₄ H ₁₀ , etc. can be mentioned. In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
CH ₂ F ₂ , CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I,
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ Cl,
Fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si(CH ₃ ) ₄ ,
Alkyl silicides such as Si(C ₂ H ₅ ) ₄ and SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be cited as effective. These second layer () forming substances contain silicon atoms, carbon 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, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ and SiH can contain halogen atoms. _{A- ( Si x _} C1 _-x ) _y
A second layer () consisting of (Cl+H) _1-y can be formed. To form the second layer () by the sputtering method, target a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer in which Si and C are mixed and synthesized. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements, if necessary. For example, if a Si wafer is used as a target, the raw material gas for introducing C and H or/and The Si wafer may be sputtered by forming a gas plasma of the above gas. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as necessary by using Si and C as separate targets or by using a mixed target of Si and C. This is done by sputtering inside.
As the raw material gas for introducing C, H and obtain. 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, e.g.
Preferred examples include He, Ne, Ar, and the like. The second layer () in the present invention is carefully formed to provide its required properties as desired. In other words, substances containing Si, C, and optionally 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 C _1-x ) _y ( _H , For example, to provide the second layer () with the main purpose of improving electrical withstand voltage, a-(Si _x C _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 C _1-x ) _y (H,X)
_1-y is created. On the surface of the first layer () a-(Si _x C _1-x ) _y (H,
When forming the _second layer ( ) consisting of a-(Si _x C _1-x ) having the desired properties
It is desirable that the temperature of the support during layer formation be strictly controlled so that _y (H,X) _1-y can be formed as desired. In the present invention, the formation of the second layer (2) is carried out by selecting an optimal range as appropriate in accordance with the method of forming the second layer (2) in order to effectively achieve the desired purpose. Preferably, the temperature is 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 the sputtering method is advantageous, but when forming the second layer () using these layer forming methods, the discharge power during layer formation is determined as well as the support temperature described above. Rua
-(Si _x C _1-x ) _y It is one of the important factors that influences the characteristics of X _1-y . _The discharge power condition for effectively producing a-(Si _x C _1-x ) _y , more preferably 20-250W, optimally
It is desirable that the power be 50 to 200W. The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr,
More preferably, it is about 0.1 to 0.5 Torr. In the present invention, the values of the support temperature and discharge power for forming the second layer () are preferably in the ranges described above, but these layer forming factors are determined independently and separately. a-(Si _x C _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 carbon atoms contained in the second layer (2) in the photoconductive member of the present invention is determined in the same way as the production conditions of the second layer (2), such that the second layer (2) has the desired properties that achieve the object of the present invention. This is an important factor in the formation of the layer (). The amount of carbon 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 C _1-x ) _y (H,X) _1-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ". However, 0<a<1 ),
Amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C _1-b ) _c H _1-c ". However, 0<b, c<1) , an amorphous material (hereinafter referred to as "a-(Si _d
C _1-d ) _e (H,X) _1-e ”. However, 0<d, e<
It is classified as 1). In the present invention, the second layer () is a-Si _a
When composed of C _1-a , the amount of carbon atoms contained in the second layer ( ) is preferably from 1×10 ⁻³ to
It is desirable that the content be 90 atomic %, more preferably 1 to 80 atomic %, most preferably 10 to 75 atomic %. That is, if expressed as a in the above a-Si _a C _1-a , a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25 to 0.9. In the present invention, the second layer () is a-(Si _b
When composed of C _1-b ) _c H _1-c , the amount of carbon atoms contained in the second layer ( ) is preferably 1×10 ⁻³
~90 atomic%, more preferably 1~
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%.
It is desirable that the hydrogen content be within these ranges, and photoconductive members formed with hydrogen contents within these ranges can be sufficiently applied as excellent materials in practical applications. That is, if expressed as a-(Si _b C _1-b ) _c H _1-c above, b is preferably 0.1 to 0.99999, more preferably 0.1
~0.99, optimally 0.15-0.9, c preferably 0.6
~0.99, more preferably 0.65~0.98, optimally 0.7~
A value of 0.95 is desirable. The second layer () is a-(Si _d C _1-d ) _e (H,X)
_1-e , the content of carbon atoms contained in the second layer () is preferably 1 x 10 ^-3 to 90 atomic%, more preferably 1 to 90 atomic%.
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 18 atomic%, and optimally 2 to 20 atomic%.
It is preferable that the halogen atom content be 15 atomic %, and photoconductive members prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms, which may be included as necessary, is preferably 19 atomic % or less, more preferably 13 atomic % or less. That is, d in the previous a-(Si _d C _1-d ) _e (H,X) _1-e ,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
It is desirable that it be between 0.82 and 0.99, most preferably between 0.85 and 0.98. The number range of the layer thickness of the second layer () 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 thickness of the second layer () is determined by the amount of carbon 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 0.004μ.
It is desirable that the thickness be ~20μ, optimally 0.005~10μ. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pb, 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. 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,Pd,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to use
It is considered to be 10μ or more. 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 SiF ₄ gas diluted with He (purity 99.99%, hereinafter referred to as SiF ₄ /He)
It is abbreviated as ) cylinder, 1105 is NH ₃ 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 1122 of gas cylinders 1102 to 1106 are used.
~1126, confirm that leak valve 1135 is closed, and inlet valve 1112~1
116. 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, gas from gas cylinder 1105
NH ₃ gas valves 1122, 1123, 112
4 and outlet pressure gauges 1127, 1128, 1
Adjust the pressure of 129 to 1Kg/cm ² and open the inflow valve 11.
12, 1113, 1114 gradually, the mass flow controllers 1107, 1108, 1109
Let them flow into each other. Subsequently, the outflow valve 11
17, 1118, 1119, auxiliary valve 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
The outflow valves 1117 and 111 are adjusted so that the ratio between the GeH ₄ /He gas flow rate and the NH ₃ 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 flow rate of NH ₃ gas is controlled by the valve 1118 manually or by an externally driven motor, etc. according to a pre-designed rate of change curve.
The distribution concentration of nitrogen atoms contained in the formed layer is controlled by appropriately changing the opening of the layer. 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. In order to contain halogen atoms in the second layer (), for example, SiF ₄ gas and C ₂ H ₄ gas, or by adding SiH ₂ gas to this and forming 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 1121 are closed, and the auxiliary valve 11
32 and 1133 and fully open the main valve 1134 to temporarily evacuate the system to high vacuum, as necessary. The amount of carbon atoms contained in the second layer () is, for example, SiH ₄ gas in the case of glow discharge,
The flow rate ratio of the C ₂ H ₄ gas introduced into the reaction chamber 1101 can be changed as desired, or if the layer is formed by sputtering, sputtering of the silicon wafer and graphite wafer can be used to form the target. It can be controlled as desired by changing the area ratio or by changing the mixing ratio of silicon powder and graphite powder and molding the target. The amount of halogen atoms (X) contained in the 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 as electrophotographic image forming members (Samples No. 11-1 to No. 13-
4) were prepared respectively (Table 2). The concentration distribution of germanium atoms in each sample is shown in FIG. 16, and the distribution concentration of nitrogen atoms in each sample is shown in FIG. Each sample obtained in this way was placed in a charging exposure experimental device and corona charged at 5.0KV for 0.3 seconds.
A light image was immediately irradiated. The optical image was generated using a tungsten lamp light source, and a light intensity of 2lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a charged developer (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
Transferred onto transfer paper with 5.0KV corona charging,
All samples had excellent resolution, and clear, high-density images with good gradation reproducibility were obtained. In the above, the same toner image forming conditions were used, except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a tungsten lamp as the light source, and an electrostatic image was formed. When the image quality of the 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 23-4) as electrophotographic image forming members were prepared on a cylindrical Al substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. 15.
were created respectively. (Table 4). The concentration distribution of germium atoms in each sample is shown in FIG. 16, and the distribution concentration of nitrogen 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 Sample Nos. 11-1, 12-1, and 13 of Example 1 except that the conditions for creating the layer () were as shown in Table 5.
Each of the electrophotographic image forming members (Samples No. 11-1-1 to 11-1-8,
12-1-1 to 12-1-8, 13-1-1 to 13-1-
24 samples of 8) were created. Each of the electrophotographic image forming members thus obtained was individually installed in a copying machine, and the electrophotographic image forming members corresponding to each example were prepared under the same conditions as described in each example. For each, the overall image quality of the transferred image was evaluated and the durability was evaluated through repeated and continuous use. Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability after repeated and continuous use. Example 4 Sample No. 11 of Example 1 except that when forming the layer (), the target area ratio of the silicon wafer and graphite was changed and the content ratio of silicon atoms and carbon atoms in the layer () was changed. Each of the image forming members was produced by the same method as in Example 1-1. After repeating the image forming, developing, and cleaning steps approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 7 were obtained. Ta. Example 5 The same procedure as in Example 1 was performed except that when forming the layer (), the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the layer (). Each of the image forming members was prepared in exactly the same manner as Sample No. 12-1. For each of the image forming members thus obtained, the steps up to transfer were repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 8 were obtained. Example 6 When forming the layer (), SiH ₄ gas, SiF ₄ gas,
Images were obtained in exactly the same manner as Sample No. 13-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in the layer () was changed by changing the flow rate ratio of C ₂ H ₄ gas. Each of the forming members was created. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed, 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. 11-1 of Example 1, except that the layer thickness 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
× = Causes image defects

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

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

[Table] 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 configuration diagram for explaining the layer configuration of the photoconductive member of the present invention, and FIGS. 2 to 10 each illustrate the distribution state of germanium atoms in the first layer (). Explanatory diagrams for the purpose, Figures 11 to 14
The figures are explanatory diagrams for explaining the distribution state of nitrogen atoms in the first layer (2), Fig. 15 is a schematic explanatory diagram of the device used in the present invention, Fig. 16,
FIG. 17 is a distribution state diagram showing the distribution state of each atom in each embodiment of the present invention. 100...Photoconductive member, 101...Support, 102
...first layer (), 103...second layer ().

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and 1 to 9.5× with respect to the sum of silicon atoms and silicon atoms.
a photoconductive first layer composed of an amorphous material containing 10 ⁵ atomic ppm germanium atoms; and an amorphous material containing silicon atoms and 1×10 ^-3 to 90 atomic % carbon atoms. Layer thickness made up of material
A photoconductive member for electrophotography, comprising a photoreceptive layer consisting of a second layer with a thickness of 0.003 to 30μ, the photoreceptor layer containing nitrogen atoms, and a nitrogen atom in the layer thickness direction. The distribution concentration of atoms is C(1),
First layer region C(3), C(2) with a layer thickness of 0.003 to 100μ
(1), third layer region with layer thickness 0.003-80μ (3), layer thickness
It has a second layer region (2) of 0.003 to 100μ in this order from the support side, and the distribution concentration C(3) is relative to the sum of silicon atoms, germanium atoms, and nitrogen atoms.
It is said to be 10 atomic ppm to 67 atomic%, and C
(3) A photoconductive member for electrophotography, wherein C(2) and C(1), and at least one of C(1) and C(2) is not 0. 2. The photoconductive member for electrophotography according to claim 1, wherein the first layer contains hydrogen atoms. 3. A photoconductive member for electrophotography according to claims 1 and 2, wherein the first layer contains halogen atoms. 4. The photoconductive member for electrophotography according to claim 1, wherein the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness direction. 5 Claim 1 in which the distribution state of germanium atoms in the first layer is uniform in the layer thickness direction
A photoconductive member for electrophotography as described in 1. 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.