JPH0225175B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to photoconductive members for electrophotography that are sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
Must have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], have absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, have fast photoresponsiveness, and have the desired dark resistance value. 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 made of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there is a need to improve the overall characteristics in terms of usage environment characteristics and stability over time, and there are points 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 repeatedly used for a long period of time, fatigue due to repeated use accumulates and a so-called ghost phenomenon occurs in which an afterimage occurs. In addition, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur. 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 in semiconductor lasers currently in practical use. Furthermore, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that long wavelength light cannot be used effectively. On the other hand, if the amount of irradiated light that reaches the support without being sufficiently absorbed in the photoconductive layer increases, the reflectance of the support itself for the light that passes through the photoconductive layer will decrease. When it is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "blurring" of images. This effect becomes greater as the irradiation spot is made smaller in order to increase the resolution, and is a major problem especially when a semiconductor laser is used as the light source. Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the type, or other atoms are included in order to improve other properties, but the manner in which these constituent atoms are contained is In some cases, problems may arise with 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 is particularly important when the support is
There are issues that need to be resolved in terms of stability over time, as often occurs with drum-shaped supports used in the field of electrophotography. 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
As a result of intensive research and study on a-Si from the viewpoint of its applicability and applicability as a photoconductive member used in electrophotographic image forming members, we found that a-Si has a silicon atom as its base material and a hydrogen atom ( Amorphous materials containing at least one of H) or halogen atoms (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as the generic term " a-Si(H,X)”
The photoconductive member, which is designed and created by specifying the layer structure of the photoconductive member, which has a layer that exhibits photoconductivity, as described below, has outstanding practical advantages. It not only exhibits characteristics, but also surpasses conventional photoconductive members in all respects, especially as a photoconductive member for electrophotography, and
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 resistant to light fatigue. The main object of the present invention is to provide a photoconductive member for electrophotography that has excellent durability, 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 for electrophotography that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and a support, and between each laminated layer, and to provide a dense and stable structural arrangement. An object of the present invention is to provide a high quality photoconductive member for electrophotography. Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member for electrophotography, which has sufficient performance and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere. Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a photoconductive member for electrophotography that has high signal-to-noise ratio characteristics and good electrical contact with a support. The photoconductive member for electrophotography of the present invention (hereinafter simply referred to as "photoconductive member") includes a support for the photoconductive member, and is disposed on the ^support ,
A first layer region (G) with a layer thickness of 30 Å to 50 μ consisting of an amorphous material containing ppm germanium atoms and a layer thickness consisting of an amorphous material containing silicon atoms (but not germanium atoms) 0.5~90μ second
A first layer exhibiting photoconductivity having a layer thickness of 1 to 100 μm and having a layer structure in which a layer region (S) is provided in order from the support side, and a silicon atom and 1×10 ⁻³ to 90 atomic%
layer thickness composed of an amorphous material containing carbon atoms of
and a second layer with a thickness of 0.003 to 30μ, the first layer region (G) contains a substance controlling conductivity of 0.01 to 5×10 ⁴ atomic ppm, and the first layer contains It is characterized by containing 0.001 to 50 atomic% of nitrogen atoms. 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, and it has high sensitivity and 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. In addition, the photoconductive member of the present invention has a first layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously applied at high speed for a long time. Can be used repeatedly. Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse. Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings. FIG. 1 is a schematic diagram schematically showing the layer structure 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 second layer () 103 having a free surface 106 on one end face. The first layer ( ) 102 is the support 1
a-Si containing germanium atoms from the 01 side
(H,X) (hereinafter abbreviated as “a-SiGe(H,X)”), a first layer region (G) 104;
It has a layer structure in which a second layer region (S) 105 made of a-Si(H,X) and having photoconductivity is laminated in order. The germanium atoms contained in the first layer region (G) 104 are continuous and uniform in the layer thickness direction of the first layer region (G) 104 and in the in-plane direction parallel to the surface of the support 101. It is contained in the first layer region (G) 104 in a distributed manner. In the photoconductive member 100 of the present invention, at least the first layer region (G) 104 contains a substance (C) that controls conduction properties, and the first layer region (G) 104 has a desired amount of The conduction properties are given. In the present invention, the first layer region (G) 104
The substance (C) that controls the conduction properties contained in
It may be uniformly contained in the entire layer region of the first layer region (G) 104, and the first layer region (G) 1
It may be contained so as to be unevenly distributed in some layer regions of 04. Substance (C) that controls conduction properties in the present invention
When the substance (C) is contained in the first layer region (G) so as to be unevenly distributed in a part of the layer region (G), the layer region (PN) in which the substance (C) is contained
is preferably provided as an end layer region of the first layer region (G). In particular, when the layer region (PN) is provided as the end layer region on the support side of the first layer region (G), the substance (C) contained in the layer region (PN) By appropriately selecting the type and its content as desired, it is possible to effectively prevent charge of a specific polarity from being injected from the support into the first layer (2). In the photoconductive member of the present invention, a substance (C) capable of controlling conduction properties is contained in the first layer region (G) constituting a part of the first layer (2).
As mentioned above, evenly throughout the layer region (G),
Alternatively, the substance (C) is contained so as to be unevenly distributed in the layer thickness direction, and further, the substance (C) is also contained in the second layer region (S) provided on the first layer region (G). It's a good thing. When the substance (C) is contained in the second layer region (S), the type, amount and content of the substance (C) contained in the first layer region (G) are determined. Depending on the method, the type and amount of the substance (C) to be contained in the second layer region {S), and the manner in which it is contained are appropriately determined. In the present invention, when the substance (C) is contained in the second layer region (S), preferably the substance (C) is contained in the layer region including at least the contact interface with the first layer region (G). It is desirable to include a substance. In the present invention, the substance (C) may be uniformly contained in the entire layer region of the second layer region (S), or may be uniformly contained in a part of the layer region. is also good. When both the first layer region (G) and the second layer region (S) contain a substance (C) that controls conduction characteristics, the substance (C) in the first layer region (G) It is desirable that the layer region containing the substance (C) and the layer region containing the substance (C) in the second layer region (S) be in contact with each other. Further, the substance (C) contained in the first layer region (G) and the second layer region (S) is contained in the first layer region (G) and the second layer region (S). They may be of the same type or different types, and their content may be the same or different in each layer region. However, in the present invention, if the substance (C) contained in each layer region is the same in both, the content in the first layer region (G) is increased sufficiently. Alternatively, it is preferable that substances (C) of different types with different electrical characteristics are contained in each desired layer region. In the present invention, at least the first layer ()
By containing a substance (C) that controls the conduction properties in the first layer area (G) constituting the layer area, the layer area containing the substance C [first layer area (G)
The conduction properties of the layer (which may be part or all of the layer region) can be arbitrarily controlled as desired, but such materials include the so-called
Examples of impurities in the semiconductor field include impurities, and in the present invention, for a-SiGe (H,
Examples include a p-type impurity that provides p-type conduction characteristics, and an n-type impurity that provides n-type conduction characteristics.
Specifically, p-type impurities include atoms belonging to Group 3 of the periodic table (Group atoms), such as B (boron),
There are Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. As n-type impurities, atoms belonging to group of the periodic table (group atoms),
For example, P (phosphorus), As (arsenic), Sb (antimony),
Bi (bismuth), etc., and particularly preferably used are P and As. In the present invention, the content of the substance (C) that controls conduction properties in the layer region (PN) is determined by the conduction properties required for the layer region (PN) or the layer region (PN). When PN) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, the relationship with other layer regions provided in direct contact with the layer region (PN) and the characteristics at the contact interface with the other layer regions is also considered, and the material controlling the conduction characteristics is determined. The content is selected as appropriate. 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
It is desirable that the amount is 5×10 ³ atomic ppm. In the present invention, the content of the substance (C) that controls conduction characteristics in the layer region (PN) containing the substance (C) is preferably 30 atomic ppm.
As described above, by setting the concentration to more preferably 50 atomic ppm or more, optimally 100 atomic ppm or more, for example, when the substance to be contained is the above-mentioned p-type impurity, the free surface of the second layer () is It is possible to effectively prevent the injection of electrons from the support side into the first layer () when subjected to polar charging treatment, and when the substance to be contained is the above n-type impurity. can effectively prevent the injection of holes from the support side into the first layer () when the free surface of the second layer () is subjected to polar charging treatment. In the above case, as mentioned above, in the layer region (Z) excluding the layer region (PN),
The layer region (PN) may contain a substance (C) that controls conduction characteristics with a conduction type polarity different from the conduction type polarity of the substance (C) that controls conduction characteristics contained in the layer region (PN), or The substance (C) that controls conductivity and has the same conductivity type may be contained in an amount much smaller than the actual amount contained in the layer region (PN). In such a case, the content of the substance controlling the conduction characteristics contained in the layer region (Z) may be determined as desired depending on the polarity and content of the substance contained in the layer region (PN). Therefore, it should be determined appropriately, but preferably 0.001 to 1000 atomic
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity is included in the first layer (). It is also possible to provide a layer region containing a substance in direct contact with a layer region, and to provide a so-called depletion layer in this contact region. 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. Thus, a depletion layer can be provided. In the present invention, germanium atoms are not contained in the second layer region (S) provided on the first layer region (G), and the first layer does not contain germanium atoms in such a layer structure. By forming parentheses, 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. In addition, the distribution state of germanium atoms in the first layer region (G) is such that germanium atoms are continuously distributed in the entire layer region, so that the distribution state of germanium atoms in the first layer region (G) and the second layer region is different. The first layer region (S) has excellent affinity with the first layer region (S), and when a semiconductor laser or the like is used, the second layer region (S) absorbs almost no light on the long wavelength side. Substantially complete absorption can be achieved in the layer region (G), and interference due to reflection from the support surface can be prevented. Further, in the photoconductive member of the present invention, each of the amorphous materials constituting the first layer region (G) and the second layer region (S) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface. In the present invention, the content of germanium atoms contained in the first layer region (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1. ~10×
¹⁰⁵ atomic ppm, preferably 100 to 9.5×
10 ⁵ atomic ppm, optimally 500 to 8×10 ⁵ atomic
Preferably in ppm. In the present invention, the layer thickness of the first layer region (G) and the second layer region (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the photoconductive member to ensure that the photoconductive member formed has the desired properties. In the present invention, the layer thickness of the first layer region (G)
T _B is preferably 30 Å to 50 μ, more preferably 40
It is desirable that the thickness be 50 Å to 30 μ, most preferably 50 Å to 30 μ. Further, the layer thickness T of the second layer region (S) is preferably 0.5 to 90μ, more preferably 1 to 80μ, and optimally 2 to 50μ. The sum (T _B +T) of the layer thickness T _B of the first layer region (G) and the layer thickness T of the second layer region (S) is based on the characteristics required for both layer regions and the first layer. () It is appropriately determined as desired when designing the layers of the photoconductive member, based on the mutual organic relationship with the properties required for the whole. In the photoconductive member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
It is desirable that appropriate numerical values be selected for each so as to satisfy the relationship T _B /T≦1. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦08 is satisfied. In the present invention, the content of germanium atoms contained in the first layer region (G) is 1×
In the case of 10 ⁵ atomic ppm or more, it is desirable that the layer thickness T _B of the first layer region (G) be as thin as possible, preferably 30μ or less, more preferably
It is desirable that the thickness be 25μ or less, optimally 20μ or less. In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, as well as improving the adhesion between the support and the first layer Nitrogen atoms are contained in the layer ( ). The nitrogen atoms contained in the first layer () are
It may be evenly contained in the entire layer region of the first layer (), or it may be contained and unevenly distributed only in a part of the layer region of the first layer (). In addition, the distribution state of nitrogen atoms is such that the distribution concentration C(N) is
The first layer () may be uniform or non-uniform in the layer thickness direction. In the present invention, when the main purpose of the layer region (N) containing nitrogen atoms provided in the first layer () is to improve photosensitivity and dark resistance,
If it is provided so as to occupy the entire layer area of the first layer () and the main purpose is to strengthen the adhesion between the support and the first layer (), the first layer It is provided so as to occupy the end layer area on the side of the support in parentheses. In the former case, the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. It is desirable that the amount be relatively large in order to achieve this goal. In addition, in order to achieve both the former and the latter at the same time, a relatively high concentration is distributed on the support side, and a relatively low concentration is distributed on the second layer () side of the first layer (). Or, in the layer region (N), the distribution state of nitrogen atoms is such that nitrogen atoms are not actively included in the region on the second layer () side of the first layer (). It should be formed as follows. 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. It can be selected as appropriate depending on the organic relationship. In addition, when another layer region is provided in direct contact with the layer region (N), the characteristics of the other layer region and the characteristics at the contact surface with the other layer region are determined. The content of nitrogen atoms is appropriately selected taking into consideration the relationship. The amount of nitrogen atoms contained in the layer region (N) 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~
It is desirable that it be 40 atomic%, optimally 0.003 to 30 atomic%. In the present invention, 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 _N
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 _N 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 preferably 30 atomic% or less, more preferably 30 atomic% or more.
It is desirable that it be 20 atomic % or less, optimally 10 atomic % or less. 2 to 10 show typical examples of the distribution state of nitrogen atoms contained in the layer region (N) of the photoconductive member in the present invention in the layer thickness direction. In Figures 2 to 10, the horizontal axis represents the distribution concentration C of nitrogen atoms, the vertical axis represents the layer thickness of the layer region (N), and _tB represents the position of the end surface of the layer region (N) on the support side. , t _T indicates the position of the end surface of the layer region (N) on the side opposite to the support side. That is, the layer region (N) containing nitrogen atoms is formed as a layer from the t _B side toward the t _T side. FIG. 2 shows a first typical example of the distribution state of nitrogen atoms contained in the layer region (N) in the layer thickness direction. In the example shown in FIG. 2, from the interface position _tB where the surface where the layer region (N) containing nitrogen atoms is formed and the surface of the layer region ( _N ) contact, the nitrogen Layer region (N) where nitrogen atoms are formed while the atomic distribution concentration C takes a constant value of _C1
The concentration C2 is higher than the concentration C2 than the position _t1 , and the interface position _tT is higher than the concentration _C2 .
It has been gradually and continuously reduced until . At the interface position _tT , the distribution concentration C of nitrogen atoms is _C3 . In the example shown in FIG. 3, the distribution concentration C of _the contained nitrogen atoms gradually and continuously decreases from the concentration C ₄ until reaching the position t _T from the position _t
The distribution state is formed so that the concentration is _C5 . In the case of Fig. 4, the distribution concentration C of nitrogen atoms from position t _B to position t ₂ is a constant value of concentration C ₆ ,
The distribution concentration C is gradually and continuously reduced between position _t2 and position _tT , and the distribution concentration C is substantially zero at position _tT (here, substantially zero means that the amount is below the detection limit). ). In the case of FIG. 5, the distribution concentration C of nitrogen atoms is
From position t _B to position t _T , the concentration C ₈ is gradually decreased continuously, and becomes substantially zero at position t _T . In the example shown in FIG. 6, the nitrogen atom distribution concentration C is constant at a concentration _C9 between the position _tB and the position _t3 , and the concentration _C10 at the position _tT . 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 nitrogen atoms decreases linearly from the concentration C ₁₄ to substantially zero. In FIG. 9, from position _tB to position _t5 , the distribution concentration C of nitrogen atoms is lower than the concentration _C15 .
An example is shown in which the concentration is linearly decreased to C ₁₆ and the concentration C ₁₆ is kept at a constant value between position t ₅ and position t _T. In the example shown in FIG. 10, the distribution concentration C of nitrogen atoms is a concentration C ₁₇ at position t _B , and at first it gradually decreases from this concentration C ₁₇ until reaching position t ₆ , and then at t ₆ it decreases slowly. Near the position, the concentration decreases rapidly to a concentration _C18 at the position _t6 . Between position t ₆ and position t ₇ , the concentration decreases rapidly at first, and then slowly decreases to C ₁₉ at position t ₇ , and between position t ₇ and t ₈ , is gradually reduced 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 nitrogen atoms contained in the layer region (N) in the layer thickness direction, in the present invention, on the support side , the layer region (N) has a portion where the distribution concentration C of nitrogen atoms is high, and the distribution state of nitrogen atoms has a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. It is set in. In the present invention, the layer region (N) containing nitrogen atoms constituting the first layer () is a localized region containing relatively high concentration of nitrogen atoms toward the support side, as described above. (B) is desirable, and in this case, the adhesion between the support and the first layer () can be further improved. The above localized region (B) can be explained using the symbols shown in FIGS. 2 to 10, by 5μ from the interface position _tB .
It is desirable that it be established within In the present invention, the localized region (B) may be the entire layer region (L _T ) up to 5μ thick from the interface position t _B , or may be a part of the layer region (L _T ). In some cases, it may be done. Whether the localized region is a part or all of the layer region (L _T ) is determined as appropriate depending on the characteristics required of the first layer () to be formed. In the localized region (B), the maximum value Cmax of the distribution concentration of nitrogen atoms is preferably 500 atomic ppm as the distribution state of nitrogen atoms contained therein in the layer thickness direction.
As described above, it is desirable that the layers be formed in such a manner that a distribution state can be obtained, more preferably at least 800 atomic ppm, and most preferably at least 1000 atomic ppm. That is, in the present invention, the layer region (N) containing nitrogen atoms has the maximum distribution concentration within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the structure be formed so that Cmax exists. In the present invention, 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 present invention, in order to form the first layer region (G) composed of a-SiGe (H, It is made by vacuum deposition method. For example, in order to form the first layer region (G) 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, A-SiGe (H, ) may be formed. In addition, when forming by sputtering, a target composed of Si or a combination of the target and Ge is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using two of the configured targets or a mixed target of Si and Ge, source gas for supplying Ge diluted with diluent gas such as He or Ar as necessary.
If necessary, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas, and the raw material for supplying Ge is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas. The target may be sputtered while controlling the gas flow rate according to a desired rate of change curve. In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Law (EB Law)
It can be carried out in the same manner as in the sputtering method, except that the evaporated material is heated and evaporated by a method such as the like, the evaporated material is passed through a desired gas plasma atmosphere, and the 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 , GeH 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. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be gasified. 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 , BlF 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 BiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing a halogen atom, the material gas that can supply Si together with the material gas for supplying Ge is used. The first layer region (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer region (G) containing halogen atoms according to the glow discharge method, basically:
For example, silicon halide, which is the raw material gas for Si supply, germanium hydride, which is the raw material gas for Ge supply, and gases such as Ar, H ₂ , He, etc. are mixed at a predetermined mixing ratio and gas flow rate. A first layer region (G) is deposited on the desired support by introducing a first layer region (G) into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases. G), but in order to make it easier to control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases. A layer may be formed by doing so. 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 both the sputtering method and the ion plating method, in order to introduce halogen atoms into the layer to be formed, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I and other hydrogenated germanium halides, halides containing hydrogen atoms as one of their constituents, GeF ₄ , GeCl ₄ , GeBr ₄ ,
Germanium halides such as GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances may also be mentioned as useful starting materials for forming the first layer region (G). I can do it. Halides containing hydrogen atoms in these substances are introduced into the layer when forming the first layer region (G), and at the same time hydrogen atoms are extremely effective in controlling electrical or photoelectric properties. Since halogen is also introduced, it is used as a suitable raw material for halogen introduction in the present invention. In order to structurally introduce hydrogen atoms into the first layer region (G), in addition to the above, H ₂ , SiH ₄ ,
Silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or a germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H _Ten ,
Germanium hydride such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ , etc. and silicon or silicon compound for supplying Si coexist in the deposition chamber and discharge is performed. This can also be done by causing In a preferred example of the present invention, the amount of halogen atoms (H) contained in the first layer region (G) of the photoconductive member to be formed, or the amount of halogen atoms (X), or the amount of hydrogen atoms and halogen atoms The sum of the quantities (H+
X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 30 atomic%, optimally 01 to 25 atomic%
It is preferable to set it as %. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the support, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms (X) can be controlled. What is necessary is to control the amount of the starting material used, introduced into the deposition system, the discharge power, etc. In the present invention, in order to form the second layer region (S) composed of a-Si(H,X), the starting material () for forming the first layer region (G) described above is The starting material (starting material for forming the second layer region (S)) excluding the starting material that becomes the raw material gas for supplying Ge is used to form the first layer region (G).
It can be carried out according to the same method and conditions as in the case of forming. That is, in the present invention, to form the second layer region (S) composed of a-Si(H,X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. This is accomplished by using a vacuum deposition method. For example, by using the glow discharge method, a second
In order to form the layer region (S), basically, in addition to the above-mentioned raw material gas for supplying Si that can supply silicon atoms (Si), a gas for introducing hydrogen atoms (H) or/and A raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a-
A layer made of Si(H,X) may be formed. or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into the deposition chamber for sputtering. In the layer region (PN) constituting the first layer (), a substance (C) that controls conduction properties, for example, a group atom or a group atom, is structurally introduced to contain the substance (C). To form a layer region (PN) in which a first layer (PN) is formed, a starting material for introducing a group atom or a starting material for introducing a group atom is introduced into a deposition chamber in a gaseous state during layer formation. ) may be introduced together with other starting materials for forming. As a starting material for such introduction of group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group atom include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ , BCl ₃ ,
Examples include boron halides such as 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 ,
AaCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₅ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. In the 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 using the glow discharge method to form the layer region (N), a material for introducing nitrogen atoms is added to the starting material selected from among the starting materials for forming the first layer (N) as desired. Starting materials are added. As such a starting material for introducing nitrogen atoms, most gaseous substances having at least elemental atoms as constituent 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. These can also be used by mixing them in a desired mixing ratio. 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 nitrogen atoms (N). 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. Gaseous or gasifiable nitrogen such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), etc. , nitrides, azides, and other nitrogen compounds. 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 (O) 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 (O) into the layer region (N) include oxygen (O ₂ ), ozone (O ₃ ), nitrogen monoxide (NO), and nitrogen dioxide (NO ₂ ), nitrogen monooxide (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 ) , lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H). etc. can be mentioned. To form a layer region (N) containing nitrogen atoms by sputtering, a single crystal or polycrystalline Si wafer or a Si ₃ N ₄ wafer or a Si and
This can be carried out by sputtering a wafer containing a mixture of Si ₃ N ₄ 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 sputtering deposition chamber, 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. or at least a hydrogen atom (H) or/and a halogen atom (X)
This is done by sputtering in a gas atmosphere containing as constituent atoms. As the raw material gas for introducing nitrogen 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) of nitrogen atoms contained in the layer region (N) is ) in the layer thickness direction to form a layer region (N) having a desired depth pofile, in the case of glow discharge,
This is accomplished by introducing a starting material gas for introducing nitrogen atoms whose distributed concentration C(N) is to be changed into the deposition chamber while appropriately changing the gas flow rate according to the 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 some commonly used method, such as manually or by using an externally driven motor. At this time,
The rate of change in the flow rate does not have to be linear, and a desired content rate curve can also be obtained by controlling the flow rate according to a pre-designed rate-of-change curve using, for example, a microcomputer. 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 form a desired depth profile of nitrogen atoms in the layer thickness direction by changing the depth profile in the layer thickness direction, first, as in the case of the glow discharge method, the starting point for introducing nitrogen 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 Si ₃ N ₄ is used, this can be achieved by changing the mixing ratio of Si and Si ₃ N ₄ in advance in the thickness direction of the target. Ru. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the second layer region (S) constituting the first layer () to be formed,
Or the sum of the amounts of hydrogen atoms and halogen atoms (H+X)
is preferably 1 to 40 atomic %, more preferably 5 to 30 atomic %, and optimally 5 to 25 atomic %. 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,X) _{1-y can} be performed by glow discharge method, sputtering method, ion plantation method, ion plating method, This is done by an electro beam method or the like. These manufacturing methods are selected and adopted as appropriate based on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The advantage is that it is relatively easy to control the manufacturing conditions for manufacturing the photoconductive member, and the second layer () in which carbon atoms and halogen atoms are created together with silicon atoms.
The glow discharge method or the sputtering method is preferably employed because of the advantages such as ease of introduction into the interior. 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. In order to form the second layer containing () by the glow discharge method, the raw material gas for forming a-(Si _x C _1-x )y(H,X) _1-y is diluted as necessary. The mixture is mixed with a gas 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.
What is necessary is to deposit a-(Si _x C _1-x )y(H,X) _1-y on the first layer ( ) already formed on the support. In the present invention, a-(Si _x C _1-x )y(H,X) _1-
The raw material gas for forming _y is a gaseous substance or gasified substance whose constituent atoms are at least one of silicon atoms (Si), carbon atoms (C), hydrogen atoms (H), and halogen atoms (X). Most of the gasified materials available can be used. When using a raw material gas containing Si as one of Si, C, H, and X, for example, a raw material gas containing Si and a raw material gas containing C, as necessary. Depending on the situation, it is used by mixing with a raw material gas containing H as a constituent atom or/and a raw material gas containing X as a constituent atom at a desired mixing ratio, or with a raw material gas containing Si as a constituent atom and a raw material gas containing C and H as a constituent atom. A raw material gas containing atoms and/or a raw material gas containing X as constituent atoms are also mixed at a desired mixing ratio, or
Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing Si, C and H as constituent atoms, or Si,
A raw material gas having three constituent atoms, C and X, can be mixed and used. 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- _C4H10 ) _, pentane ( _C5H12 ), ethylene hydrocarbons include ethylene ( _C2H4 ), propylene ( _C3H6 ) _, butene- ₁ ( _{C4H8 )} , butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), Butyne (C ₄ H ₆ ), halogen gases such as fluorine, chlorine, bromine, and iodine as single halogens, FH, HI, HCl, HBr as hydrogen halides, BrF, ClF, ClF ₃ , ClF as interhalogen compounds ₅ , _BrF5 ,
BrF ₃ , IF ₇ , IF ₅ , ICl, IBr, silicon halides include SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br, SiCl ₂ Br ₂ ,
SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₃ Cl,
SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , silicon hydride such as SiH ₄ , Si ₂ H ₈ , Si ₄ H ₁₀ , etc.
You can list the types, etc. 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 ,
Si(C ₂ H ₅ ) ₄ , especially alkyl silicide, SiCl(CH ₃ ) ₃ ,
Silane derivatives such as halogen-containing alkyl silicides such as SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These second layer () 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. ₂ Cl ₂ , SiCl ₄ or SiH ₃ Cl, etc. at a predetermined mixing ratio are introduced in a gaseous state into an apparatus for forming the second layer () to generate a glow discharge _. 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 single crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C. 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 having the desired properties depending on the purpose is used. -(Si _x C _1-x )y(H,X) _1-y is formed,
The selection of the production conditions is made strictly according to desire. 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 the 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 it will have a certain degree of resistance to the irradiated light. As an amorphous material with sensitivity, a-(Si _x C _1-x )y(H,
X) _1-y is created. 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. The temperature is preferably 20 to 400°C, more preferably 50 to 350°C, and optimally 100 to 300°C. The glow discharge method is used to form the second layer () because it is relatively easy to finely control the composition ratio of the atoms that make up the layer and control the layer thickness compared to other methods. Adoption of the sputtering method is advantageous, but when forming the second layer () using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, a−(Si _x
C _1-x )y(H,X) This is one of the important factors that influences the characteristics of _1-y . The discharge power conditions for effectively producing a-(Si _x C _1-x ) _y (H, Preferably 10~300W, more preferably 20~
250W, optimally 50-200W is desirable. 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 () in the photoconductive member of the present invention is the same as the production conditions of the second layer (), and the amount of carbon atoms contained in the second layer () is determined such that the desired characteristics that achieve the object of the present invention are obtained. is an important factor for 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-
The amorphous material indicated by _y can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-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 _b
C _1-b ) _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 1 × 10 ^-3 ~
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-Si _a C _1-a above, a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99,
Optimally it is between 0.25 and 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 1 to 80 atomic %. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 40 atomic%.
It is desirable that the hydrogen content be 35 atomic%, most preferably 5 to 30 atomic%, and the photoconductive member formed when the hydrogen content is in this range is excellent and can be sufficiently applied in practice. be. 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 to
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 preferably 90 atomic%, optimally 10 to 80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, more preferably 1 to 20 atomic%.
It is desirable that the halogen atom content be 18 atomic %, most preferably 2 to 15 atomic %, and photoconductive members prepared with a halogen atom content in this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably
It is desirable that it be 19 atomic % or less, more preferably 13 atomic % or less. That is, d of the previous a-(Si _d C _1-d ) _e (H,X) _1-e ,
If expressed as e, d is preferably 0.1~
0.99999, more preferably 0.1-0.99, optimally 0.15
~0.9, e is preferably 0.8~0.99, more preferably
It is desirable that it be between 0.82 and 0.99, most preferably between 0.85 and 0.98. The numerical 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 required for each layer () in relation to the thickness of the first layer (). It is necessary to appropriately determine the desired characteristics based on the organic relationship 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 it 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, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinylchloride, polyvinylidene chloride, polystyrene, polyamide, glass ceramic paper, etc. are usually used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a forming member, it is desirable to have an endless belt shape or a cylindrical shape 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
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. 11 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the diagram include
The raw material gas for forming the photoconductive member of the present invention is sealed, for example, 110
2 is SiH ₄ gas diluted with He (99.999% purity,
Hereinafter, it will be abbreviated as SiH ₄ /He. ) cylinder, 1103 is He
_GeH4 gas diluted with (purity 99.999% or less)
Abbreviated as GeH ₄ /He. ) cylinder, 1104 is B ₂ H ₆ gas diluted with He (purity 99.99%, hereinafter referred to as B ₂ H ₆ /
Abbreviated as He. ) cylinder, 1105 is NH ₃ gas (purity 99.999%) cylinder, 1106 is H ₂ gas (purity
99.999%) cylinder. In order to flow these gases into the reaction chamber 1101, the valves of gas cylinders 1102 to 1106, 1
122-1126, make sure that the leak valve 1135 is closed, and also check that the inflow valve 1112
~1116 After confirming that the outflow valves 1117 to 1121 and 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 the first layer () on the cylindrical substrate 1137, SiH 4 /He gas from the gas cylinder 1102, SiH ₄ /He gas from the gas cylinder 1102;
GeH ₄ /He gas from 103, gas cylinder 1104
From B ₂ H ₆ /He gas, gas cylinder 1105
Open valves 1122 to 1125 to supply NH ₃ gas and set the pressure at outlet pressure gauges 1127 to 1130 to 1Kg/cm ²
, gradually open the inflow valves 1112 to 1115, and then open the mass flow controllers 1107 to 1115 gradually.
1110 to have husbands and husbands flow in. Subsequently, the outflow valves 1117 to 1120 and the auxiliary valve 1132 are gradually opened to allow the husband's gas to flow into the reaction chamber 1101. At this time, the SiH ₄ /He gas flow rate and
GeH ₄ /He gas flow rate and B ₂ H ₆ /He gas flow rate and NH ₃
The outflow valves 1117 to 1120 are adjusted so that the ratio with the gas flow rate becomes a desired value, and the reaction chamber 11
01 so that the pressure reaches the desired value
Adjust the opening of the main valve 1134 while checking the reading of 36. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the heating heater 1138, the power supply 1137
140 is set to a desired power to generate a glow discharge in the reaction chamber 1101, and the glow discharge is maintained for a desired time to form boron atoms (B) and nitrogen atoms (N) in a desired layer thickness on the substrate 1137. Contains a-SiGe
A layer region (B,N) composed of (H,X) is formed. At the stage when the layer regions (B, N) are formed to a desired layer thickness, the outflow valves 1118, 1119, 11
20 on the layer regions (B, N) by maintaining the glow discharge for the desired time according to the same conditions and procedures, except for completely closing each of the layers 20 and changing the discharge conditions as necessary. A layer region (S) composed of a-Si (H, ) is completed. During the formation of the first layer (2), the flow of B ₂ H ₆ /He gas or NH ₃ gas into the deposition chamber is stopped after a desired period of time has elapsed after the start of the layer formation. Therefore, the thicknesses of the layer region (B) containing boron atoms and the layer region (N) containing nitrogen atoms can be arbitrarily controlled. Also, according to a desired rate of change curve, the deposition chamber 110
By controlling the gas flow rate of NH ₃ gas to the layer region (N), the distribution state of nitrogen atoms contained in the layer region (N) can be formed as desired. When halogen atoms are contained in the first layer (), glow discharge may be generated by further adding, for example, SiF ₄ gas to the above gas. In addition, when containing halogen atoms instead of hydrogen atoms in the first layer (), the above
Instead of SiH ₄ /He gas and GeH ₄ /He gas,
SiF ₄ /He gas and GeF ₄ /He gas may be used. 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 ₄ gas to this and form the second layer () in the same manner as above. It is accomplished by Needless to say, when forming each layer, all the outflow valves except for the necessary gas outflow valves are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 1101. In order to avoid gas remaining in the gas piping leading from the outflow valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, and the auxiliary valve 1 is closed.
132 and 1133, and open the main valve 1134.
If necessary, fully open the system and evacuate the system to high vacuum. For example, in the case of glow discharge, the amount of carbon atoms contained in the second layer (2) is determined by adjusting the flow rate ratio of SiH ₄ gas and C ₂ H ₄ gas introduced into the reaction chamber 1101 as desired. Alternatively, when forming a layer by sputtering, when forming the target, change the sputter area ratio of the silicon wafer and graphite wafer, or change the mixing ratio of silicon powder and graphite powder to form the target. It can be controlled as desired by molding. The amount of halogen atoms (X) contained in the second layer () is determined when the raw material gas for introducing halogen atoms, for example SiF ₄ gas, is
This is achieved by adjusting the flow rate when introduced into the interior. 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 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Table 1 to obtain an electrophotographic image forming member. The image forming member thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately irradiated with a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the imaging member surface by cascading a chargeable developing agent (including toner and carrier) over the imaging member surface. the toner image on the imaging member;
When transferred onto transfer paper using a 4.0kV Kona charge, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Example 2 Using the manufacturing apparatus shown in FIG. 11, layers were formed in the same manner as in Example 1 except that the conditions shown in Table 2 were used to obtain an electrophotographic image forming member. Regarding the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1 except that the charge polarities of the charge polarity phenomenon agents were reversed. Clear image quality was obtained. Example 3 Layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Table 3 were changed using the manufacturing apparatus shown in FIG. 11 to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 4 In Example 1, GeH ₄ /He gas and
Electrophotographic image formation was carried out in the same manner as in Example 1, except that the content of germanium atoms contained in the first layer was changed as shown in Table 4 by changing the gas flow rate ratio of SiH ₄ /He gas. Each member was created. Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 4 were obtained. Example 5 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 5. For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 5 were obtained. Example 6 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical Al substrate under the conditions shown in Tables 6 to 8 to produce each electrophotographic image forming member (sample No. 601, 602, 603) were obtained. Each of the image forming members thus obtained was placed in a charging exposure experimental device, corona charged at 5.0 kV for 0.3 seconds, and immediately exposed to a light image. The optical image was generated using a tungsten lamp light source, and a light intensity of 2 lux·sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on each imaging member surface by cascading a chargeable developing agent (including toner and carrier) over each imaging member surface. When the toner images on each image forming member were transferred onto transfer paper using Kona charging at 5.0 kV, clear, high-density images with excellent resolution and good gradation reproducibility were obtained. Example 7 Using the manufacturing apparatus shown in FIG. 11, layer formation was carried out in the same manner as in Example 1 except that the conditions shown in Tables 9 and 10 were used to form electrophotographic image forming members ( Sample Nos. 701 and 702) were obtained. For each of the image forming members thus obtained,
When an image was formed on a transfer paper under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 8 Using the manufacturing apparatus shown in FIG. 11, layers were formed in the same manner as in Example 1 except that the conditions shown in Tables 11 to 15 were used to form each electrophotographic image forming member (sample). No. 801 to 805) were obtained. When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained. Example 9 In Example 1, the light source was an 810 nm GaAs semiconductor laser (10 mW) instead of the tungsten lamp.
Example 1 was carried out under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using
When the image quality of the toner-transferred image was evaluated using an electrophotographic image forming member prepared under the same conditions as described above, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained. Example 10 Table 1 of Example 1 and Example 6 except that the conditions for creating the second layer () were as shown in Table 16.
Each of the electrophotographic image forming members (sample No. 12
-401~12-408, 12-701~12-708, 12-801~
12−808 72 samples) 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 17 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 11 The same procedure as Example 1 was performed except that when forming the second layer (), the target area ratio between 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 imaging members was made in a similar manner. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated approximately 50,000 times, and the images were evaluated.
The results shown in the table were obtained. Example 12 When forming the second layer (), SiH ₄ gas and C ₂ H ₄
Each of the image forming members was produced in exactly the same manner as in Example 1, except that the content ratio of silicon atoms and carbon atoms in the second layer (2) was varied by changing the gas flow rate ratio. After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each line forming member thus obtained, image evaluation was performed.
The results shown in the table were obtained. Example 13 When forming the second layer (), SiH ₄ gas, SiF ₄
An image forming member was prepared in exactly the same manner as in Example 1, except that the content ratio of silicon atoms and carbon atoms in the second layer () was changed by changing the flow rate ratio of gas and C ₂ H ₄ gas. I created each of them. 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 20 were obtained. Example 14 Each of the imaging members was made in exactly the same manner as in Example 1, except that the layer thickness of the second layer (2) was changed. Image formation, development, as described in Example 1
The cleaning process was repeated to obtain the results shown in Table 21.

【table】

【table】

【table】

【table】

[Table] ◎: Excellent ○: Good

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

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【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...
Approximately 200℃ Germanium atom (Ge)-free layer...
Approximately 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 nitrogen atoms in the husband layer region (N). FIG. 11 is a schematic explanatory diagram of the apparatus used to produce the photoconductive member of the present invention in Examples. 100...Photoconductive member, 101...Support, 1
02...First layer (), 103...Second layer (), 104...First layer region (G), 105...
...Second layer region (S).

Claims (1)

[Scope of Claims] 1. A support for a photoconductive member for electrophotography, and a layer thickness composed of an amorphous material disposed on the support and containing germanium atoms in an amount of 1 to 10×10 ⁵ atomic ppm. A first layer region (G) with a thickness of 30 Å to 50 μ and a second layer region (S) with a layer thickness of 0.5 to 90 μ made of an amorphous material containing silicon atoms (but not containing germanium atoms) are on the support side. a first layer exhibiting photoconductivity with a layer thickness of 1 to 100 μm and having a layer structure provided in this order;
A layer with a thickness of 0.003~ made of an amorphous material containing silicon atoms and 1×10 ^-3 ~90 atomic% carbon atoms.
30 μm of the second layer, and the first layer region G
The first layer contains a substance controlling conductivity of 0.01 to 5×10 ⁴ atomic ppm, and the first layer contains a substance controlling conductivity of 0.01 to 5×10 4 atomic ppm.
A photoconductive member for electrophotography characterized by containing 50 atomic% of nitrogen atoms. 2. The photoconductive member for electrophotography according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. 3. For electrophotography according to claim 1 or 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Photoconductive member. 4. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table. 5. The photoconductive member for electrophotography according to claim 1, wherein the substance controlling the conductivity is an atom belonging to Group 3 of the periodic table.