JPS60101542A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain stable performance, excellent photosensitivity on a long wavelength side and good durability by consisting of a photoreceptive layer of the 1st conductive layer composed of a-SiGe and the 2nd layer composed of a-SiC, incorporating N in the 1st layer and forming specifically distributed densities in the layer thickness direction. CONSTITUTION:A photoconductive layer has a base 101 and a photoreceptive layer consisting of the 1st layer I 102 constituted of a-SiGe and exhibiting photoconductivity and the 2nd layer II103 constituted of a-SiC. N atom is incorporated into the layer I 102 and said layer has the 1st layer region 104, the 3rd layer region 106 and the 2nd layer region 105 in which the densities distributed in the layer thickness direction thereof are made to respectively C1, C2, C3. The C3 does not independently attain the max. value and when any among C1-3 is 1 or 0, the other two are not 0 and are not equal. The H atom or halogen atom is incorporated into the layer I 102 and the distribution condition of Ge may be uniform or nonuniform. A material governing conductivity, for example, the atom of the III group or V group is incorporated. Electrical, optical and photoconductive characteristics such as dark resistance, photosensitivity, photoresponsiveness, environmental characteristics, stability with age, etc. are improved overall by the above-mentioned constitution.

Description

[Detailed description of the invention]

The present invention is directed to light (here, light in a broad sense, ultraviolet light s>p, a
The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as r-visible light, infrared light, X-rays, r-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 and has a photocurrent (Ip) of 8N ratio.
)/dark current (Id)), have absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, have fast photoresponsiveness, have a desired dark resistance value, and be harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as 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-8i) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion/reading device is described in DE 2933411. The components have comprehensive characteristics in terms of electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, usage environment properties such as moisture resistance, and stability over time. The reality is that there are points that can be further improved that require improvements in characteristics. For example, when applied to an electrophotographic image forming member, it is difficult to simultaneously achieve high light sensitivity and high dark resistance. In the past, it has often been observed that residual potential remains in the φ during use, and if this type of photoconductive member is used repeatedly for a long time, fatigue due to repeated use will accumulate and an afterimage will occur. In many cases, disadvantages such as a so-called ghost phenomenon or a gradual decrease in response when used repeatedly at high speeds occur.Furthermore, the a-8i has a lower wavelength range than the short wavelength side of the visible light region. Therefore, the absorption coefficient in the long wavelength region is relatively small, and in order to match it with semiconductor lasers that are currently in practical use, commonly used halogen lamps and fluorescent lamps can be used as light sources. In this case, there is still room for improvement in that the light on the long wavelength side cannot be used effectively. , when the amount of light reaching the support increases without being absorbed sufficiently,
When the support itself has a high reflectance for light transmitted through the photoconductive layer, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "single blur" in the image. This effect becomes more serious as the irradiation spot is made smaller in order to increase the resolution, and becomes a serious problem especially when a semiconductor laser is used as the light source. Furthermore, when forming a photoconductive layer using a-8j material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer. That is, for example, the lifetime of photo'carriers 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 the dark area. This occurs in many cases. Furthermore, if the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or the layer may peel off as time passes after it is taken out of the vacuum deposition chamber for layer formation and left in the air. This resulted in problems such as the formation of cracks. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that need to be solved in terms of stability over time. Therefore, while efforts are being made to improve the properties of the A-8i material itself, there is a need to develop a material that will solve all of the above-mentioned problems when designing photoconductive members. The present invention has been made in view of the above points, and a-8i
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms (8i ) and a germanium atom (Ge) as a matrix, an amorphous material containing at least a hydrogen atom (H) or a hydrogen atom (X, ),
Wr Hn Hydrogenated amorphous silicone/L/manium, halogenated amorphous silicone/L/7asilicon germanium, or halogen-containing water-purple amorphous silicon germanium [hereinafter referred to as "a-8i" generically]
A photoconductive member designed and created with the structure of a photoconductive member having a photoreceptive layer exhibiting photoconductivity composed of Ge (using H, X) as described below. The material is not only a material that exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. This invention is based on the discovery that the electrical, optical, and photoconductive properties are stable at all times, and that the absorption spectrum characteristics on the long wavelength side are excellent. It is an all-environment type that is not limited by the usage environment, has excellent photosensitivity characteristics on the long wavelength side, and is extremely resistant to light fatigue. A main object of the present invention is to provide a photoconductive member that is rarely 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, and has a high optical response. Another object of the present invention is to provide a photoconductive member that has excellent adhesion between a layer provided on a support and the support and between laminated layers.
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer 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 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 obtain high-quality images with high density, clear noftones, and high resolution. be. Yet another object of the invention is high temperature sensitivity. 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 of the present invention exhibits photoconductivity and is made of an amorphous material that is compatible with the support for the photoconductive member. a photoreceptive layer consisting of a first layer and a second layer made of an amorphous material containing silicon atoms and carbon atoms, the first layer containing phoneme atoms; The distribution concentration in each layer thickness is C(1). C(3), C(2> first layer region, third layer region,
It is characterized by having the second layer regions in this order from the support side (however, C(3) alone does not reach the maximum, and C(1), C(2), C(3) If any one of them is 0, the other two are not 0 and are not equal). The light guide member of the present invention designed to have the above-mentioned layer structure solves all of the above-mentioned problems.
Extremely superior electrical and optical performance. 71 shows photoconductive properties, and 71 shows air pressure resistance and use environment characteristics. In particular, when applied as an image forming member for electrophotography, it has no influence on image formation, has stable electrical characteristics, and has high sensitivity and a high signal-to-noise ratio. It has excellent light fatigue resistance, repeated use characteristics, and high brightness.
It is possible to stably and repeatedly obtain high-quality images with high resolution and clear Harndt images. In addition, the photoconductive member of the present invention has a photoreceptive layer formed on the support, which is strong and has excellent adhesion to the support, and can be continuously repeated at high speed for a long time. When you use it, you can. 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 undiscovered photoconductive member will be described in detail with reference to the drawings. FIG. 1 is a schematic structural 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. 1 includes a support 101 for the photoconductive member, and an a-8iG
A first layer (1) 102 consisting of e(H,X), containing nitrogen atoms and having photoconductivity, and a second layer (II)
103. 64-4) The 'germanium atoms contained in J@(1) 102 may be contained so as to be evenly distributed in the second layer (1) 102, or may be contained in the layer thickness. Although it is contained in all directions, the distribution concentration may be non-uniform. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniform. It is necessary for the content to be uniformly distributed in order to make the properties uniform in the in-plane direction.In particular, in the thickness direction of the first layer (1) 102, it is necessary to contain it evenly. and the side opposite to +111 where the support 101 is provided (free surface i 0 of the photoreceptive layer
G 1llI ) towards the support 101111
11. The distribution of the first layer (I) is made such that the distribution is more concentrated on the side of the interface between the photoreceptive layer and the support 101, or the distribution is the opposite. ) 102. In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the first layer (J) is as follows:
In the layer thickness direction, it is desirable that the above-mentioned distribution state be avoided, and that a uniform distribution state be achieved in the in-plane direction parallel to the surface of the support. First layer (1) of photoconductive member 100 shown in FIG.
102 contains nitrogen atoms, and the distribution concentration in the layer thickness direction is C(1).
) 104, the second layer region (2) with a value of C(2)
105, the third layer region (3) with a value of C(3)
106. In the present invention, the above-mentioned item 1. Second. Each third layer region does not necessarily have to contain nitrogen atoms in any of the three layer regions, but any one of the three layer regions does not necessarily have to contain nitrogen atoms.
If one layer region does not contain nitrogen atoms,
The other two layer regions always contain nitrogen atoms,
In addition, the distribution concentration of nitrogen atoms in the layer thickness direction in these layer regions must be different. Clogging, distribution # stable C (1
), C(2), C(31), it is necessary to form each layer region so that the other two are not 0 and are not equal. )-V, it is possible to effectively prevent the 1LL charge from being injected into the photoreceptive layer from the free surface 106 side or the support 101 side when the band irt ribs are cut. It is possible to improve the dark resistance of the receptor layer itself and the adhesion between the support 101 and the photoreceptor layer. The first layer (1) 102 has practically sufficient photosensitivity and dark resistance, and can sufficiently prevent charge injection into the first layer (1) i02, and the 10th layer (1) 10
In order to effectively transport the photocarriers generated in the second layer, the distribution concentration C(3) of nitrogen atoms in the third layer region should be set so that the distribution concentration C(3) of nitrogen atoms in the third layer region does not reach its maximum value alone. It is necessary to design layer 0 (1) 102. In this case, it is preferable to design the first layer (1) 102 so that the thickness of the layer region of the feeder 3 is sufficiently thicker than that of the other two layer regions. Preferably, the first layer (1) 102 is designed so that the layer thickness of the third layer region is one-fifth or more of the layer thickness of the first layer (1) 102. the law of nature. In the present invention, the thickness of the first layer area (1) and the second layer area (2) is preferably 0.003 to 3.
0μ, preferably o:oo4-20μ, optimally 0.
It is desirable that the thickness be 0.005 to 10μ. Further, the layer thickness of the third layer region (3) is preferably 1
~100μ, more preferably 1-80μ, optimally 2-5
It is desirable that it be 0μ. The first layer region (1) and the second layer region (2) are made to mainly function as a so-called charge injection blocking layer that prevents charge injection into the first layer (1). Like the first layer of sea (
1), the first layer region (1) and the second layer region (1) are designed.
The layer thickness of each layer region (2) is preferably 10 μm at the maximum. When designing the photoreceptive layer so that the third layer region (3) mainly functions as a charge generation layer, the layer thickness of the third N region (3) should be determined according to the photoreceptor used. It can be determined as desired depending on the absorption coefficient of light. In this case, if a photoreceptor, which is normally used in the field of electrophotography, is used, the layer thickness of the third no region (3) may be about 10 μm at most. In order for the 30th layer region (3) to primarily function as a charge transport layer, it is desirable that the layer thickness be at least 5 μm. In the present invention, the nitrogen atom content distribution concentration C (ln, C
(The maximum values of 2L and C(3) are silicon atoms,
Preferably 67 atomic%, more preferably 50 atomic% based on the sum of germanium atoms and nitrogen atoms
mic%, preferably 40 atomic%. Also, the distribution concentration C(1). When ct2+, C(3) is not O, the minimum value is preferably 1 atomic I! for the sum of silicon, germanium, and nitrogen atoms. a, more preferably 50; Jtomic ym, optimally 1
It is desirable to set it to 00゛atomicIFl. FIGS. 2 to 10 show typical examples in which the distribution state of germanium atoms contained in the first layer (1) in the layer thickness direction is non-uniform. If! 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first Jf indicating photoconductivity.
jr (indicates the layer thickness of IJ, tB is the position of the surface of the layer on the support side, tT is the first layer (1) on the opposite side to the support side
indicates the position of the surface. That is, the first layer (1) containing germanium atoms is formed from the tB side toward the tT side. FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer (IJ) in the layer thickness direction. The surface on which the first layer (1) is formed and the first layer (1jI)
Up to a position 1° from the interface position 1f, tn where the surface contacts the surface of (1), the distribution concentration C of germanium atoms takes a constant value CI, and germanium atoms form the first layer ( 1), and from the position t1 to the interface position 1T, the distribution concentration is gradually and continuously decreased from the distribution concentration C2. At the interface position 1T, the distribution concession C of germanium atoms is assumed to be C3. In the example shown in FIG. 3, the distribution concentration C of the germanium atoms contained in 1 gradually and continuously decreases from the concentration C6 until reaching the position tT, and reaches the concentration Ill at the position 1T. The entire distribution state is formed such that it becomes Cs. In the case of Fig. 4, the distribution concentration C of germanium atoms is kept at a constant value C0 from position 1B to position t, and gradually and continuously decreases between position Fitz and position D. , at position 1T, the distribution concentration C is substantially zero (this is the case where r1 is detected as substantially zero (below the limit). In the case of Fig. 5, the distribution of germanium atoms is The degree C is gradually decreased from the concentration C8 from the position t[I to the position Ntr, and becomes substantially zero at the position 1. In the example shown in FIG. °The distribution concentration C of germanium atoms is between position 1B and position 13.
is a constant value, and at position 1. In this case, the concentration is C1o. Between position 1s and position 1, the distribution concentration C is linearly decreased from position t3 to multiple positions tT by 4≧. In the example shown in FIG. 7, the distribution concentration C is at the position ts
The concentration C11 is kept at a constant value until the position t.
, up to one position, the density is C82 and the density is C1! It is said that the distribution state decreases in a linear function until . In the example shown in figure M8, position 1. 1 leading to many positions tT, the distribution fA degrees C of germanium atoms is the concentration C1,
It decreases in a linear function so as to substantially reach zero. In FIG. 9, from position tB to multiple positions t, the distribution concentration C of germanium atoms is smaller than the concentration Cu.
An example is shown in which the concentration is linearly decreased to I6 and the concentration C1 is kept at a constant value between positions t and tT. In the example shown in FIG. 10, the distribution concentration C of germanium atoms is at the concentration CI? Until reaching the position t6, the concentration is initially reduced from this concentration CI7, and near the position t6, it is rapidly decreased to the concentration C18 at the position t. Between position t and position t7, the concentration is first rapidly decreased, and then gradually decreased to become concentration CI at position t, and between position t7 and position t8, the concentration CI is extremely low. The density is gradually decreased until it reaches the density C20 at position t8. Between position t and position 1T,
The concentration C2o is reduced 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 (1) in the layer thickness direction, in the present invention, , on the support side, the distribution of germanium atoms has a part with a high degree C, and on the field lnj LT side, the distribution concentration C of germanium atoms has a part where the distribution concentration C is lowered by 0 degrees along the axis on the support side. One preferred example is where the state is provided in the first layer (1). The 10th layer (1) constituting the photoconductive member of the present invention preferably has a relatively high concentration of germanium atoms on the support side or, conversely, on the free surface side. It is desirable to have a localized region (A) containing . For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (A) be provided within 5 μm from the interface position tB. The above-mentioned localized region (A) may be the entire layer region (LT) from the interface position 1B to a thickness of 5 μm, or the layer region (LT) may be
LT). Whether the localized region (A) is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the first layer (1) to be formed. The localized region (5) 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 or more, or more, relative to the sum of the germanium atoms and the silicon atoms. Preferably 5000 atomic (P or more, optimally I
It is desirable that the layer be formed so as to obtain a distribution state of 10' atomic 11 m or more. That is, in the present invention, the first layer (1) containing germanium atoms is formed on the support side. Layer thickness from 5μ or less (
The maximum value Cmax of the distribution concentration in the layer region from 1B to 5μ thick
It is preferable that it be formed so that In the present invention, the content lid for germanium atoms contained in the first layer (11) may be appropriately determined as desired so as to effectively achieve the object of the present invention, but the and preferably 1 to 9.5 x 1
05 atomic p, good value is 100~8
×105atO111AC solution, optimally 500~7
It is preferable to set it to X 105 atomic pplc. Is the distribution state of germanium atoms in the first layer (1) such that germanium atoms are continuously distributed in the entire layer region, and the germanium atoms are distributed in the layer thickness direction? If a change is given in which C decreases from the support side toward the free surface of the C-receiving layer, or vice versa, the rate of change curve of the distribution concentration C? By arbitrarily designing the layer as desired, the first layer (1) having desired characteristics can be realized as desired. For example, the distribution concentration C of germanium in the first layer (1) is set to be sufficiently high on the support side and as low as possible on the free surface side of the photoreceptive layer. By imparting changes to the distribution concentration curve of germanium atoms, it is possible to achieve high photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively short wavelengths, including the visible light region, and 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 No. 10 No. 1 (1) on the support side, the light intensity when using a semiconductor laser is reduced. Light on the long wavelength side that cannot be fully absorbed on the laser irradiation surface side of the photoreceptive layer can be substantially completely absorbed in the support side end layer region of the photoreceptive layer, and light from the support surface can be absorbed completely. Interference due to reflection can be effectively prevented. In the photoconductive member of the present invention, the first /i! (1) contains nitrogen atoms. The nitrogen atoms contained in the first layer (1) may be evenly contained in the entire layer area of the first layer (1) satisfying the above conditions, or (1)
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 determined in the first layer (1
) The overall thickness is non-uniform in the layer thickness direction as described above, but the first. Second. In each third layer 111,
Uniform in the layer thickness direction. 8B 11 to 15 show typical examples of the distribution state of nitrogen atoms in the entire 10th layer (1). still,
d used without reservation in explaining these figures.
The self name has the same meaning as used in FIGS. 2 to 10. In the example shown in FIG. 11, from position IB to multiple positions t, the distribution concentration C(N) of nitrogen atoms is a constant value C□;

[From 9 to position 1T, the distribution concentration C of cap atoms (
N) is constant at C22. In the example shown in FIG. (N) is set to C24, and the distribution concentration C(N) of nitrogen atoms is set to C2 from position t11 to position 1T, and the distribution concentration C(N) of nitrogen atoms is decreased in three steps. In the example of FIG. 13, the distribution concentration C(N) of nitrogen atoms is C2 at the position t, the horizontal position (t in '!), and the position i#,
From 'u to position tT, the distribution concentration of nitrogen atoms C(N)←
It is said to be tCwt. In the example of FIG. 14, from position tB to position (2,'-I1.
Then, the distribution concentration C(N) of nitrogen atoms is C6, and (rL
Position t, 4' from JtB! ! Then, the distribution concentration of nitrogen atoms C
(N) is assumed to be C2, and the distribution concentration C(N) of nitrogen atoms is assumed to be C1° from position t14 to position tT. In this way, the distribution concentration C(N) of nitrogen atoms is increased in three stages. In the example of FIG. 15, position 1. Many positions t1. Up to, the distribution concentration C(N) of nitrogen atoms is C3I, and from position fit+: to position tta, the distribution concentration C(N) of nitrogen atoms is C
112, and from position tl11 to position tT, the distribution concentration C(N) of nitrogen atoms is φ as CSS. The distribution concentration C(N) of nitrogen atoms is made high on the support side and the free surface side. In the present invention, the layer region (N) containing nitrogen atoms provided in the first layer (1) (the above-mentioned 11th, 2nd.
If the main purpose is to improve the photosensitivity and dark resistance, the third layer (consisting of at least two layer regions) should be the entire layer of the first layer (1). In order to prevent charge injection from the free surface of the photoreceptive layer, it is provided near the interface on the free surface side to strengthen the adhesion between the support and the photoreceptive layer. When the main purpose is to achieve this, the support side end layer region (
E). In the first case mentioned above, the content of nitrogen atoms contained in the layer region (N) is relatively low in order to maintain high photosensitivity, and in the second case the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain a high photosensitivity, and in the second case the content of nitrogen atoms contained in the layer region (N) is kept relatively low in order to maintain high photosensitivity; In the third case, it is desirable to use a relatively large amount in order to prevent the injection of the liquid, and in the third case, to ensure that the adhesion to the support is strengthened. In addition, in order to achieve the above three simultaneously, it should be distributed at a relatively high concentration on the support side, at a relatively low concentration at the center, and in the interfacial layer region on the free surface side. The layer region (
N) It may be formed inside. In the present invention, the layer region (
The content of nitrogen atoms contained in N) depends on the characteristics required for the layer region (N) itself, or when the layer region (N) is provided in direct contact with the support, the content of the nitrogen atoms in the support It can be selected as appropriate based on the organic relationship, such as the relationship with the properties at the contact interface with the material. In addition, when another layer region is provided in direct contact with the layer region (to), 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 present in the layer region (N) can be determined as desired depending on the properties required of the photoconductive member to be formed, but it is preferably from 0.001 to 50
atomic%, more preferably 0.002 to 40
It is desirable that the content be atomic%, most preferably 0.003 to 30 atomic%. In the present invention, even if the layer region (N) occupies the entire first layer Id (1) or does not occupy the entire first layer (1), the layer thickness T of the layer region (N) . If the proportion of the first layer (1) in the layer thickness T is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (N) In the case of the present invention, the ratio of the layer thickness T of the layer region (N) to the layer thickness T of the first layer (I) is two-fifths or more. The upper limit of the amount of nitrogen atoms contained in the layer region (N) is preferably 30
atomic% or less, preferably 20 atoms
It is preferable to set the amount to 10 atomic C% or less, most preferably 10 atomic C% or less. In the present invention, the layer region (N) containing nitrogen atoms constituting the first #jNl has a relatively high concentration of hard JA atoms near the support side and the free surface side, as shown in the upper part. In the former case, it is possible to further improve the adhesion between the support and the photoreceptive layer. It is possible to measure the same as above. The localized region (13) can be explained using the symbols d 11 xl to FIG. 15, such as the interface layer 1+'! l-1
It is preferable that the localized region (is) be provided within 5μ from Bt or tT.
It may be the entire no region (L, ) up to 5μ thick from B or tT, or it may be a part of the layer region (LT). Whether the localized region (B) is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the first R& (1) to be formed. The localized region (B) has a distribution concentration of nitrogen atoms ic' (N) (7
) Maximum value Cm a x is preferably 500 atomic
ppi+ or more, more preferably 800 atomic p
As mentioned above, it is preferable that the layer be formed in such a manner that the concentration is optimally 1000 atomic ppm or more and a Sarel-like distribution state can be obtained. That is, in the present invention, the layer region (N) containing nitrogen atoms has a layer thickness of 5 μm from the support side or the free surface side.
(5 μ thick layer region from tn or t, r)
It is desirable to form the ip degree C(N) so that there is a maximum value Cmax. In the present invention, the halogen atoms (X) contained in the first layer (1) as necessary include fluorine,
Examples include 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 (1) are improved by containing a substance (C) that controls the conductive properties in the first layer (1). It can be arbitrarily controlled as desired. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, S1()e(H, X
), n-type impurities and n
Gives type conduction properties! Examples include l-type impurities. Specifically, the n-type impurity is an atom belonging to Group I of the periodic table (Group Atom), for example, B (#Jl) R
), Al (7luminium), Ga (gallium), I
n (indium). There are Tl (thallium), etc., and 13. is particularly preferably used. It is Ga. As n-type impurities, atoms belonging to V h of the periodic table (
MV group atoms), e.g. P Glut), As (arsenic)
, sb (antimony), Ei (bismuth), etc., and P is particularly preferably used. It is As. In the present invention, the content of the substance (C) that controls conduction properties contained in the first layer (1) is as follows:
The conductive properties required for the layer (1) or the relationship with the properties at the contact interface with the support with which the second layer (1) is provided in direct contact are selected depending on the organic relationship. I can do it. In addition, when the substance controlling the conduction properties is contained in the first layer (1) locally in a desired layer region of the second layer (1), in particular, , when impregnating the first layer (1) in the support side end layer region, the characteristics of the other layer region provided in direct contact with the layer region and the contact with the other layer region. The relationship with the properties at the interface is also considered,
The content of the substance controlling the conduction properties is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the first layer (1) is preferably 0.01 to 5 x 10' atomic P, which is more suitable. 0.5~l x 10' atomic pp
, the optimum value is preferably 1 to 5×103103atoppn. In the present invention, the content of the substance (C) in the layer region containing the substance (q) that governs the conduction properties is preferably 3 Q atomic yp or more, more preferably 50
atomiccp or higher, optimally 1001003t
In the case of OIF or more, it is desirable that the substance (C) be locally contained in a part of the layer region of the first layer (1), particularly at the support side edge of the first layer (1). It is desirable to make it unevenly distributed in the sublayer region (M). Among the above, the support side end layer region (E) of the first layer (I)
For example, when the substance (C) to be contained is the n-type impurity, the photoreceptor can be When the free surface of the layer is subjected to polar charging treatment, it can effectively prevent the movement of electrons injected from the support side into the photoreceptive layer, and the substance to be contained can be In the case of impurities, when the free surface of the photoreceptive layer is charged to e-polarity, it is possible to effectively prevent the movement of holes injected from the support side into the photoreceptor layer. In this way, when the end layer region (E) contains a substance that dominates the conduction characteristics of one polarity, the first layer (1
), that is, the layer region (Z) excluding the end layer region (B), may contain a substance that controls conduction characteristics of other polarity, or The substance that governs the conduction properties of the same polarity may be contained in an amount much smaller than the actual amount contained in the end layer region (E). In such a case, the content of the substance (C) that controls the conduction characteristics contained in the layer region (Z) is determined by the polarity and content of the substance contained in the end layer region (Z). Although it is determined appropriately according to desire, it is preferably 0.001 to 1000 atomic F, more preferably 0.05 to 500 atomic PF+, and optimally 0.1 to 200 atomic pP. In the present invention, when the end layer region (E) and the layer region (Z) contain the same type of substance that controls conductivity, the content in the layer region (Z) is preferably is preferably 30
It is desirable that it be less than or equal to atomic P . In addition to the above-mentioned cases, in the present invention, a layer region containing a substance controlling conductivity having one polarity in the first layer (1) and a conductivity having the other polarity are included. It is also possible to provide a so-called depletion layer in the contact region by directly contacting a layer region containing a substance that controls the depletion layer. For example, in the first M(1), the layer region containing the p-type impurity and the layer region containing the n-type impurity of the previous dpi are provided so as to be in direct contact with each other, so that the so-called p n+ij :4 can be formed to provide a depletion layer. In the present invention, the first layer (1) composed of a-8iGe (H, done by law. For example, to form the first layer (1) consisting of a-8iGe(H,x) by glow discharge method, basically silico/atoms (Si) can be supplied. 8+ raw material gas for supply, raw material gas for Ge supply that can supply germanium atoms (Ge), and raw material gas for introducing hydrogen atoms (n) and/or raw material for introducing halogen atoms (X) as necessary. A gas is introduced at a desired gas pressure into a deposition chamber whose interior can be evacuated to generate a glow discharge within the deposition chamber, thereby depositing a-
A layer consisting of 8iGe (H,X) may be formed. Further, in order to contain germanium atoms in a non-uniform distribution state, a layer made of a-8iGe (HSX) may be formed while controlling the distribution concentration of germanium atoms according to a desired rate of change curve. In addition, in the case of forming by the 1-Nong method, Si is formed in an atmosphere of an inert gas such as Ar 1He or a mixed gas based on these gases.
or the target and Ge
Using two targets made up of
If necessary, use a mixed target of Ge and He. The raw material gas for supplying Ge diluted with a diluted gas such as Ar is mixed with gas for introducing hydrogen atoms (H) and/or halogen atoms (X) according to necessity. This is accomplished by introducing the desired gas into a deposition chamber and creating a plasma atmosphere of the desired gas. In order to make the distribution of germanium atoms non-uniform, 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 blating 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. (HB method), etc., and the flying evaporates are passed through the desired gas plasma atmosphere.
This can be done in the same manner as in the sputtering method. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH,, s i , H,, 8 plates,
】■6.8 Silicon hydride (silanes) in a gaseous state such as i, H, o, etc. or which can be gasified are mentioned as effective, especially ease of handling during layer creation work, 8j S i f (4, Si, II6,
are listed as preferred. Substances that can be used as raw material gas for supplying Ge include (J
e H,, Qe2H6, Gc, ■l, , Ge, H,
, ,Ge,Hl, ,Ge,Hl, . Ue7tl,..., Ge811,8, Uc, H20% germanium hydride in a gaseous state or which can be gasified is considered to be effectively used, especially for ease of handling during layer preparation work and for Ge supply. In terms of efficiency, etc., (ieH
,,Oe,H,,Ge,11. Preferred examples include many halogen compounds that are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives. Preferred examples include halogen compounds in a gaseous state or which can form into scum. Further, in the present invention, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be turned into dregs and have silicon atoms and halogen atoms as constituent elements, can also be cited as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CeF, C/F, BrF%,
Interhalogen compounds such as BrF5, HF3, F7, and Ce1 can be mentioned. Specifically, as a silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, for example, 8
Preferred examples include silicon halides such as i, FitFa, and SiC/4S8iBr4. When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. A first layer (1) of a-8iGe containing halogen atoms can be formed on a desired support without using silicon oxide scum. When manufacturing a light-receiving layer containing halogen atoms according to the glow discharge method, basically, for example, silicon halide, which serves as a raw material scrap for supplying Si, germanium hydride, which serves as a raw material scrap, for supplying Ge, and Ar, H2. , He, etc. are introduced into the deposition chamber where the photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. , which can form the first layer (1) on a desired support,
In order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. Moreover, each gas may be used not only individually but also in a mixture of multiple types at a predetermined mixing ratio. In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blating method,
What is necessary is to introduce a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms into the deposition chamber to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, hydrogen gas, or the above-mentioned 7-ranium gases 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 the raw material residue for introducing halogen atoms, but in addition, HF, HC/. I (Br, hydrogen halide such as HI, 8 iH, F,
,SiH,I, ,8iH,C1t, 8iMCI! s,
Halogen-substituted silicon hydride such as 8iH, Br, , 8iHBr3, and GeHF8, GeHt Fz, G e L
F SG e HCIs, GeH2C/, GeH3C
1s GeHBrHlGel (, Br2, GeH3B
r % GeH, I-3,1, GeH2I2, GeH
, hydrogenated germanium halides such as I, halides containing hydrogen atoms as one of their constituent elements, GeF, GeC, etc.
1, GeBr, 5GeI GeF4, GeCl,
Germanium halides such as GeBr2, Ge I, etc.
Gaseous or gasifiable substances such as the following may also be mentioned as useful starting materials for forming the first layer (1). Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the 10th layer (1), 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. To structurally introduce hydrogen atoms into the first layer (I),
In addition to the above, or SiH4, Si, 几, si, Ru,
Si, H,. With germanium or a germanium compound for supplying Ge, or GeH,
%Ge2H6,Ge5Hs 5Ge4Hto %G
e5H12, Ge6H14, Ge7 几. , GeaHls
, Geg Xun. This can also be carried out by causing germanium hydride such as the like and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to generate a discharge. In a preferred embodiment of the present invention, the amount of hydrogen atoms (lυ) contained in the first layer (1) of the light guide member to be formed is
Or... halogen atom (xiO%, or the amount of hydrogen atoms and halogen atoms (Hx) is preferably 0
．． 01-40 atomic%, more preferably 0,05
~30 atomic%, optimally 0.1-25 at
It is preferable to make it omic. In order to control the amount of hydrogen atoms Ill or/and halogen atoms (XI) contained in the first layer (1), for example, the support temperature or/and hydrogen atoms (groups or) containing hydrogen atoms fXI can be controlled. The amount of the starting material introduced into the deposition system, the discharge force, etc. may be controlled. To provide the region tN), the starting material for introducing nitrogen atoms is added to the above-described first layer (I) during the formation of the first layer (I).
I) It may be used together with the starting material for formation, and may be contained in the layer to be formed while controlling its amount. When a glow discharge method is used to form the layer region tNl, 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 (1) described above. It will be done. 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. Nitrogen atoms tN) used to form the layer region (N)
Starting materials that can be effectively used as raw material gases for introduction include N as a constituent atom or N and H as constituent atoms, such as crab crystals), ammonia (N8), hydrazine ( Hz NNHz), hydrogen azide (HN, ),
Mention may be made of gaseous or cassifiable nitrogen such as ammonium azide (NH4N5), 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 (F3N) and nitrogen tetrafluoride (F4 N!
) and other halogenated nitrogen compounds. In the present invention, in order to further enhance the effect obtained by nitrogen atoms in the layer region (N), oxygen atoms can be further contained in addition to nitrogen atoms. Examples of raw material gases for introducing oxygen atoms include oxygen (O2) and ozone (O2).
3), -nitrogen oxide (NO), nitrogen dioxide (N02), -
Nitrogen dioxide (N20), nitrogen sesquioxide (Nzos), trinitrogen tetraoxide (Nto4), nitrogen sesquioxide (NzOg),
Nitrogen trioxide (NOx), lower siloxanes whose constituent atoms are silicon atoms (St), oxygen atoms (0), and hydrogen atoms (I()), such as disiloxane (H3SiO8iH,) and trisiloxane (H18i08iH20SiH1) etc. To form the layer region N by the sputtering method,
During the formation of the first 4(1), a single crystal or polycrystalline St wafer or 8i, N, wafer, or Si and 8i,
Sputtering may be performed using a wafer containing a mixture of N as a target in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for adding nitrogen atoms and optionally hydrogen atoms and/or halogen atoms can be diluted with a diluent gas as necessary for sputtering deposition. The Si wafer may be sputtered by introducing the gas into a chamber and forming a gas plasma of these gases. Alternatively, by using St and Si, ~4 as separate targets, or by using a single mixed target of St, Si, and N, in an atmosphere of diluted scum as a sputtering gas. or at least a hydrogen atom (H
This is done by sputtering in a gas atmosphere containing l or/and halogen atoms (XI as constituent atoms).The raw material gas for nitrogen use is one of the raw material gases shown in the glow discharge example mentioned above. The raw material residue for introducing nitrogen atoms can also be used as an effective gas in the case of sputtering.In the present invention, when forming the first layer (1), the layer region containing nitrogen atoms is (N), the layer region t
By changing the distribution concentration C (Nl) of nitrogen atoms contained in N) stepwise in the layer thickness direction, a desired distribution state in the layer thickness direction (
In the case of a glow discharge, the distribution concentration C (Nl
The starting material gas for the introduction of nitrogen atoms to be changed is
This is accomplished by introducing the waste into the deposition chamber while changing the flow rate of the waste appropriately according to a desired rate of change curve. For example, the opening of a given needle pulp provided in the volume of the gas flow path system may be changed appropriately by any conventional method such as manual operation or an externally driven motor. layer region) by sputtering method,
In order to form a desired distribution state (depth profile) of nitrogen atoms in the layer thickness direction by changing the distribution concentration C(N) of nitrogen atoms in the layer thickness direction stepwise in the layer thickness direction,
Firstly, as in the case of the glow discharge method, nitrogen atoms can be introduced by using a starting material in a gaseous state and changing the gas flow rate when introducing the gas into the deposition chamber as desired. be done. Second, the target for sputtering is, for example, S
If a target containing a mixture of i, Si, and N is used, this can be achieved by changing the mixing ratio of Si, Si, and N in advance in the layer thickness direction of the target. . In order to structurally introduce a substance that controls the conduction properties into the 10th layer (1), for example, a group II atom or a group V atom, it is necessary to use a group The starting material for forming the first layer (1) may be introduced into the deposition chamber in gaseous form together with the other starting materials for forming the first layer (1). Possible starting materials for introducing Group 1II atoms include those that are gaseous at room temperature and pressure, or
It is desirable to use a material that can be easily gasified at least under layer-forming conditions. Specifically, Bz
Ha, BaHto, BaI(Il, BIIHII,
BsH + Boron hydride such as BaHn, BaHI4, BF
3, boron halides such as BCl2, BBr, etc.0 In addition, AlCl, , GeC1, Ge (C
Hs), InCls, Ttct, etc. can also be mentioned. In the present invention, effective starting materials for the introduction of phosphorus atoms are PH,
Hydrogen north neighbors such as P2H4, PI (, I, PF i PFs, P
C/3, PCI! ! ,PBr,,PBr,,PI. Examples of halogen ratios include: In addition, A8Hs N
”'s, AsCl!3, AsBr3, AsF,, Sb
H,,5bF3. 8bF, , 8bCls, 5bC15
, BIHs % BIG/3, B i B rs and the like can also be mentioned as effective starting materials for use in the V lacrimal gland. In the present invention, the layer thickness of the layer region constituting the first layer (I) 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. Although it is determined as desired depending on the characteristics required for the other layer regions constituting the first layer (1) formed thereon, the lower limit and the width are preferably 30λ or more. , more preferably 40 Å or more, optimally 50 λ or more. In addition, if the substance controlling the conduction properties contained in the layer region (C1 chain content is 30 atomic or more, the upper limit of the layer thickness of the layer region is preferably 1
It is desirable that the thickness be 0μ or less, preferably 8μ or less, and optimally 5μ or less. In the photoconductive member 100 shown in FIG. 1, a twentieth layer (II) 103 is formed on the first layer (1) 102.
Has a free surface, moisture resistance, continuous repeated use characteristics,
This is provided in order to achieve the objectives of the present invention in terms of electrical pressure resistance, use environment characteristics, and durability. Furthermore, in the present invention, since each of the amorphous materials constituting the first layer (1) 102 and the second layer (...) 103 has a common constituent element of silicon atoms, it is possible to stack layers. The interface is sufficiently acidified to ensure chemical stability. The second layer (II) in the present invention is silico/)M(
St), a carbon atom (C1, and optionally a hydrogen atom or/and a halogen atom (X) (hereinafter r a-(SixCa-X)7CHSX) + -y
However, it is composed of 0<X%y<1). The second layer (II) composed of a (81XC1-X)y (H% done by. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment cost burden, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member with specific characteristics. Carbon atoms and halogen atoms can be easily introduced into the second layer (...) to be manufactured along with silicon atoms. Due to these advantages, the glow discharge method or the sputtering method is preferably employed. Furthermore, in the present invention, the second layer (It) may be formed by using a glow discharge method and a sputtering method in the same apparatus system. In order to form the second layer (I[) by the glow discharge method, a predetermined amount of the raw material gas for forming a −(5ixC+−x)y (H,X)+−y is mixed with dilution gas as needed. The mixture was mixed at a mixing ratio of 1'Jil sQ support, and the scum was mixed into a vacuum deposition chamber where a support was installed, and the introduced scum was turned into gas plasma by generating a glow discharge. On the first layer (I) already formed on the body, a - (S
izC+-x)y(HlX)I-y0 In the present invention, a-(SixCt-x)y(Hs x
)s As the raw material gas for forming y, silicon atoms (S
t), most of the gaseous substances or gasified substances whose constituent atoms are at least one of the following: When using a raw material gas having St as a constituent atom as one of the 0 8is C511z If necessary, a 7j3 family gas containing H as a constituent atom or/and 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 as a constituent atom may be used. , C and 1 (as constituent atoms) or/and It is possible to use a mixture of the raw material gas and the raw material gas whose constituent atoms are St, C, and H, or the raw material gas whose constituent atoms are St, C, and X. is a raw material gas containing Si and H as constituent ring atoms.
A raw material gas containing Si and X as constituent atoms may be mixed and used, or a raw material gas containing C as constituent atoms may be mixed and used with a raw material gas containing Si and X as constituent atoms. In the present invention, UF and CJSBr are suitable as the halogen atoms contained in the second layer (...). (2) Especially desirable is F'SC/ In the present invention, raw material gases that can be effectively used to form the second layer (II) include Mention may be made of substances that are in a gaseous state at pressure or that can be easily gasified. In the present invention, SiH4,5t2Hs, 51sHa, 5i4H, which have Si and H as constituent atoms, are effectively used as the raw material gas for forming the second layer (II). Silicon hydride gases such as silanes (SilCane), saturated hydrocarbons containing C and H as constituent atoms, e.g., having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 4 carbon atoms. Examples include acetylene-based carbonized frozen confectionery of No. 3, simple halogen, halogenated frozen confectionery, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydride. Specifically, the saturated hydrocarbons include methane (CH4),
Ethane (CtHs), Propa” (cana), n-butane (n-ctHlo), Be/Liy (CaHtz)1
．． Examples of lCfV-based hydrocarbons include ethylene (C, H
), propylene (CSa), butene-” (CaH
a), Butene-2 (C4H8), Inbutylene (C4H
a), pentene (C!IHIO), acetylene hydrocarbons such as acetylene (ctH2), methylacetylene (C3I(4), butene (C4)), and simple halogens such as fluorine, chlorine, bromine, and iodine. Examples of halogen gas and hydrogen halide include FH, I (I, HCl,
HBr, interhalogen compounds include BrF,
CI! F, CIF, XCIF, BrF, ,B
rF,,IF,,IF,,Ice,IBr, Hydrogen halide is SiF,,8i2F6,SiC/
4.5iClsBr %Si('/!Br*, 5iCe
Br,,5iC1! II,8iBr,, As the halogen-substituted silicon hydride, S iH,F,,5iH1Cr,,
81HQl,', 8iHIICI 5SiH3Br,
SiH, Br, ,5t)lBr,, As silicon hydride, silanes such as 8iH4, Si-fast 8i4111°, etc.
St 1ane), etc. In addition to these, CF4, CCe4, CBr, , CUB'
, , CH,F', ,CHsF, CH,Cl, C
Halogen-substituted paraffinic hydrocarbons such as Br, CH,I, and CzHaCl, fluorinated sulfur compounds such as SF4 and SF6, alkyl silicides such as St (CH3)I8i (Cz&)n, and 5inI! (-)s, 5iClz
Silane derivatives such as halogen-containing alkyl silicides such as (C)2.5iC1s3 can also be cited as effective. These second layer (II) forming substances contain silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio in the second layer (II) to be formed. They are selected and used as desired when forming the second layer (II). For example, 5i can easily contain silicon atoms, carbon atoms, and hydrogen atoms, and can form a layer with desired characteristics.
(CH,)4 and 5iHCes containing a halogen atom, 8[, C1,,8iC/. Alternatively, B-(SizC*-X) can be obtained by introducing 5iI (3CI!, etc.) at a predetermined mixing ratio in a gas state into the apparatus for forming the second layer (II) to generate glow discharge.
)'(C7+H), -y can form a second layer (II). To form the second tea by the sputtering method, a monocrystalline or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of St(!:C) is used as a target. If necessary, sputtering may be performed in an atmosphere of various gases containing halogen atoms and/or hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, C and H or/ The raw material gases for introducing and Alternatively, 8i and C can be used as separate targets, or by using a single mixed target of Si(!:C), hydrogen atoms and/or halogen atoms can be added as needed. This is done by sputtering in a gas atmosphere containing atoms.As the raw material gas for introducing CSH and These substances can also be used as effective substances in the sputtering method. In the present invention, the diluting gas used when forming the second layer (II) by the glow discharge method or the sputtering method is a new noble gas, e.g. ILe % Ne
% Ar etc. can be cited as suitable. The second layer (It) in the present invention is carefully formed so that its required properties are provided as desired. That is, 5iSC1 substances containing H and/or
Properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties are shown respectively. The preparation conditions are strictly selected as desired so that a-(SizC+-z)y(H,,X)ty having the following properties is formed. For example, if the second layer (II) is provided with the main purpose of improving electrical voltage resistance, a - (8izCr-x)y (HlX) It is created as an amorphous material. In addition, if a second layer (...) is provided for the purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to a certain extent, and it will be more or less resistant to the irradiated light. As an amorphous material with a sensitivity of a-(
StXCs-X)y (H% X)1-y is created. a-(8iXCt-z)y(H
, X), -y when forming the second layer (It),
The temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, a (SizC+-x)y(H-
It is desirable that the temperature of the support during layer formation be tightly controlled so that X)+-y can be created as desired. In the present invention, the formation of the second layer (n) is performed by selecting an optimal range as appropriate in accordance with the method of forming the 20th layer (n) in order to effectively achieve the desired purpose. However, the temperature is preferably 20 to 400°C, more preferably 50 to 350°C, most preferably 100 to 300°C. The glow discharge method is used to form the second layer (n) because it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. However, when forming the second layer (It) using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, is advantageous. Created a-(S1
■ (one of the important factors) that influences the characteristics of
(5iXc, -x)yx, -3' is preferably created as a discharge power condition with high productivity and effectively at lO
~300W, preferably 20-250W, optimally 5
It is desirable that the power be 0 to 200W. The gas pressure in the deposition chamber is preferably between 0.01 and I 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 (I[) are preferably within the ranges described above, but these layer formation factors are independently and separately determined. Based on the mutual organic relationship so that the second layer (II) consisting of B - (5izct -x)y (H, It is desirable that the optimum value of each layer creation factor be determined by The amount of carbon atoms contained in the second layer (It) in the light guide member of the present invention is the second )'! i (II), which is the kff factor for forming the second layer (n) that provides the desired characteristics to achieve the object of the present invention.
The amount of carbon atoms contained in the second jiii (I) in the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (n). It is. That is, the general formula a-(S i zCl-x)y (
The amorphous material represented by HlX)+ -y can be broadly classified as an amorphous material (
Hereinafter, it will be written as [a-8iBCt-B J0, however, 0
< akl), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as r a(StbCs-b
)c■, -0''. However, O < b, c < 1), an amorphous material (hereinafter referred to as r a-(
It is written as 8i(IC,-d)e(H,x)+-eJ. However, it is classified as 0<d, e<1). The present invention vc Oi-c, the 20th layer (II) is a-8iBC
16, the amount of carbon atoms contained in the second layer (n) is preferably 1×lO to 90 atomic
%, more preferably 1 to 80 atomic %, most preferably 10 to 75 atomic %. That is, the previous a -8iBCI B's a(7
), a is preferably 0.1 to 0.9999
9, more preferably 0.2 to 0.99, optimally 0.25
~0.9. In the present invention, the second layer (...) is a-(SibCs-
b) If JL is composed of clfl-c, the second layer (II
) is preferably 1×1
0 to 90 atomic '16, more preferably 1 to 90 atomic%, optimally 10 to 80 atomic%
It is preferable to set it as omic%. The content of hydrogen atoms is preferably 1 to 40 atoms.
c%, more preferably 2 to 35 atomic%, optimally 5 to 30 atomic%,
Photoconductive members formed with hydrogen contents within these ranges are well suited for practical applications. That is, the above a-(Si1)C, -b). H, - (If expressed as H, b is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, most preferably 0.15 to 0.
9, C is preferably 0.6 to 0.99, more preferably 0
．． 65 to 0.98, most preferably 0.7 to 0.95. The second layer (n) is a-(8iaC+-d)e (H,
X), -, the content of carbon atoms contained in the second layer (II) is preferably l
Xl0'~90 atomic%, more preferably 1~9
0 atomic, optimally 10-80 atomic
It is preferable to set it to c%. The content of halogen atoms is preferably 1 to 20 atomic
H, more preferably 1 to 18 atomic %, most preferably 2 to 15 atomic %, and the photoconductive member produced when the halogen atom content is within these ranges is practically sufficient. It can be applied. The content of hydrogen atoms contained as necessary is preferably 19 atomic% or less, more preferably l 3
It is desirable that the value be less than atomic% [7.
If there is a wart in the display of d or e in 6, d is preferably 0.1.
~0.99999, more preferably 0.1-0.99, optimally 0.15-0.9, e preferably 0.8-0.
99, more preferably 0.82 to 0.99, optimally 0.
It is desirable that it is 85 to 0.98. The number range of the layer thickness of the second layer (II) in the present invention is one of the important factors for effectively achieving the object of the present invention. It can be determined as desired depending on the intended purpose. In addition, the layer thickness of the second layer (It) varies in each layer region, also in relation to the amount of carbon atoms contained in the layer (It) and the layer thickness of the first layer (I). It is necessary to appropriately determine the desired characteristics based on the organic relationship depending on the required characteristics. In addition, it is desirable to consider the economical aspects including productivity and mass production. The thickness of the second layer (II) in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 30μ.
It is desirable that the thickness be 20μ, optimally [0,005 to 10μ]. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr stainless steel, A/, CrSMo,
Examples include metals such as Au5NbSTasVSTi, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr1A/
' % (-r % Mo -, Au % I r %
Rice, Ta, V, Ti, Pt. Pd, I fi20s, 5n02, j, TO(In
Conductivity can be imparted by providing a thin film consisting of z03+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, AI
! , Ags paSZn, Ni5Au, CrSMo,
A thin film of metal such as Ir, Nb, Tas V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is simulated with the metal to impart conductivity to the surface. be done. The shape of the support may be any shape such as cylindrical, belt-like, or plate-like, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape. The thickness of the support is appropriately determined so that the desired photoconductive member is formed.
However, when flexibility is required as a photoconductive member, it is made as thin as possible within a range that allows it to function as a support. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is preferable to use
10μ or more Next, an outline of an example of the method for manufacturing the photoconductive member of the present invention will be described. FIG. 16 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 1102 to 1106 in the figure are sealed with raw material gases for forming the photoconductive member of the present invention. 1102 is SiH gas (purity 99.999%, hereinafter referred to as SiH) diluted with He.
/ Abbreviated as He. ) cylinder, 1103 is diluted with He (]eH, gas (purity 99.999%, hereinafter GeH,
/ Abbreviated as He. ) cylinder, 1104 is He te diluted 8iF, gas (purity 9g, 99%, hereinafter SiF,
/He is abbreviated. ) cylinder, 1105 is NH gas (purity 99.999%) cylinder, 1106 is H2 gas (purity 9
9.999%) cylinder. In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 1106,
! Check that the j-valve 1135 is closed, and also check the inflow valves 1112 to 1116 and the outflow valve 11.
17 to 1121, confirm that the auxiliary valves 1132 and 1133 are open, and first open the main valve 1134.
is opened to exhaust the reaction chamber 1101 and each gas pipe. Next, the vacuum gauge 1136 reads approximately 5 X 10' to
When it becomes rr, the auxiliary valves 1132, 1133,
Close outflow valves 1117-1121. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, from the gas cylinder 1102 (81)
(, /He gas, GeH from gas cylinder 1103, /
1-1e gas, gas cylinder 1105J: N■・■ Open valves 1122, 1123, 1124 and set the pressure on outlet pressure gauges 1127, 1128, 1129 to 1 kf.
l/d, inlet valves 1112, 1113, 11
14 are gradually opened to allow mass 70 to flow into the controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valves 1117, 1118, 1119 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. 5i)(,/He gas flow rate and G
Outflow valves 1117 and 1118 so that the ratio of the eH,/He gas flow rate to the NH, gas flow rate becomes a desired value. 1119 and the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the substrate 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power source 1140 is set to the desired power to generate glow discharge in the reaction chamber 1101. At the same time, the flow rate of NU and gas is adjusted manually or by an external drive motor, etc., according to the pre-designed rate of change curve of valve 1.
The distribution concentration C@ of elementary atoms contained in the formed fuchu is controlled by appropriately changing the aperture 1 of 118. To form the second layer (1) on the first layer (1) formed to the desired layer thickness as described above, the same valve operation as that for forming the first scrap (1) is required. For example, by diluting each of SiH, gas, and Cz14+ gas with a diluent gas such as He as needed, glow discharge is generated according to desired conditions. In order to contain a halogen atom in the second Jffl (1), for example, add SiF4 gas and C, H, gas, or add SiH and gas to this, and add the second Wffl in the same manner as above.
This is accomplished by forming (1). 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. In order to avoid gas remaining in the gas piping leading from the valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 1134 is fully opened to temporarily drain the system. Perform operations to evacuate to high vacuum as necessary. For example, in the case of glue discharge, the amount of carbon atoms contained in the No. 20 scrap (11) is SiH4 gas, C, and H. The flow rate ratio of the gas introduced into the reaction chamber 1101 is changed as desired, or in the case of forming a layer by sputtering, the sputtering area ratio of the silicon wafer and the graphite wafer is changed when forming the target, or the sputter area ratio of the silicon wafer and the graphite wafer is changed when forming the target. It can be controlled as desired by changing the mixing ratio of powder and graphite powder and molding the target. The amount of halogen atoms (X) contained in the second layer (El) is determined by the raw material gas for introducing halogen atoms,
For example, this is accomplished by adjusting the current flowing when SiF gas is introduced into the reaction chamber 1101. Further, during layer formation, it is desirable that the substrate 1137 be rotated at a constant speed by a motor 1139 at a temperature of .degree. C. in order to make the layer formation uniform. Examples will be described below. Example 1 A cylindrical At
' Samples (samples Al1-1 to Al13-6) as electrophotographic image forming members were prepared on the substrate under the conditions shown in Table 1 (Table 2). The content distribution concentration of germanium atoms in each sample is the first
The distribution concentration of nitrogen atoms is shown in FIG. 7, and in FIG. 18. Place each sample obtained in this way in a band xi optical experiment device; 5. Perform corona charging for 0.3 sec'c with OKV,
A light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 21 ux-sec was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the imaging member by cascading a θ-charged developer (including toner and carrier) over the surface of the imaging member. The toner image on the image forming member is processed by 5. When Ilk was transferred onto transfer paper-L using OKV's corona charging, all samples had excellent resolution, and clear, high-density images with good gradation reproducibility (obtained). , the light source is 81 instead of a tungsten lamp.
Image quality of toner transfer images was evaluated for each sample under the same toner image forming conditions as in C, except that an electrostatic image was formed using a 0 nm GaAs semiconductor laser (10 mW). However, even in the case of the sample with the deviation, clear, high-quality images with excellent resolution and good gradation were obtained. Example 2 A cylinder-shaped Ag
Samples (samples A21-1 to A23-6) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 3 (Table 4). The concentration distribution of germanium atoms in each sample is shown in FIG. 17, and the distribution concentration of nitrogen atoms 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. Also, for each sample, 38℃, 8゛0%
When a repeated use test was conducted 200,000 times in an RH environment, no deterioration in image quality was observed in any of the samples. Example 3 Electrophotographic fabrication was performed under the same conditions and procedures as in Sample Shop 11-1.12-1.13-1 of Example 1, except that the conditions for creating layer (1) were as shown in Table 5. Each of the imaging members (
Sample boiled 11-1-1 to 1i-i-s, 12-1-1 to 1
2-1-8.24 samples of 13-1-1 to 13-1-8) were created. Each of the electrophotographic image forming parts obtained in this way was individually installed in a copying machine, and under the same conditions as described in each example, each of the electrophotographic image forming members corresponding to each example was prepared. We evaluated the overall image quality of the transferred image and the durability after repeated 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 The same procedure as in Example 1 was followed except that when forming layer (1), the target area ratio of silicon wafer and graphite was changed to change the content ratio of silicon atoms and carbon atoms in amorphous layer (1). Each of the imaging members was created in exactly the same manner as Sample A11-1. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated about 50,000 times, and then image evaluation was performed, and the results shown in Table 7 were obtained. Ta. Example 5 Sample A12 of Example 1 except that when forming the N(II) layer, the flow rate ratio of SiH4 gas and C2H4 gas was changed to change the content ratio of silicon atoms and carbon atoms in FI ([). Each of the image-forming members was produced by the same method as in Example 1-1. After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When the image was evaluated, the results shown in Table 8 were obtained. Example 6 When forming layer (I), 8iH gas, SiF4 gas,
C1! Except for changing the flow rate ratio of H4 gas and changing the content ratio of silicon atoms and carbon atoms in layer (1),
Each of the imaging members was made in exactly the same manner as Sample 7i13-1 of Example 1. 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 Sample A11 of Example 1 except that the layer thickness of layer (I) was changed.
Each of the image-forming members was produced by the same method as in Example 1-1. The steps of image formation, development, and cleaning as described in Example 1 were repeated, and the common layer forming conditions in the examples of the present invention shown in Table 10, Table 2, Table 4, and Table 10 and above are shown below. Substrate temperature: germanium atom (Ge) containing layer...
・About 200℃ discharge frequency: 13.56 Mll (z reaction dark reaction chamber pressure: Q, 3 Torr

[BRIEF DESCRIPTION OF THE 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 respectively show the first layer (1). 11 to 15, explanatory diagrams for explaining the distribution state of germanium atoms in the first layer <
1) An explanatory diagram for explaining the distribution state of nitrogen atoms in the
FIG. 16 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 17 and 18 are distribution state diagrams showing the content distribution concentration state of each atom in the embodiment of the present invention, respectively. . 100... Photoconductive member 101... Support body 102... First 0M (1) 103...
...Second layer (1) C -1-→-C 0C2/i C27 C(N) □ (, (N) C(N) (170υ (/7θ2) )

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, a first layer exhibiting photoconductivity composed of an amorphous material containing silicon atoms and germanium atoms, and a silicon atom and carbon a second layer made of an amorphous material containing nitrogen atoms, and the first layer contains nitrogen atoms, and the distribution concentration in the layer thickness direction is A photoconductive member characterized by a skewer having a first layer region, a third layer region, and a second layer region of C(1), C(3J, and C(2), respectively, in this order from the support side. (However, C(3) alone is unlikely to be the maximum, and C(1), C(2). If any one of C(3) becomes 0, the other two become O. (2) The photoconductive member according to claim 1, wherein the first layer contains hydrogen atoms. (3) The first layer contains halogen atoms. A photoconductive member according to claim i1 and claim 2. The photoconductive member according to claim 1. (5) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer is uniform in the layer thickness direction. Member. (6) The photoconductive member according to claim 1, h, in which the substance that controls conductivity is contained in the first part. (8) The photoconductive member according to claim 6, which is an atom belonging to group V of the periodic table. The photoconductive member described in .