JPS60138561A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member having high sensitivity and excellent durability, etc. by incorporating N so as to have the max. distributed concn. part smoothly in the layer thickness direction into the 1st amorphous layer formed with a region G contg. Si and Ge and a region S contg. Si in this order on a conductive base. CONSTITUTION:Such a layer region 105 in which Ge is distributed uniformly or at a high concn. on the base side in Si is formed on a conductive base 101. A region 106 contg. Si without contg. Ge is formed on the region 105 to provide the 1st amorphous layer 102. N is incorporated into the layer 102 so as to increase or decrease gradually in the layer thickness direction and to have the region having the max. distributed concn. near the layer surface within the layer. The 2nd amorphous layer 103 contg. Si and C is formed on the layer 102 by which a photoconductive member 100 provided with a photoreceptive layer 104 consisting of the layers 102 and 103 is obtd. The photoconductive member of an all environment type which forms the image having high quality and has excellent durability, etc. is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a photoconductive material having f1 sensitivity to electromagnetic waves such as light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). Regarding parts.

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 has a high sensitivity, a high signal-to-noise ratio [photocurrent (Ip
)/dark current (I d) ), has absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, and has a high ti! It has a dark resistance value of .

and that there is no pollution 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-5i) is a photoconductive material that has recently attracted attention.
Publication No. 855718 describes an image forming member for electrophotography,
German Publication No. 2933411 describes an application to a photoelectric conversion/reading device.

According to Heigo et al., a photoconductive member having a photoconductive layer composed of conventional A-3I has a low dark resistance value and a low light sensitivity.

Electrical, optical, and photoconductive properties such as photoresponsiveness.

The reality is that there are still areas that need to be further improved in terms of use environment characteristics such as temperature resistance and stability over time, and it is necessary to improve overall characteristics.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of When a conductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in so-called ghost development, which causes afterimages, or when used repeatedly at high speeds, responsiveness gradually decreases. There were many cases where spots appeared.

Furthermore, a-3i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when commonly used halogen lamps and fluorescent lamps are used as light sources, there is still room for improvement in that they do not waste light on the longer wavelength side effectively.

In addition, the light Q1 is not sufficiently absorbed in the photoconductive layer, and some of the light reaches the support. - If the support itself has a high reflectance for light passing through the photoconductive layer, interference due to hair reflection will occur in the photoconductive layer, causing "pockets" in the image. This is one factor.

This effect becomes larger as the irradiation spot is made smaller in order to increase the resolution, and is a serious problem especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using a-3T material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive type Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

For example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the inhibition of charge injection from the support side in a dark area is not sufficient. This often occurs.

Furthermore, if the layer thickness exceeds 10 or more layers, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes after it is left in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs particularly when the support is a drum-shaped support commonly used in the field of electrophotography, and there is a point IIf to be solved in terms of stability over time.

Therefore, while efforts are being made to improve the properties of the a-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the points set forth in "a-3t".
As a result of comprehensive research and consideration from the viewpoint of applicability and applicability as photoconductive members used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms and germanium An amorphous 4,4 material containing at least either a hydrogen atom or a halogen atom, so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium. [Hereinafter, r a -5iGe (H, Photoconductive materials designed and produced under specific conditions not only show extremely superior properties in practical use, but also surpass conventional photoconductive materials in all respects, especially in electrophotography. The present invention is based on the discovery that it has extremely excellent properties as a photoconductive member for use in applications, and that it has an absorption spectrum characteristic of +O on the long wavelength side.

The present invention has stable electrical, optical, and optical 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. The main object of the present invention is to provide a photoconductive member that is extremely resistant to light fatigue, does not exhibit any deterioration phenomenon even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to have high light sensitivity in the entire satellite light range;
In particular, it is an object of the present invention to provide a photoconductive member that is excellent in matching with a semiconductor laser and has a fast optical response.

Still another eleventh aspect of the present invention is that the W, r
It is an object of the present invention to provide a photoconductive member which has excellent i-ability, is dense and stable in terms of structural arrangement, and has high layer quality.

Still another object of the present invention is to provide a charge control system for electrostatic image formation to the 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 retention ability and has excellent electrophotographic properties with almost no deterioration in its properties even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography that has a high 0 degrees, clearly shows halftones, and can easily obtain high-resolution, high-I/X, and high-quality images. It is.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with a support.

The photoconductive member of the present invention includes a support for the photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms and provided on the support, and a first layer region (G) containing silicon atoms. a first layer comprising a photoconductive second layer region (S) made of an amorphous material and provided on the first layer region (G); It has a photoreceptive layer consisting of a second layer made of an amorphous material containing silicon atoms and carbon atoms, and the -th layer of No. 1111 has:
Contains nitrogen atoms, the concentration distribution of the nitrogen atoms in the layer thickness direction is smooth, and the maximum distribution concentration of the nitrogen atoms is
It is characterized by being located inside the first layer.

The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems and has extremely excellent electrical and optical properties.

Shows photoconductive properties, electrical pressure resistance, and usage environment properties.

In particular, when the undeveloped J photoconductive member is applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical properties are stable, and it is highly sensitive. It has a high signal-to-noise ratio at 1 bar, 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. Obtainable.

Furthermore, in the photoconductive member of the present invention, the photoreceptive layer formed on the support is strong and has excellent adhesion to the support, and can be used continuously 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 optical range, is particularly excellent in matching with a semiconductor laser, and has a fast optical response.

Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a schematic configuration diagram for explaining the layer configuration of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. and a second layer (II) 103 provided thereon. First layer (
I) 102 and the second layer (II) 103 constitute a light-receiving layer 104.

The first layer (1) 102 is made of an amorphous material (hereinafter ra-Ge) containing germanium atoms and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms.
(Si, H, Amorphous material containing one (hereinafter ra-si(H,X)
A first layer region (G) 105),
A second layer region (S) 10 exhibiting photoconductivity provided in
6.

The germanium atoms may be contained in the first layer region (G) 105 so as to be uniformly distributed in the first layer region (G) 105, or evenly distributed in the layer thickness direction. However, the distribution concentration may be non-uniform. In any case, in the first layer region (G) 105, with respect to the in-plane direction parallel to the surface of the support,
Gel Manila 1 and R- are required to be contained in a uniform distribution in order to make the properties uniform in the in-plane direction.

In particular, it is contained throughout the layer thickness direction of the first) 5(I) 102, and on the side opposite to the side where the support 101 is provided (the free surface of the light-receiving layer 104). 107 side) so that it is more distributed on the support 101 side (the interface side between the photoreceptive layer and the support 101), or the opposite distribution state is created. Germanium atoms are contained in the first layer region (G) 105.

In the photoconductive member of the present invention, as described above, the distribution state of germanium atoms contained in the first layer region (G) 105 is as described above in the layer thickness direction, and the distribution state of the germanium atoms is as described above. In the in-plane direction parallel to the surface of 101, it is desirable to have a uniform distribution state.

In the present invention, germanium atoms are not contained in the second layer region (s)ioe provided on the first layer region (G) +05. By forming the layer (I) 102, a photoconductive member having excellent photosensitivity to light in the entire range of wavelengths from relatively short and long wavelengths to relatively short wavelengths, including the 1-dimension optical region, can be obtained. Obtainable.

Further, in one of the preferred embodiments, the distribution state of atoms in the gel manila J in the first layer region (G) 105 is such that germanium atoms are continuously and uniformly distributed in the entire layer region. , the distribution concentration C of germanium atoms in the layer thickness direction decreases from the support 101 side toward the second layer region (S) 106, so that the first layer region (G)
105 and the second layer region (S) 106, by extremely increasing the distribution concentration C of germanium atoms at the end of the support lO1 as described later. , when a semiconductor laser or the like is used, the light on the long wavelength side that is almost completely absorbed by the second layer region (S) 106 is substantially absorbed in the first layer region (G) 105. It is possible to completely absorb the IJ2 and to prevent the interference caused by the IJ2 from the surface of the support 101.

FIGS. 2 to 1O show typical examples in which the distribution state of germanium atoms contained in the first layer region (G) 105 in the layer thickness direction is non-uniform.

In FIGS. 2 to 1O, the horizontal axis Ihl+ indicates the molecule of germanium atoms u y = degree C, and the vertical axis indicates the layer thickness of the first layer region (G) 105 exhibiting optical conductivity, t6 is the position of the surface of the first layer region (G) 105 on the support 101 side, and tT is the first layer region (G) on the opposite side to the support body.
The position of the surface of 105 is shown. That is, in the first layer region (G) 105 containing germanium atoms, layers are formed from one side toward the t□ side.

In the example shown in FIG. 2 in the first layer region (G) 105, FIG. From the interface position where it contacts the surface of The distribution concentration gradually and continuously decreases from C to C. At the interface position tT, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the layer region (G) 1 of il
The distribution concentration C of germanium atoms contained in 05 gradually and continuously decreases from the dark I odor C4 from position t6 to position rtt, forming a distribution state such that the concentration C1 is reached at position t□. are doing.

In the case of FIG. 4, the distribution of germanium atoms contained in the first layer region (G) 105 is 0 degrees C, which is determined by the position t from the position transport.
Up to 2, the concentration is taken as a constant value C6, and the position tU and position -tT
Gradually, i! l! Continuously decreased, jl
At t, i''j ty, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is gradually decreased continuously from the concentration C8 from the position t to the position L1. It is substantially zero at 1T.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in the position t
, and position 1J, the concentration is a constant value C9 and 1
It is concentrated at position t. Between position 1J and position t□, the distribution concentration C is linearly decreased from position 1j to position 1c.

In the example shown in FIG. 7, the first layer top M(G)1
The distribution concentration C of germanium lid contained in 05 takes a constant value of concentration C++ from position t to position t,
From the position t4 to the position t-t, there are 41 states as the concentration decreases from the concentration C4 to the concentration C1 in a -dimensional function.

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at position t8
The concentration decreases linearly from C, 4 to substantially zero up to position t.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 decreases in a sub-order function from the concentration cIr to the concentration C1 from the position 1Q to the position tE. , between position t5 and position tv, the concentration c5. An example is shown in which the value is set to a constant value.

In the example shown in FIG. 1θ, the first layer region (G)
The distribution concentration C of germanium atoms contained in 105 is a concentration C1□ at position t8, and is initially slowly decreased from this concentration C17 until reaching position Ftt,
Near position t6, the position t is rapidly decreased and
In this case, the concentration is assumed to be C1.

Between position t and position 7, the concentration decreases rapidly at first, and then gradually decreases until the concentration becomes CI9 at position t7, and extremely slowly between position t7 and position t9. and is gradually decreased, and in e
Leads to l1ffi C, o. Between position t8 and position ta, the concentration is reduced from Cj6 to substantially zero according to a curve shaped as shown in the figure.

From the north, according to Figures 2 to 10, the first layer area (G)
As described in some of the typical examples of the distribution state of germanium atoms contained in 105 in the layer thickness direction, in the present invention, on the support lO1 side, there is a part with a high distribution concentration C of germanium atoms. , when the first layer region (G) 105 is provided with a distribution state of germanium atoms having a portion where the distribution concentration C is considerably lower on the interface t□ side than on the support 101 side, One of the preferred examples
It is mentioned as one of the

The first layer region (G
) 105 is preferably a localized region (A
) is desirable.

For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 1O, the interface position 1! It is desirable that the layer be provided within 5 points from l in the layer thickness direction.

The J2 localized region (A) may be the entire layer region (LA) up to 5#1° thick from the interface wLB, or it may be a part of the layer region (L7). In some cases.

Whether the localized region (A) is to be a part or all of the layer region (L) is determined as appropriate depending on the characteristics required of the first layer region (G) 105 to be formed.

In the localized region (A), as a distribution state of germanium atoms contained therein in the layer J1 direction, the maximum value Cl1lax of 4iC degree for germanium atoms is preferably 1000 atoms ppn+ or more with respect to the sum with silicon atoms. It is desirable that the layer be formed in such a manner that a distribution state can be obtained, more preferably 5,000 atomic ppm or more, and optimally 1xlO atomic ppm or more.

That is, in the present invention, the first layer region (G) 105 containing germanium atoms has a distributed concentration within 51 L in layer thickness from the support 101 side (layer region from 18 to 5 thick). It is preferable to form so that a maximum value Cmax exists.

In the present invention, the content of germanium atoms contained in the first layer region (G) 105 may be determined as desired so as to effectively achieve the object of the present invention, but silicon For the sum with atoms, preferably l
-10XIO' atoms ppm, more preferably 100~
9.5XlO゜atomic ppm, optimally 500-8X
It is desirable that the content be 10'-7-ppm.

The distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is on the support lot side. If a decreasing change is given from 0 to 107 toward the free surface 107 of the photoreceptive layer 104, or vice versa, the rate of change curve of the distribution concentration C can be arbitrarily designed as desired. By doing so, it is possible to realize the first layer region (G) 105 having the required characteristics as desired.

For example, the distribution concentration C of germanium atoms in the first layer region (G) 105 is sufficiently increased on the support lot side, and as low as possible on the free surface 107 side of the photoreceptive layer 104. By applying a change in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light in the entire range of wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition to being able to achieve
It is possible to effectively measure interference prevention +j· against interfering light such as laser light.

In the present invention, the layer thickness T6 of the first layer region (G) 105
is preferably 30A to 50IL, more preferably 30IL.

Further, the layer thickness T of the second layer region (S) 106 is preferably 0.5 to 90 pL, more preferably 1 to 80 pL, and most preferably 2 to 50 g.

The layer thickness T8 of the first layer region (G) 105 and the second layer region (
S) The sum of the layer thicknesses T (T, +T) of 106 is the phase 1 of the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer.
Based on the organic relationship between them, it is determined as desired when designing the layers of the photoconductive member.

In the photoconductive part 4 of the present invention, the above (TB+T)
The numerical range of is preferably 1 to 100 IL, more preferably 1 to 80 IL, and optimally 2 to 50 #L.

In a more preferred embodiment of the present invention, the layer thickness TB and the layer thickness T described in item 1 are each appropriately selected to satisfy the relationship Tn/T≦1. It is desirable to

The number of layer thickness TB and layer thickness T in the above case II′j
More preferably, Tn/T≦0.9,
Optimally, it is desirable that the values of layer thickness TB and layer thickness T be determined so that the relationship T B /T≦0.8 is satisfied.

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is 1X10 atoms ppm or more, the layer thickness Ts of the first layer region (G) 105 is It is desirable to make it fairly diluted, preferably 30 pL.
Hereinafter, it is more preferably 25μ or less, most preferably 20g or less.

In the present invention, the layer thickness of the first layer region (G) 105 and the second layer region (G) 105 are
The layer thickness of the layer region (S) 106 is one of the important factors for effectively achieving the object of the present invention. , due care must be taken in designing the photoconductive member.

In the photoconductive member of the present invention, high photosensitivity and high dark resistance are achieved, as well as improved adhesion between the support and the photoreceptor. In (I) 102, a layer region (N) containing nitrogen atoms is provided. Nitrogen atoms may be contained in the entire layer region of the first layer (I) 102, or may be contained only in a part of the layer region of the first layer (I) 102, so that they are omnipresent. You can let me.

In the present invention, the distribution state of nitrogen atoms in the layer region (N) is uniform in the in-plane direction parallel to the surface of the support lO1, but is uniform in the in-plane direction parallel to the surface of the support lO1. It is non-uniform in the thickness direction.

In the example shown in FIG. 11, the distribution concentration C(N
) is the position t from the surface position of the first layer 102 on the support side.
The concentration is q1 in the layer region from position t to position t. In the layer region up to, the concentration increases rapidly from position t to position t16, and reaches the peak value q of the distribution concentration at position too. In the layer region from position t, 6 to position R, t++, the distribution concentration C(N) of nitrogen atoms is at position t.
The concentration decreases rapidly as it approaches l+, and reaches the concentration q1 at the −r102th surface position t□ on the opposite side from the support 101.

In the example shown in FIG. 12, the distribution concentration C(N
) is the concentration q in the layer region from position t8 to position t+z
, in the layer region from position t to position t13, there is a rapid increase from position t+x to position tlJ, and position t1m
The distribution concentration has a peak value C,4 at , and decreases to almost zero as it approaches position t1 in the layer region from position tlJ to position t.

In the example shown in FIG. 13, the distribution concentration C(N
) from position 1B to position t2. In the layer region from qf to q6, it increases gradually from qf to q6, and reaches the peak value q6 of the distribution concentration at position t11, and in the layer region from position i t to position tT, it increases rapidly as it approaches position 1. Decreased,
At position t7, the density becomes Cj2.

In the example shown in FIG. 14, the distribution concentration C(N
) is at position t, degree q7, and from position Rte to position t3.
It decreases as it approaches position t1. The concentration becomes q8.

In the layer region from position tlr to position tI6, nitrogen o;
(Child distribution cl!', :C(N) is r degrees C, 9't'
constant. Position t5. In the layer region from to position t17, the distribution concentration of nitrogen atoms increases, and the distribution concentration C(N) at position t17 of plate 0i, φ takes a peak value q.

In the layer region from position t17 to position t, the distribution concentration C(N) of nitrogen atoms decreases to a concentration C, . . . at position tT.

In the present invention, when the main purpose of the layer region (N) containing the nitrogen source f- provided in the -0 first layer (I) 102 is to improve photosensitivity and dark resistance, First layer (I
) 102, and in order to prevent charge injection from the free surface of the photoreceptive layer, it is provided so as to occupy the vicinity of the interface on the free surface side, and is provided so as to occupy the entire layer area of the support and the photoreceptive layer. When the main purpose is to strengthen the adhesion between the first layer (I) 102 and the support side end layer region (
E).

In the case of the above first objective, the nitrogen atom-containing acid contained in the layer region (N) is relatively small in order to maintain high photosensitivity, and in the case of the above second objective, the nitrogen atom-containing acid contained in the layer region (N) is kept free of the photoreceptive layer. In order to prevent charge injection from the surface, a relatively large amount is added, and the third
For this purpose, it is desirable to use a relatively large amount in order to ensure enhanced adhesion to the support.

In addition, in order to simultaneously achieve the three conditions described in -1-1, it is necessary to distribute the concentration at a relatively high concentration on the support side and at a relatively low concentration at 0 degrees in the center. + In the interface layer region on the surface side, a distribution state of nitrogen atoms such as a larger number of nitrogen atoms may be formed in the layer region (N).

In the present invention, nitrogen ++ in the layer region (N) containing nitrogen element r- provided in the second layer (I) 102;
<Containment 1- of r- is due to the characteristics required of the layer region (N) itself, or when the layer region (N) is provided in direct contact with the support 101, the property between the layer region (N) and the support 101. contact force°
Yellow+R can be used as appropriate in terms of organic relationships such as the relationship with surface characteristics.

In addition, when another layer region is provided in direct contact with the layer region (N), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region may also be determined. Taking into consideration, the content of nitrogen atoms is selected as appropriate.

j, 1 of "nitrogen + t; The sum of atoms and nitrogen atoms (rT (S 1
GeN)), preferably C1,OO
It is desirable that the content be 1 to 50 atomic %, more preferably 0.002 to 40 atomic %, and optimally 0.003 to 30 atomic %.

In the present invention, the layer region (N) is the first layer (I) 102
Or, even if it does not occupy the entire area of the first layer (I) 102, the ratio of the layer area (N) (7) layer thickness To to the layer thickness T of the first + 13 (I) 102 When the amount is sufficiently large, it is desirable that the content of nitrogen atoms contained in the layer region (N) be sufficiently smaller than the value in tiij.

In the present invention, the layer thickness T of the layer region (N).

If the ratio of the first layer (I) to the layer thickness T of 1.02 is 2/5 or more, the layer area (N)
Is it contained inside? ;, the elementary atom (,1 of -1, limit,
In particular, it is preferably 30 atomic % or less, more preferably 20 atomic % or less, and optimally 10 atomic % or less based on T (SiGeN).

In the present invention, a layer region containing nitrogen atoms (, N
) is a localized region (1) in which nitrogen atoms are relatively highly concentrated 1 (1 and 01) in the near-f force on the support 101 side and/or the second layer (IT) '103 side as described above. B), and in this case, between the support 101 and the first layer (I) 102,
: It is possible to further improve one's personality and to improve one's acceptance.

The localized area (13) is preferably provided within 5 jt from the surface of the first layer (I) 102 on the support 101 side and the first layer (II) 103 side.

In the present invention, the localized region (B) is located on the support of the first layer (I) 102 or on the first layer (I) 102.
II) Layer area (L,) up to 5μ thick from the surface on the 103 side
In some cases, it may be the whole of the layer region (LT), or it may be a part of the layer region (LT).

Whether the localized region (B) is to be a part or all of the layer region (LT) is determined as appropriate depending on the QLR properties required of the photoreceptive layer 104 to be formed.

The localized region CB) is defined as the distribution state of the nitrogen atoms contained therein in the layer thickness direction at the maximum value Cmax of the distribution concentration C(N) of nitrogen atoms, preferably 500 1,000 ppm or more, more preferably I~ preferably 800 ppm or more 1-1 optimally 10
It is desirable that the layer be used in such a way that it can be in a state where it can be removed by more than 00w ppm.

[11j In the present invention, the first layer (I) 10
The layer region (N) containing two mountains of nitrogen atoms has a concentration of min'/I' within a layer thickness of 58 L from the surface of the support 101 side or the second layer (II) 103. /13 big i'iCma! It is desirable that it be formed so that it exists.

・In the k invention, the first layer (1j, 02
Specific examples of the halogen source -f contained in the compound include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the photoconductive member of the present invention, the first layer region (G) 105 in which gel contains nium atoms and/or the second layer region (S) 10 in which no kermanium atoms are contained.
6 contains a substance (D) that governs the conduction properties, so that the layer region (G) can control the conduction properties of the layer region (S) as desired. , can be controlled. In the present invention, the layer region (PN) containing the substance (D) that controls conduction properties is the first layer (PN).
I) It may be provided in part or all of 102. Alternatively, the layer region (P N ) may be provided in a part or part of the layer region (G) or (S).

The substances (D) that govern such conduction 4 and 11 are:
The so-called impurities in the semiconductor field can be mentioned, and in 51 JI, pA! ! Examples include a P-type impurity that imparts conductive properties and an n-type impurity that imparts n-type conductive properties. Specifically, p-type impurities include atoms that belong to Group Ⅰ of the periodic table (Group 1II, 1+I'), such as Ishibomoto (B), Aluminum A (A), Gallium (Ga), and Indium. (In), thallium (TJD, etc.), and particularly preferably used are B and Ga.As n-type impurities, atoms belonging to group V of the periodic table (group V atoms) are used. , for example, phosphorus (p), by silicon (A's), antimony (sb,), bismuth (Bi)
etc., and P and As are particularly preferably used.

In the present invention, the first 13 (I) to 2 t
The inclusion 111j of the substance (D) that governs the characteristics contained in the material (D) is the conductive property required for the second layer (I) 102, or the fact that the second layer (I) 102 directly Support provided in contact with +i
It can be selected as appropriate depending on the organic relationship, such as the relationship with 1.

Also, Ino of 1iFi: Substance that controls conductive properties (D)
In particular, when the first layer (I) 102 contains locally in a desired layer region of the second layer (I) 102, the first ff(I) 102, the characteristics of other layer regions provided in direct contact with this layer region and the other F! In the present invention, the content of the substance (D) that governs the conduction properties is appropriately selected taking into consideration the relationship with the properties at the contact interface with the region.6 In the present invention, the first layer (I') Conduction contained in 1024. The content of the substance (D) that dominates the r cell is preferably 0.01 to 5 x IO atoms ppm,
/71” suitably 0.5 to lXlO4 atomic ppm,
The optimum content is preferably 1 to 5 x 10 atomic ppm.

In the present invention, the content of the substance (CD) in the layer region (PN) containing the substance (D) that controls conduction properties
t, preferably less than 30 atomic ppm-1-1 IIf
Suitably 50 atoms ppm or more, optimally lOO atoms p
pm or more, the substance (D
) is preferably contained locally in a part of the layer region of the first layer (I) 102, especially in the first layer (I) 102.
It is preferable that the particles be unevenly distributed in the support side end layer region (E).

(1) Among the above, by containing the substance (D) that controls the conductive characteristics in the first layer region (E) at the support side end of the first layer (I) 102 in a content not less than the above-mentioned value. ,
For example, if the substance (D) is the above p-type impurity,
When the free surface 107 of the photoreceptive layer 104 is subjected to polar charging treatment, the movement of electrons injected from the support 101 side into the photoreceptive layer 104 can be effectively prevented;
When the substance controlling the conduction characteristics is the n-type impurity, when the free surface lO7 of the photoreceptive layer 104 is charged to e polarity, the photoreceptor layer 104 is charged from the support 101 side.
It is possible to effectively prevent the movement of holes injected therein.

In this way, when the support-side end layer region (E) contains a substance ('D) that controls conduction characteristics of one polarity, the remaining layer region of the first layer (I) 102, That is, the layer region (Z) excluding the support side end layer region (E)
may contain a substance that controls the conduction characteristics of the other polarity, or a substance that controls the conduction characteristics of the same polarity may be added to the actual material contained in the end layer region (E) on the side of the support 15. It's even less than a song; you can also make it M and include I.

In such a case, the substance (D) contained in the layer region (Z) that controls the conduction 46 may be the substance contained in the support 11 side end layer region (E). pole I
11 and the content of 1it, but preferably 0.001-1000 atomic ppm, more preferably 0.05-500 atomic ppm. The content is preferably 0.1 to 200 atomic ppm.

In the present invention: 1. When the same type of substance governing conductivity is contained in the special body side end layer region (E) and the layer region (Z), the content j- of the material in the layer region (Z) is preferably It is desirable that the amount is 30 atomic ppm or less. In addition to the above-mentioned cases, in the present invention, the first layer (I) 102 includes: - a layer region containing a substance controlling conductivity having a force polarity; It is also possible to provide a so-called depletion layer in the contact layer region by providing it in direct contact with a layer region containing a substance governing conductivity. 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 (i) 102 so as to be in direct contact with each other, so that the so-called p-n A junction can be formed to provide a depletion layer.

In the present invention, the first layer region (G) 105 composed of a-Ge (S i , H, The vacuum 14 utilized is formed by the product method. For example, by glow discharge method, a −G
The first layer region composed of e (Si, H, X) (
G) To form 105, basically a source gas for supplying germanium atoms that can supply germanium atoms, a source gas for supplying silicon atoms that can supply silicon atoms, and a source gas for introducing hydrogen atoms as necessary. and/or the raw material gas for introducing halogen atoms by reducing the internal pressure.
) is introduced into a deposition chamber at a desired pressure state to cause a glow discharge in the deposition chamber, and a-Ge (S
It is sufficient to form a layer consisting of i, H, X). Furthermore, in order to include the germanium atoms in the first layer region (G) 105 in a non-uniform manner, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve. −
A layer consisting of Ge (S i , TI , X) may be formed. In addition, in the sputtering method, for example, a target composed of silicon atoms, or a target composed of silicon atoms, or a germanium source and a target composed of silicon atoms, is used in a 774 gas mixture using an inert gas such as Ar or He, or these gases as a pace. Using two targets composed of r- or a mixed target of silicon atoms and germanium original T-, if necessary, dilute [Ii] with a diluent gas of He or Ar\. The raw material gas for supplying gel manila J and atoms and, if necessary, the gas for introducing hydrogen atoms and/or halogen atoms into the deposition chamber for sputtering,
A first layer region (G) 105 is formed by forming a plasma atmosphere of a desired gas. In this sputtering method, when the distribution of germanium atoms is made non-uniform, the gas flow rate of the raw material gas for supplying the germanium source-r is controlled according to the desired change i +llt line, and the above-mentioned All you have to do is sputtering the target.

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. Heat and evaporate by resistance heating method or electron beam method (EB method), etc.
The first layer region (G) 105 can be formed in the same manner as in the sputtering method except that a light source is passed through a desired gas plasma atmosphere.

Substances that can be used as raw material gas for supplying silicon atoms used in the present invention include 5IH4, SiiH1, S
Silicon hydride (silanes) in a gaseous state or which can be gasified as i, 'H1, Sr*, H15 can be cited as one that can be effectively used, especially for ease of handling during layer creation work, silicon atoms In terms of supply efficiency, S iH,, S
1lH4 is preferred.

Gel Manila 1. j;
Ge, Hg, G e4H1,, Ge, Hll, G e,
H,4,G e7H,4,G e,H,t,Ge,H,
Germanium hydride in a gaseous state such as O or which can be gasified is mentioned as one that can be effectively used, especially in the production of one layer 1' + ease of handling during work, and good germanium atom supply efficiency - 4i GeH4, Ge, H6, G
e, H, are listed as preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the invention, such as gaseous or gasified halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include the following halogen compounds. Furthermore, it can be made into gaseous 7mj or gasified, which contains silicon atoms and halogen atoms as constituent elements. Hydrogen compounds containing halogen atoms are also effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, IJ chloride, halogen gas, iodine, BrF, C1F, Obun et al., BrF, Br.
Examples include interhalocene compounds such as F, IF, IF7, I(4, and IBr).

Examples of polycompounds containing a halogen element f, so-called halogen atom-substituted silane derivatives include, for example, S +zF4.5iiFz, SiCζ, SiB r4
The halogenated arsenic compound of ¥ can be mentioned as one of the most frightening.

When forming the characteristic photoconductive member of the present invention using a glow discharge method using such a silicon compound containing halogen atoms, the material gas for supplying germanium atoms and the
Hydrogenation as a raw material gas that can supply silicon atoms to
11S forming the first layer region (G) 105 consisting of a, -3iGe containing a desired support 1゛O1-H)\rogen atoms can be obtained without using an elementary gas.

When manufacturing the first layer region (G) 105 containing halogen atoms according to the glow discharge method, No. The first layer region (G
) 105 and generates a glow discharge to form a plasma atmosphere of the gas 9, thereby depositing the first layer region (G
) 105, but in order to make it easier to control the introduction ratio of hydrogen atoms, it is also desirable to use gases of elementary compounds containing hydrogen atoms in addition to these gases. A layer may be formed by mixing acids.

In addition, each gas may be used not only as a single type but also as a mixture of multiple types at a predetermined mixing ratio.

In order to introduce halogen atoms into the first layer region (G) 105 formed in either the sputtering method or the ion blating method, the above-mentioned halogen compound or the above-mentioned halogen j5; It is sufficient that a gas of a monoatomic compound is placed in a deposition chamber by four people to form a plasma atmosphere of the residue.

In addition, when introducing hydrogen atoms into the first layer region (G) 105, raw material scraps for hydrogen atom introduction, such as I2,
Alternatively, gases such as silanes and/or germanium hydride as described above may be introduced into a deposition chamber for sputtering 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.
In addition, hydrogen halides such as HF, HCfl, HBr, HI, S i HjF2, S iH YuI, etc.
S i l(, C island, 5iliC sentence, S i H, B
rs, S i HB r, "9rr) halogen-substituted silicon hydride, and G e HF,, G e HjFj,
G e H, F, G e HCl,, GeH, C1,,
G e H, Cl, GeHBrJ, GeH, Br,,G
eH,Br,GeHIj,Ge■(,1,,G
e H, I 9c7) Hydrogenated halogenated germaniumuno, a halide containing a hydrogen atom as one of its constituent elements,
GeF4, G e CgL,.

G e B r4 , G e I4, G e F,,G
The first layer region ('G
) 105 The starting material for the formation river is C.

Among these substances, halides containing hydrogen p; Since hydrogen atoms, which are extremely effective for control, are also introduced, they are used as a suitable source l) for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G) 105, in addition to the above, H or S t H+, 5i
zHx, Si, H@, Si4H+a, etc. c7) Hydrogenated urea with germanium or a germanium compound for supplying germanium atoms, or GeH4, G'eJ
H1, G e3Hg, G e4H1e, G e3P5
z,Ge7H,4,Ge7H,1,Ge7H+l
Ge? This can also be carried out by causing germanium hydride such as 11) and silicon or a silicon compound for supplying silicon atoms to exist in a deposition chamber to generate a discharge.

In a preferred embodiment of the invention, the first layer that can be formed? r
H, + of the hydrogen element r contained in the t region (G) 105), or :lX of the halogen atom, or the sum (H+X) of the hydrogen element -r and the halogen atom, Ir preferably, o ,,oi
~40 atomic %, more preferably 0.05 to 30 atomic %, optimally o, i to 25 Jj; (preferably child %).

In order to control the falsification of hydrogen atoms and/or halogen atoms contained in the first layer region (G) 105, for example, the support temperature and/or hydrogen atoms can be controlled.

Alternatively, the introduction of the starting material used to contain the halogen atom into the IllJll system, the discharge force, etc. may be controlled.

In the present invention, the second
The layer region (S) 106 is the first layer region (G) described above.
Starting materials (II) for forming the second layer region (S) 106 from the starting materials (I) for formation of 105 excluding the starting materials that will become the raw material gas for supplying germanium atoms
) can be formed according to the same method and conditions as when forming the first layer region (S) 106.

That is, in the present invention, the second layer region (G) 105 composed of a-3i (H, Formed by law. For example, to form the second layer region (S) 1-06 composed of a-3i (H, 7.
Together with the raw material scraps for supplying silicon atoms, a raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms as necessary is introduced into a deposition chamber whose interior can be depressurized to generate a glow discharge within the deposition chamber. A layer consisting of a-5j (H, In addition, when forming by a sputtering method, for example, when sputtering a target made of silicon atoms in an atmosphere of an inert gas such as Ar or He, or a moderate gas based on these gases, hydrogen atoms are Or/and a gas for introducing halogen atoms may be introduced into the deposition chamber for sputtering. In the present invention, the amount of hydrogen atoms, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the second layer region (S) 106 to be formed is preferably is desirably 1 to 40 atomic %, more preferably 5 to 30 atomic %, most preferably 5 to 25 atomic %.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (I) 102, the first layer (I) 1
In the formation of 02, the starting material for introducing nitrogen atoms is used together with the starting material for forming the first layer (I) 102, and the -j- is controlled and contained in the formed layer. “You should do it.

When a glow discharge method is used to form the layer region (N), nitrogen chloride (commercially available) is added to a material selected as desired from among the starting materials for forming the first W (I) 102 described above. starting materials are added. As such a starting material for introducing nitrogen atoms, most of the dregs-like substances having at least nitrogen atoms as constituent atoms or gasified substances that can be gasified can be used.

For example, raw material waste whose constituent atoms are silicon atoms, raw material gas whose constituent atoms are nitrogen atoms, and water Jz as necessary.
Either raw material gas containing r- or/and halogen atoms is mixed at a desired mixing ratio, or raw material gas containing silicon atoms and nitrogen atoms and hydrogen atoms are used. or mix a raw material gas containing silicon atoms and a raw material gas containing three constituent atoms: silicon atoms, nitrogen atoms, and hydrogen atoms, also at a desired mixing ratio. It can be used in combination with.

Alternatively, a raw material gas having nitrogen atoms as constituent atoms may be mixed with a raw material gas having silicon atoms and hydrogen atoms as constituent atoms.

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms used when forming the layer region (N) has nitrogen as a constituent atom, or has nitrogen and hydrogen as constituent atoms. For example, nitrogen (N2), ammonia (NHJ)
), hydrogen azide (HN□), ammonium azide (NH,N,), gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides It is possible to list the following. In addition to the introduction of nitrogen atoms, halogen atoms can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4
Examples include halogenated nitrogen compounds such as N, ).

In the present invention, the layer region (N) may further contain oxygen atoms in addition to nitrogen atoms in order to further enhance the effect obtained by nitrogen atoms.

Examples of raw material gases for introducing oxygen atoms into the layer region (N') include oxygen (0,), ozone (
Oj), -nitrogen oxide (NO), nitrogen dioxide (Noyo)
, - Nitrogen dioxide (Nyo0), Nitrogen sesquioxide (NyoOl
), Nitrogen oxide (Nyo04), Nitrogen sesquioxide (Nyo05), Nitrogen trioxide (N, OJ) Disiloxane ( HjS i OS i HJ) Trisiloxane (I
Examples include lower siloxanes such as IJSiO3iHjO9iH, ).

To form the layer region (N) by the sputtering method, when forming the first layer (I) 102, a single crystal or polycrystalline silicon wafer or an IfSi3N4 wafer, or silicon atoms and 51g1% Sputtering may be carried out by using a wafer containing a mixture of as a target and sputtering them in various gas atmospheres.

For example, if a silicon wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and then the material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and a deposition chamber for sputtering is prepared. The silicon wafer may be sputtered by introducing the gas into the silicon wafer and forming a gas plasma of these scum.

Alternatively, silicon atoms and Si and N4 can be used as separate targets, or by using a single target mixed with silicon atoms and 5ijN4, in an atmosphere of dilution gas as a sputtering gas, or at least Sputtering may be performed in a gas atmosphere containing hydrogen atoms and/or halogen atoms 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 example of glow discharge described above can be used as an effective gas also in the case of suba-interning.

In the present invention, when a layer region (N) containing nitrogen atoms is provided when forming the first layer (I) 102, the distribution of nitrogen atoms contained in the layer region (N) Concentration C (N)
is changed in the layer thickness direction to obtain the desired distribution state in the layer thickness direction (
depth profile) In order to form the right layer region (N), in the 41 cases of glow discharge, the distribution concentration CCN
) may be introduced into the deposition chamber while changing the gas flow force appropriately according to a desired rate of change curve. For example, the opening 1-1 of a predetermined needle valve provided in the waste flow path system 4 may be appropriately changed by any commonly used method, such as manually or by using an externally driven motor. At this time, for example, a microcomputer or the like may be used to control the flow section according to a predesigned rate of change curve to obtain a desired curve.

When forming the layer region (N) by a sputtering method, the distribution concentration C(N,) of nitrogen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (N,) of nitrogen atoms in the layer thickness direction.
In order to form a depth profile, firstly, as in the case of the glow discharge method, the starting material for the introduction of nitrogen atoms is used in a gaseous atmosphere, and when the gas is introduced into the deposition chamber. This is accomplished by appropriately changing the gas flow rate as desired.

Second, as a target for sputtering, for example, a target 7 made of a mixture of silicon atoms and S+iN4 is used.
), this can be done by changing the mixing ratio of silicon atoms and Si3N4 in advance in the layer thickness direction of the target.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, to structurally introduce group II atoms or g5v group atoms f-, when forming one layer, the starting material for group II atoms or the starting material for WSV group atoms to be introduced is in a gas state. It may be introduced into the deposition chamber together with other starting materials for forming the second region (S) 106. As a starting material for use in such a Group 1 raw material, it is desirable to use a material that is in the form of a scum at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Such a number ■
Specifically, the starting materials for the introduction of boron atoms are B, H,, B4H5,, BfII, and Br.
ll1. Examples include hydrogenated hydrogen atoms such as BtHl-B7H5L and BtH,4, and halogenated hydrogen atoms such as oFl, sci, and BBra. In addition, A
M C, liu, G e C island, G e (CHa)
, I n Cua, T u C9,3, etc. may also be mentioned.

As a starting material for group V Hara Chihiro, the one that is effectively used in undeveloped IJIJ is phosphorus, and for Hara Chihiro four people, P
Hydrogen north end of H,, I-1,, etc., PH, I, PF,,
PF,,PCu,,p c Kai, PBr3, P'Bry
, P I, and the like are mentioned. In addition, A
sHj, AsF,, As C9, B, As B
r6, A s Fs, SbH,, 5bF1.5bFf,
sbcm, 5bC1,, B i H,, B1Cu,, B
i, Br3. etc. can also be cited as effective starting materials for group V atom conduction.

In the present invention, the layer thickness of the layer region (PN) that constitutes the first layer ('I) 102, contains a substance that controls the conductive properties, and is provided unevenly on the support 1 '01 side. as,
It is determined as desired according to the characteristics required of the layer region (PN) and other layer regions forming the first layer (I) 102 formed on the layer region (PN). However, the lower limit is preferably 50A or more. Further, the content yli of the substance controlling the conduction properties contained in the layer region (PN) is 30 atoms p.
pm or more, the upper limit of the layer thickness of the layer region (PN) is preferably 10 W or less, preferably 8 hi or less, and optimally 5 μ or less.

In the photoconductive member 100 shown in FIG. 1, a second layer (II) 103 formed on a first layer (I) 102
has a free surface, mainly 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 (I) 102 and the second layer (II) 103 has a common constituent element of silicon atoms, both Chemical stability is sufficiently ensured at the laminated interface of layers (I) 102 and (II) 103.

The first layer (II) 103 in the present invention is an amorphous material (hereinafter referred to as r a -(
S ixc+ -x) y(H,X)+-yJHowever, 0
<x, y<1).

The formation of the second layer 103 (11) composed of a (Si=C+-x)y(H,X)+-y can be performed using glow radiation 1L method, sputtering method, ion plantation method, ion plate ink IJl': is carried out by the method, electron beam method, etc. These manufacturing methods may be selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, manufacturing scale, and the desired characteristics of the photoconductive member to be produced, or may be used to Advantages include that it is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and that it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the second layer (II) 103 to be manufactured. A glow discharge method or a sputtering method is preferably employed.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same system to form the second layer (II) 10.
3 may be formed.

To form the second layer (103) by the glow discharge method, a − (S ixc<−1−) y (H, X )
The raw material gas for forming 1-y is mixed with a dilution gas at a predetermined ratio as necessary, and introduced into the deposition chamber for vacuum deposition where the support lot is installed, and the introduced gas of,
The first layer (I) 102, which has already been formed on the support 101, is converted into a gas plasma by generating a glow discharge, and a −(−3:xC+−x)y(H
, X)+-y may be deposited.

In the present invention, a-(SixC+-x)y (H,
The raw material gas for forming Most of the following are used (1)
Ru.

When using a raw material gas having a silicon atom as one of silicon atoms, carbon atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas having a silicon atom as a constituent element r and a constituent atom having carbon atoms. A raw material gas containing a hydrogen atom and/or a raw material gas containing a halogen atom, if necessary, into a desired one.
A raw material gas containing silicon atoms as constituent atoms and a raw material gas containing carbon atoms and hydrogen atoms or/and a raw material gas containing halogen atoms as constituent atoms are used in a mixed ratio. This is also JJl of Tokoro 91! Mixed in a combined ratio, or original gas with silicon atoms as constituent atoms = 1 gas and raw material gas with three constituent atoms: silicon atoms, carbon atoms, and hydrogen atoms, or three constituent atoms: silicon atoms, carbon atoms, and halogen atoms It can be used in combination with a raw material gas having constituent atoms.

Alternatively, a raw material gas containing carbon atoms as constituent atoms may be mixed with a raw material gas containing silicon atoms and hydrogen atoms, or a raw material gas containing silicon atoms and halogen atoms as constituent atoms may be used. A raw material gas containing carbon atoms as a constituent atom may be mixed with the raw material gas.

In the present invention, halogen atoms contained in the second layer (II) 103 are preferably fluorine, chlorine, bromine,
Iodine, especially fluorine, J), 1, +i' is preferred.

In the present invention, raw material gases that can be effectively used to form the second layer (II) 103 include:
Examples include substances that are in a gaseous state at room temperature and pressure, or substances that can be easily gasified.

In the present invention, SiH, 'S i, HA, S
i3H@, S i4H,. Silane such as
Silicon hydride gas such as e), carbon atoms and hydrogen atoms as the constituent f, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and 2 to 3 carbon atoms Examples include acetylenic hydrocarbons J, hydrogen simple substance, halogenated water 'V', interhalogen compounds, silicon halides, halogen-substituted silicon islands, and silicon hydride.

Specifically, saturated hydrogen (methane (C) (4
), ethane (C,ll1), propane (C,He)
, n-butane (n -Cd(,,), pentane (Cg
H,, ), ethylene hydrocarbons include ethylene (
C=HA), propylene (C=HA), butene-1 (
C4H, ), butene-2 (c,tHt), imbutylene (C,H,), pentene (C,H,.), acetylene hydrocarbons include acetylene (CjH), methylacetylene (C,L ), butyne (c, H,), and halogen alone: F7. Also, chlorine, bromine, iodine halogen gas, and hydrogen halides include FHlHl, HCI
, HBr, and interhalogen compounds include B r F ,
CJJF, CIFJ, C%F, BrFr
B r F3, IF, , IF, , ICI, IBr, silicon halides include S i F4, S fJ'a,
S i C sentence. .

SiCM, Br, 5iCu, Br,, 5iCuBr3,
S i Cl, I, S i B r4, halogen-substituted silicon hydride, S i H, F,, S i H, C
11,5i) (Cmu, S i H, C sentence, S iH, B
r, 5i) t, Br, l, S i HB r,.

As silicon hydride, S i H4, S LHs, S
i4H,.

Silanes, etc., etc. can be mentioned.

In addition to these, CF, , CCl, , CBr4, CHF3,
CH,F,,CH,F, CH,Cl,CH3Br,
CH,I.

Halogen-substituted paraffinic hydrocarbons such as CYH, C1, etc.
Fluorinated sulfur compounds such as SF4 and SFA, 5t(CH
ri4. S 1 (alkyl silicide such as qH mountain, SiC structure (CH,)s, S ic 314 (':'Ha, S
Silane derivatives such as halogen-containing alkyl silicides such as i Cl, CH, etc. can also be mentioned as effective.

These second layer (II) 103-forming substances contain silicon raw material, carbon atoms, halogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the second layer (II) 103 to be formed. It is selected and used as desired when forming the second layer (II) 103 so that it contains atoms.

For example, the inclusion of silicon atoms, carbon atoms, and hydrogen atoms can be easily achieved in 1) and 11. A layer with desired properties can be formed with S i ((1:II,), and halogen atoms are included (7) S i HCl,
S 1HpCL.

The first layer (IT), 1
03 By introducing into the device of the formation river and avoiding the generation of glow emission '+IS, a -(Sixc+-X) V
(CJlj+H)+-111% growling first layer (II)
1 '03'e Shadow formation is possible.

To form the second layer (II) 103 by the sputtering method, a monocrystalline or polycrystalline silicon wafer, a graphite wafer, or a wafer containing a mixture of silicon atoms and carbon atoms is used as a target. 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 you use silicon wafers by binding them,
Raw material gases for introducing carbon atoms, hydrogen atoms, and/or halogen atoms are diluted with diluting gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma of these gases. Alternatively, the silicon wafer may be sputtered using the sputtering method, or alternatively, silicon atoms and carbon atoms may be used as separate targets, or by using a single target containing a mixture of silicon atoms and carbon atoms. Sputtering may be performed in a gas atmosphere containing hydrogen atoms and/or halogen atoms depending on the situation. As a material serving as a raw material gas for introducing carbon atoms, hydrogen atoms, and halogen atoms, the material for forming the second layer (II) 103 shown in the glow discharge example described above is a material that is also effective in the sputtering method. can be used as

In the present invention, the so-called rare gas, such as He, Ne, Ar
, etc. are also suitable.

The first layer (II) 103 in the present invention is formed deeply (1) so that the required properties can be provided in 91 ways. That is, silicon atoms, jk elementary atoms, 1. Substances that contain water, IN atoms, and/or halogen It;f atoms have structural forms ranging from crystalline to amorphous, depending on the conditions of their creation, and gas-physical properties. , properties ranging from conductive PI to semiconducting properties to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, desired properties depending on the purpose a −(S rxc+ −x) with
The preparation conditions are strictly selected as desired so that y(H,X)+-y is formed. For example, to provide the second layer (II) 103 with the main purpose of improving electrical voltage resistance, a-(S :xC+=x)y (Ht
'

In addition, when the second layer (II) 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and it becomes less resistant to the irradiated light. As an amorphous material with a certain degree of sensitivity, a −(S ixc+ −x ) y(H,X)+
-y is created.

On the surface of the first layer (I) 102, a-(SixC+-X
)y (H,X)+-y second layer (II)1
The temperature of the support lot during layer formation is an important factor that influences the structure and properties of the formed layer. It is desirable that the temperature of the support during layer formation be strictly controlled so that SixC1-x)y (H,X)t7y can be formed as desired. In the present invention, the second layer ('II) 103 for effectively achieving the desired purpose
The formation of the second layer (II) 103 is carried out by appropriately selecting the optimum range according to the formation method, but the temperature of the support during layer formation is preferably 20 to 400°C, more preferably It is desirable that the temperature is 50 to 350°C, most preferably 100 to 300'C.

To form the second layer (II) 103, glow discharge is used to form the second layer (II) 103, since delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. However, when forming the second layer (II) 103 by the layer forming method '9, the discharge temperature during layer formation is This is one of the important factors that influence the characteristics of a − (S ixc+ −x )yX+−y where power is created: f.

A having the characteristics for achieving the objective of the present invention
-(S ixc+ -x)yX+-y is preferably produced effectively with good productivity as a discharge power condition of 10 to 300 W, more preferably 20 to 250 W, @
It is desirable that the power is suitably 50 to 200W.

The gas pressure in the deposition chamber is preferably 0.01 to I Torr.
, more preferably about 0.1 to 0.5 Torr.

In the present invention, for creating the second layer (II) 103, the support temperature and the desired number of discharge powers (1 ft K range) may be mentioned, but these layer creation factors are independent. The desired characteristics a - (S 1xC1-x) V (H
,

Second layer (II) 103 in the photoconductive member of the present invention
The carbon atom acid contained in the second layer (TI) 103
This is an important factor for forming the second layer (II) 103 that provides the desired characteristics to achieve the object of the present invention. Second layer (II) 1 in the present invention
The amount of carbon atoms contained in 03 is the same as that of the second layer (Il,)
It can be determined as desired depending on the type of amorphous material constituting 103 and its characteristics.

That is, the general formula a -(SixC+-X) y(H,
The amorphous material denoted by

However, O<a<1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as r a -(S
It is written as ibC+-b)c H+-cJ. However, 0<b,
c<1), and an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (
Hereafter, ra-(SidC+-d) e (H,X)+-
It is written as eJ. It is classified as 1).

In the present invention, the second layer (II) 103 is a-5ia
When composed of C+-a, the amount of carbon atoms contained in the second layer (II) 103 is preferably 1×lθ to 90
atomic %, more preferably 1 to 80 atomic %, optimally 10 to 80 atomic %
A desirable content is 75 atomic %. That is, if expressed using the above a-S 1aCr-a chisel, a is preferably 0.1 to 0.99999, more preferably 0.
2 to 0.99, optimally 0.25 to 0.9.

In the present invention, the second layer (II) 103 is a-(S
When composed of ibc+-b)c Hj-c, the amount of carbon atoms contained in the second layer (II) 103 is preferably 1 x lO to 90 at%, more preferably 1
The content of hydrogen atoms is preferably 1 to 40 at%, more preferably 2 to 35 at%, most preferably 10 to 80 at%. A hydrogen content of 5 to 30 atom % is desirable, and photoconductive members formed with hydrogen content in this range are excellent in practical applications and can be sufficiently applied.

That is, the previous a −(S ibc+−b) Hl−c(7
), b is preferably o, t~0.99999
, more preferably 0.1 to 0.99, optimally 0.15 to
0.9, C is preferably 0.6 to 0.99, more preferably 0.65 to 0.98, optimally 0.7 to 0.95.

The second layer (II) 103 is a −(S idc+−d
)e (H,'X)1-e, the content j of carbon atoms contained in the second layer (II)
, 7- is &r preferably IXIσ ~ 90 atomic %,
The content of halogen atoms is more preferably 1 to 90 at%, most preferably 10 to 80 at%, and the content of halogen atoms is 1 to 90 at%.
- is preferably 1 to 20 atom %, more preferably 1 to 18 atom %, and optimally 2 to 15 atom %, and the halogen atom content is within this range. The photoconductive member prepared in this case can be sufficiently applied to practical applications, and the content of the hydrogen element f-, which may be contained as necessary, is preferably 19 atomic % or less, more preferably is desirably 13 atomic % or less.

That is, the previous a −(SidC+−d) e (H,X)
If expressed as d and e of +-e, d is preferably 0.1
~0.99999, more preferably 0.1-0.99, optimally 0.15-0.9, e is (Ir preferably 0.8-0.
Desirably, it is 0.99, more preferably 0.82-0.99, optimally 0.85-0.98.

The number range of the layer thickness of the second layer (II) 103 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.

Moreover, the layer thickness of the second layer (II) 103 is the same as that of the layer (II) 1
The amount of carbon atoms contained in 03 and the first layer (I) 10
The relationship with the layer thickness in 2 must be appropriately determined based on organic relationships according to the characteristics required for each layer area, and in addition, productivity and mass production It is desirable to consider economic efficiency as well.

The layer thickness of the second layer (II) 103 in the present invention is preferably 0.003 to 30 l, more preferably 0.0
It is desirable that the value is between 0.04 and 20 p, most preferably between 0.005 and 10 p.

The support 101 used in the present invention may be electrically conductive or electrically insulating.

Examples of the conductive support include NiCr, stainless steel, An, Cr, Mo, Au, Nb, Ta, V, Ti, and P.
Examples include metals such as T, Pd, and alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate I, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Films or sheets of synthetic resins such as polystyrene and polyamide, glass, ceramics, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, NiCr1, A
Cr, Mo, Au, Ir, Nb, Ta, ■, T
Conductivity can be imparted by providing a thin film consisting of i, Pt, Pd, In20t, SnOY, ITO(In, Oj+SnOJ, etc.), or a synthetic resin film such as a polyester film. Ba,
NiCr, An, Ag, Pb, Zn, Ni, Au, Cr
, Mo, Ir, Nb, Ta, V, Ti, Pt, etc., on the surface by vacuum evaporation, electron beam deposition, sputtering, etc., or by laminating the surface with the above metal. conductivity is suspected.

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 shown in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support lot is appropriately determined so as to form a desired photoconductive member, but if flexibility is required as a photoconductive member, the thickness of the support lot may be determined to ensure that it does not fully exhibit its function as a support. It is made as thin as possible within this range. In such a case, from the viewpoint of manufacturing the support, handling, mechanical strength, etc., the support 3. The thickness of Ol is preferably 10 mm or more.

Next, an outline of an example of the method for manufacturing the light guide member of the present invention will be explained.

FIG. 15 shows an example of a photoconductive member manufacturing apparatus.

In the figure, gas cylinders indicated by 1102 to 1106 are electrically sealed with raw material gas for forming the photoconductive member of the present invention.
As an example, 1102 is II e
S i H4 gas (purity 99.999%)
, hereinafter abbreviated as SiH4/He. ) cylinder, 1103 is H
GeH4 gas diluted with e (purity 99.999%, hereinafter abbreviated as G, eH4/He) cylinder, 1104
is NH3 gas (purity 99-99%) cylinder, 1105
is a He gas (99.999% purity) cylinder, l l O
, 6 is a H Yugas (purity 99.999%) cylinder.

In order to flow these dregs into the reaction chamber 1101, valves 1122 to 1126 of gas cylinders 1102 to 1106,
Check that the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 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 of the vacuum gauge 1136 becomes approximately 5X10 Torr, the auxiliary valves 1132, 1133 and the outflow valve 11
71-1121 are closed.

Next, to give an example of forming a photoreceptive layer on the cylindrical substrate 1j37J2 as a support, SiH4/He gas from the gas cylinder 1102 and GeH4/He gas from the knife sponge 1103 are used. , the NH and waste from the waste cylinder 1104 are removed from the valve 11.
22,1123.1124 open and outlet pressure gauge 112
By adjusting the pressure of 7,1128°1129 to 1 kg/crn' and gradually opening the inlet valves 1112, 1113, and 1114, the mass flow controller 1107
1108 and 1110 respectively. Subsequently, outflow valve 1117, 1118°1119, auxiliary valve 1
132 is gradually opened to allow each gas to flow into the reaction chamber 1101.

At this time c7) S iH4/ [1e gas warmth and G
e The outflow valves 1117 and 11 are adjusted so that the ratio of the H4/He gas flow: Ii and the NH gas flow r beam is the desired value.
18° 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. and)S
The temperature of the body 1137 is raised to 50~ by the heating heater 1138.
After confirming that the temperature is set within the range of 400°C, set the power supply 1140 to the specified power ψ and turn on the reaction chamber 1'l.
A glow discharge is generated in the O1, and at the same time, the opening L1 of the valves 1118 to 1120 is appropriately changed by applying G e H4/He gas and manual or externally driven motors, etc. according to a pre-designed change rate curve. The flow rate of the N 2 H gas is adjusted, thereby controlling the distribution concentration C(N) of germanium atoms and nitrogen atoms contained in the layer formed.

2, the first layer region (G) 105 is coated on the substrate 11371 to a desired layer thickness by maintaining glow discharge for a desired time.
form. At the stage where the first layer region (G) 105 has been formed to the desired layer thickness, the outflow valve 1116 is completely closed and the desired layer is formed according to the same conditions and procedures, except for changing the discharge conditions as necessary. By maintaining the glow discharge for a period of time, a second layer region (S) 106 substantially free of germanium atoms can be formed on the first layer region (G) 105.

First layer region (G) 105 and second layer region (S) 1
In order to contain the substance (D) that controls conductivity in 06, the first layer region (G) 105 and the second layer region (S
) 106, for example, a gas such as B, H, PHj, etc. may be added to the gas introduced into the deposition chamber 1101.

A first layer CI) 102 is thus formed on the substrate 1137.

First layer (I) 1 formed to a desired layer thickness as described above
To form the second layer (II) 103 on the 02, for example, each of SiH4 gas and CJH4 gas is converted into He by the same valve operation as in the formation of the first layer 102(I). The diluent gas may be diluted with a diluent gas such as the like, and then supplied into the reaction chamber 1101 to cause glow discharge according to desired conditions.

In order to contain halogen atoms in the second layer (II) 103, the second layer (II) 103 is formed in the same manner as above using, for example, SiF4 gas and C2H4 gas, or by adding SiH gas to this. do it.

Needless to say, all the outflow valves other than the gas outflow valves required when forming each layer are closed, and when forming each layer, the waste used to form the previous layer is inside the reaction chamber 1101 and the outflow valve is closed. 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 and the auxiliary valves 1132 and 1133 are opened to prevent the main/<lube 1134
If necessary, fully open the system to create a high vacuum in the system.

The amount of carbon atoms contained in the second layer (II) 103 can be determined by, for example, changing the flow rate ratio of SiH4 gas and CyuH4 gas introduced into the reaction chamber 1101 in the case of glow discharge as desired. Alternatively, when forming a layer by sputtering, by changing the sputter area ratio of silicon powder and graphite wafer when forming the target, or by changing the mixing ratio of silicon powder and graphite powder and molding the target. It can be controlled as desired. The amount of halogen atoms contained in the second layer (II) 103 can be adjusted by adjusting the flow rate of a raw material gas for introducing halogen atoms, for example, when introduced into the SiF4H4 gas reaction chamber 1101. be done.

Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Same flow side 1 Using the manufacturing apparatus shown in FIG. 15, a sample (sample No. 1-1) was prepared as an image forming member for electronic reciprocity under the conditions shown in Table 1 on a cylindrical Al J& body as a support. −
17-4) were prepared respectively (Table 2).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 6 shows the distribution concentration of nitrogen atoms, and FIG. 17 shows the nitrogen atom content distribution concentration.

Each sample thus obtained was placed in a charging exposure experimental device, corona charged for 3 seconds (sec), and immediately irradiated with a light image.

The light image uses a tungsten lamp light source, 25 Luxa
A light amount of sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the sample (imaging member) by cascading the surface of the sample (imaging member) with a developer (containing toner and carrier) having a positive charge. 5. The toner image on the sample.
When transferred onto transfer paper using a corona charge of 0 KV, clear high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

”-instead of the light source and the tungsten lamp, an 810 nm GaAs semiconductor laser (10 mW) was used.
The image quality of the toner transfer images was evaluated for each sample under the same toner image forming conditions except that the electrostatic image was formed using A clear, high-quality image with good gradation reproducibility was obtained.

Samples zl (sample Nos. 21-1 to 27-4) as image forming members for electrophotography were prepared on a cylindrical A-shaped substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. 15. (Table 4).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 6 shows the concentration distribution of nitrogen atoms, and FIG. 17 shows the nitrogen atom content distribution concentration.

When each of these Samples 1 was subjected to 91 11 image evaluation tests similar to those in Example 1, all samples provided high quality toner transfer images. Also, for each sample, 3
When a repeated use test was conducted 200,000 times in an environment of 8°C, 180% R11, no deterioration in image quality was observed in any of the samples.

Example 3 Sample No. 11-1.1 of Example 1 except that the preparation conditions for the second layer (I[) +03 were as shown in Table 5.
Each of the electrophotographic image forming members (No, 11-1-1-11-
1-8.12-1-1 to 12-1-8, 13-1-1
-13-1-8) were created. Each of the electrophotographic image forming members obtained in this way was individually installed in a copying machine, and each image forming member for electrophotography corresponding to each example was printed under the same conditions as described in each example. Therefore, we evaluated the overall image quality of the transferred image and evaluated its durability through repeated and continuous use.

Table 6 shows the results of the overall image quality evaluation of the transferred image of 6 trials F1 and the evaluation of durability after repeated continuous use.

Example 4 Example 1 except that when forming the second layer (positive) 103, the target area ratio between the silicon wafer and the graphite was changed and the content ratio of silicon atoms and carbon atoms in the layer (11) was changed. Each of the image forming members was prepared in exactly the same manner as in Trials I'lNo and Ill. For each of the image forming members thus obtained, the image forming and cleaning steps 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.

Example 5 Second layer (I[)+03. Sample No. 12- of Example 1 except that when forming the layer, the flow rate ratio of SiH4 gas and C,H,1' gas was changed to change the ratio of the content of silicon atoms and carbon atoms in the layer (It). Each of the imaging members was made in exactly the same manner as in Example 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 I performed the image lit value, the results were as shown in Table 8 (fl)
Ta.

Example 6 When forming the second group (I) 103 layer, 5i) 14 gas,
By changing the flow ratio of SiF4 gas and CJIJf gas, the layer (
Each of the image forming members was created in exactly the same manner as Sample No. 13-1 of Example 1, except that the content ratio of silicon atoms and carbon atoms in 1) was changed.

Each of the imaging members thus obtained was subjected to approximately 5 imaging, developing, and cleaning steps as described in Example 1.
After repeating the process several times, image evaluation was performed and the results shown in Table 9 were obtained.

Example 7 Each of the image forming members was created in exactly the same manner as in Sample No. 111 of Example 1, except that the layer thickness of the second layer (I[) 103 was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 1θ.

The layer forming conditions in the examples of the present invention shown in Table 10 onwards are shown below.

Substrate temperature: germanium atom (Ge) containing layer...approximately 2
00℃ Germanium Ijir-F (G e ) non-containing layer
・・About 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram 1M for explaining the layer structure of the light guide member of the present invention, and FIGS. 2 to 1O are the distribution of germanium atoms in the first layer (I), respectively. The explanatory diagrams for explaining the state, FIGS. 11 to 14, show the first layer (
I) An explanatory diagram for explaining the distribution state of nitrogen atoms in
FIG. 15 is a schematic explanatory diagram of the device used in the present invention;
FIGS. 16 and 17 are distribution state diagrams showing the content distribution concentration state of each atom in the embodiment of the present invention, respectively. Zoo... Photoconductive member 101... Support 102... First layer (I) 103... Second layer (II) 104... Photoreceptive layer Applicant: Canon Corporation Figure 1 C C Figure 11 Figure 12 C (N)

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member; a first layer region (G) made of an amorphous material containing germanium atoms and provided on the support; and a first layer region (G) comprising an amorphous material containing germanium atoms; A second layer region (S) exhibiting photoconductivity is formed of an amorphous material containing
) and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and carbon atoms, The first layer contains nitrogen atoms, the concentration distribution of the nitrogen atoms in the layer thickness direction is smooth, and the maximum distribution concentration of the nitrogen atoms is inside the first layer. Element. (2) The photoconductive member according to claim 1, wherein at least one of the first layer region (G) and the second layer region (S) contains hydrogen atoms. (3) Claims 1 and 2 contain a halogen element f- in at least one of the first layer region (G) and the second layer region (S). photoconductive member. (4) The photoconductive member according to claim 1, wherein the distribution state of atoms in the gel manila 1 in the first layer region (G) is non-uniform. (5) Germanium source r in the first layer region (G)
The photoconductive member according to claim 1, wherein the distribution state of - is uniform. (7) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (8) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to Group V of the periodic table.