JPS60140259A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain good and stable electrical, optical and photoconductive characteristics, good photosensitive characteristic on a long wavelength side and excellent mechanical strength and durability by providing a photoreceptive layer having the specific layer constitution of a-SiGe(H, X) on a base. CONSTITUTION:A photoconductive member has a base 101 and a photoreceptive layer 104 consisting of the 1st layer 102 which is constituted of amorphous material contg. a Ge atom and has the 1st layer region G105 provided on the base and the 2nd layer region S106 provided on the region G105 and having photoconductivity and the 2nd layer 103 which is provided on the layer 102 and is constituted of an amorphous material contg. Si and O atoms. An N atom is incorporated into the layer 102 and the concn. thereof is so distributed as to be smooth in the layer thickness direction and that the max. distributed concn. exsits in the layer 102. H and halogen atoms are incorporated into either of the layer regions G and S. The distribution condition of Ge in the region G may be ununiform or uniform and further a material governing conductivity such as the IIIgroup or V group atom is incorporated into the region G.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, etc.). Regarding.

Photoconductive materials that form photoconductive layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity, SN, ratio [photocurrent (IP)
, )/high dark current (Idl), absorption spectrum characteristics that match the spectrum I/L characteristics of the electromagnetic waves to be irradiated, fast photoresponsiveness, desired dark resistance value, and resistance to the human body during use. On the other hand, solid-state imaging devices are required to have characteristics such as being non-polluting and being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on these points, optical i and electric z have recently been attracting attention.
The material is amorphous silicon (hereinafter referred to as a-8i). Application to photoelectric conversion and reading devices is described.

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

Electrical, optical, and photoconductive properties such as photoresponsiveness.

The reality is that there are points that can be further improved in terms of use environment characteristics such as moisture resistance and meridional stability, and furthermore, it is necessary to improve the overall characteristics.

For example, when applying it to an electrophotographic image forming member and trying to achieve both high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use. 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 a commonly used halogen lamp or fluorescent lamp is used as a single light source, there is still room for improvement in that long wavelength light cannot be used effectively.

In addition, if the irradiated light is not absorbed sufficiently in the photoconductive layer and the amount of light reaching the support increases,
If the support itself has a high reflectance for light passing through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, causing "pockets" in the image. .

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

Furthermore, when the photoconductive layer is composed of a-Si material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are 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 photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There are many cases.

Furthermore, when the layer thickness exceeds 10-odd micrometers or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs 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-3t material itself, when designing photoconductive members, it is necessary to take measures to solve all of the problems described in 1-1.

The present invention has been made in view of the above-mentioned points, and it is concerned with the applicability and applicability of a-Si as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has silicon atoms and germanium atoms as its base and contains at least either hydrogen atoms or halogen atoms, so-called hydrogenated amorphous silicon germanium, and halogenated amorphous silicon. Germanium or halogen 7-containing hydrogenated amorphous silicon germanium [hereinafter referred to generically as r a
-5iGe('H,X)J] to #6ti,
Photoconductive members designed and produced with a photoreceptive layer that exhibits photoconductivity as described below have extremely excellent properties in practical use. It is superior in all respects to conventional photoconductive materials, especially as a photoconductive material for electrophotography, and has an absorption spectrum on the long wavelength side. The present invention is based on the discovery that it has excellent properties.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to have high photosensitivity in the entire visible 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 object of the present invention is to provide excellent adhesion between a layer provided on a support and a support, and between each laminated layer, and to provide a dense and stable structural arrangement. It is an object of the present invention to provide a high quality photoconductive member.

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 excellent electrophotographic properties with almost no deterioration in its properties observed even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member for electrophotography that can easily produce high-quality images with high density, clear halftones, and high resolution.

Still 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. The first layer region (G) is composed of an amorphous material.
A first layer having a photoconductive second layer region (S) provided thereon, and an amorphous material provided on the second layer and containing silicon atoms and # atoms. The first layer contains nitrogen atoms, and the concentration distribution of the nitrogen atoms in the layer thickness direction is smooth, and the maximum concentration of the nitrogen atoms is In. The concentration is characterized in that it is 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 photoconductive member of the present invention 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 has high sensitivity and high sensitivity. It has a high signal-to-noise ratio, is resistant to light fatigue, has good repeated use characteristics, has high density, and has clear halftones.
In addition, high-resolution, high-quality images can be stably and repeatedly obtained.

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 repeatedly used continuously at high speed for a long time. can do.

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse.

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

FIG. 1 is a schematic configuration diagram 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. 1 includes a support 101 for the photoconductive member, a first layer (I) 102 provided on the support 101, and 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 (I) 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.
(Sj, H, An amorphous material containing at least one (hereinafter ra-9i (H,
X) J), the first layer region (G) 105
a photoconductive second layer region (S) 1 provided thereon;
0-6.

Germanium atoms are distributed evenly and uniformly in the first layer region (G) 105.
05, or it may be contained evenly in the layer thickness direction, but the distribution concentration may be non-uniform. In both cases, the first layer region (G) 1
In 05, it is necessary for germanium atoms to be uniformly distributed and evenly contained in the in-plane direction parallel to the surface of the support in order to make the properties uniform in the in-plane direction. be.

In particular, it is contained evenly in the layer thickness direction of the first layer (I) 102, and once on the side opposite to the side where the support 101 is provided (the free surface of the photoreceptive layer 104). 107 side)
The support 101 side (the photoreceptive layer and the support 1
The germanium atoms are contained in the first layer region (G) 105 so that they are distributed more toward the interface side with the first layer region (G) 105 or vice versa.

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 distribution1. In the present invention, the second layer region (S) provided on the first layer region (G) 105 ) 106 does not contain germanium atoms, and by forming the first layer (I) 102 in such a layered structure, it is possible to emit light from relatively short and long wavelengths to relatively long wavelengths, including the visible light region. It is possible to obtain a photoconductive member that has excellent photosensitivity to light having wavelengths in the entire wavelength range.

Further, in one of the preferred embodiments, the distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously and evenly distributed throughout the entire layer region, and germanium atoms are evenly distributed throughout the layer region. Since the distribution concentration C of atoms in the layer thickness direction is given a change that decreases from the support lot side toward the second layer region (S) 106, the first layer region (G) 1
05 and the second layer region (S) 106, and by extremely increasing the distribution concentration C of germanium atoms at the side edge of the support 101 as described later, When a semiconductor laser or the like is used, the light on the long wavelength side, which is almost completely absorbed by the second layer region (S) 106, is substantially completely absorbed in the first layer region (G) 105. It is possible to absorb the light and prevent interference due to reflection from the surface of the support 101.

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

2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G) 105 exhibiting photoconductivity, and t represents the support 101. tT indicates the position of the surface of the first layer region (G) 105 on the side opposite to the support side. That is, in the first layer region (G) 105 containing germanium atoms, layers are formed from the t side to the 1 side.

In the example shown in FIG. 2, in the first layer region (G) 105, FIG. Interface position where the surface of 101 contacts 1. From 1. Up to the position 1., the distribution concentration C of germanium atoms takes a constant value of 01 and is contained in the first layer (I), and up to the position 1. From C to interface position tT, the distribution concentration gradually and continuously decreases from C. At the interface position Htv, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the first layer region (G) 1
The IO concentration C of the germanium atoms contained in 05 gradually and continuously decreases from the concentration C4 from the position 1B to the position 0, forming a distribution state in which the concentration C1 is reached at the position t7.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is constant at a concentration c6 from position t to position t1, and from position t2 to position f!
l is gradually and continuously decreased between d and d, and at position t7, the minute AjC degree C is substantially zero (here, substantially zero means that it is less than the detection limit amount). ).

In the case of FIG. 5, the distribution concentration J&C of germanium atoms contained in the first layer region (G) 105 is gradually decreased from the concentration C9 from position 1B to position D, and It is substantially zero at position t.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at position 1
Between B and position tJ, degree C is -j round function at position 1. The position has been reduced to even more.

In the example shown in FIG. 7, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 takes a constant value of concentration C++ from the position axis to position -, and from position t
From position 4 to position D, the distribution state is such that the concentration decreases linearly from the concentration CIJ to the concentration CI.

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in position 1.
The concentration decreases in a linear manner from Q+ to substantially zero as the concentration approaches the position.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 varies from position t8 to position 1. Until the concentration ω is reached, the concentration is decreased linearly from the concentration ω to the concentration Qb, and between the position 1.1 and the position ta,
An example in which the concentration q is set to a constant value is shown.

In the example shown in FIG. 10, the first layer region (G)
The distribution concentration C of germanium atoms contained in 105 is a concentration q7 at a position t8, and is slowly decreased from this concentration C/7 until reaching a position attn, and then at a position t6.
In the vicinity of the position , the concentration is rapidly decreased to a concentration C5# at the position t4.

position t, and position t1. The distance between t7 and t7 is decreased rapidly at first, and then slowly decreased until position t7.
The density becomes cd at the position t, and gradually decreases very slowly between the positions t and t, and reaches the density C4 at the position t2. Position 1. and between position 1T,
The concentration cJ is decreased according to a curve shaped as shown in the figure so as to become more substantially zero.

2. According to FIGS. 2 to 10, the first layer region (G
) As described above, some 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 portion with a high distribution concentration C of germanium atoms. However, 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 than that on the support body 101 side with the interface on the 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, it is desirable that the localized region (A) be provided within 5 IL in the layer thickness direction from the interface position 1.

The above localized region (A) may be the entire layer region (L) from the interface position t to a thickness of 5 mm, or may be a part of the layer region (LT). .

Whether the localized region (A) is 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), the distribution state of the germanium atoms contained therein in the layer thickness direction is such that the maximum value Cmax of the distribution concentration of germanium atoms is the sum of the distribution concentration of germanium atoms and silicon atoms.
Preferably 1000 atomic ppm or more, more preferably 50
00 atomic ppm or more, optimally lXl0 atomic ppm or more.”
In other words, in the present invention, the first layer region (G) 105 containing germanium atoms is formed from the support 101 side. It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5 PL (layer region from 1 B to 5 PL thick).

In the present invention, the content of germanium atoms contained in the first layer region (G) 105 is determined as desired so as to effectively achieve the object of the present invention, Preferably 1 to 1O
×lO atoms ppm, more preferably lOO~9.5X
10 atoms ppa+, optimally 500-8 X I
It is desirable to set it as Oj'' atoms-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 small when exposed to light from the support 101 side. If a decreasing change is given to the free surface 107 of the receiving layer 104 or vice versa, the rate of change curve of the distributed concentration C can be arbitrarily designed as desired. Accordingly, the first layer region (G) 105 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer region (G) 105 is sufficiently increased on the support 101 side, and as low as possible on the free surface 107 side of the photoreceptive layer 104. By applying changes in the distribution concentration C such as
It is possible to achieve high photosensitivity to light in the entire wavelength range from relatively short wavelengths to relatively short wavelengths, including the f-visual light region, and to prevent interference with coherent light such as laser light. can be measured effectively.

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

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 pL.

The layer thickness Ts of the first layer region (G) 105 and the second layer region (
S) The sum of the layer thicknesses T (TB+T) of 106 is determined based on the organic relationship between the properties required for both layer regions and the properties required for the photoreceptive layer as a whole. It is determined as desired during design.

In the photoconductive member of the present invention, the above numerical range of (TB+T) is preferably 1 to 100μ, more preferably 1
~80g, optimally 2-50IL.

In a more preferred embodiment of the present invention, the above layer thickness T
B and layer thickness T are desirably selected to have appropriate numerical values for each, preferably so as to satisfy the relationship TB/T≦1.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, preferably the relationship TB/T≦0.9, optimally T n /T≦0.8 is satisfied. It is desirable that the values of layer thickness Tn and layer thickness T be determined in the same manner. 'In the present invention, the content of germanium atoms contained in the first layer region (G) 105 is l x 10'
In the case of atomic ppm or more, the first layer region (G) 105
The layer thickness TB is desirably made quite thin, preferably 30 JL or less, even more preferably 25 JL or less, and optimally 20 JL 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, so it is necessary to ensure that the formed photoconductive member has sufficient desired properties. To,
Sufficient precautions α need to be taken when designing the photoconductive member.

In the photoconductive member of the present invention, the first layer ( I) A layer region (N) containing nitrogen atoms is provided in 102. Nitrogen atoms may be contained uniformly in the entire layer region of the first layer (I) 102, or may be contained in only a part of the layer region of the first layer (I) 102. It may be allowed to exist.

In the present invention, the distribution state of nitrogen atoms in the layer region (N) is such that the distribution concentration C(N) is uniform in the in-plane direction parallel to the surface of the support 101, but the layer thickness It is non-uniform in direction.゛In the example shown in Figure 1.1, the distribution concentration of nitrogen atoms C (
N) from the surface position tB of the first layer 102 on the support body side to position 1. The concentration is q1 in the layer region up to the point t.
In the layer region from 9 to position tto, the concentration increases rapidly from position t9 to position t, and the distribution concentration reaches a peak of 4tt CJI at position Lo. Position t. from position tll
The distribution concentration of nitrogen atoms C(N) in the layer region up to
decreases rapidly as it approaches position 1++, and support 1
The concentration q at one surface position of the first layer 102 on the opposite side from 01
, becomes.

In the example shown in FIG. 12, the distribution concentration C(N
) is at position 1. In the layer region from point W ta to position Lx, the concentration C decreases, and in the layer region from point W ta to position tlJ, it rapidly increases from position tin to position Er4, and reaches the peak value q4 of the distribution concentration at positions t and J, and reaches position t. , 3 to position t,
In the layer region up to, it decreases to almost zero as the position approaches the end.

In the example shown in FIG. 13, the distribution concentration C(N
) increases gradually from - to CJ4 in the layer region from position t# to position t14, reaches the peak value Csd of the Iri concentration at position -, and approaches position () in the layer region from position ts to position t1. It decreases rapidly as the number N
At t7, the concentration becomes qr.

In the example shown in FIG. 14, the distribution concentration C(N
) is the concentration Q at position t8? So, position 1. The position also decreases as it approaches t, and reaches the concentration CJ at positions t and c.

In the layer region from position 111 to position L/6, the distribution concentration C(N) of nitrogen atoms is the first in the concentration CJt.In the layer region from tn to position tT, the distribution concentration C(N) of nitrogen atoms decreases to a concentration q1 at the position.

In the present invention, when the main purpose of the layer region (N) containing nitrogen atoms provided in the first layer (I) 102 is to improve photosensitivity and dark resistance, the layer region (N) containing nitrogen atoms provided in the first layer (I) 102 is 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 between the support and the photoreceptive layer. When the main purpose is to strengthen the adhesion between the layers, the support side end layer region (E
).

In the case of the above first objective, the content of nitrogen atoms 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 content of nitrogen atoms 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 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 nitrogen atom content in the nitrogen atom-containing layer region (N) provided in the first layer (1) 102 depends on the characteristics required for the first layer region (N) itself or the layer. In the case where the region (N) is provided in direct contact with the support lot, the eye can be selected appropriately depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support lO1. I can do it.

In addition, when another layer region is provided in direct contact with the layer region (N), the characteristics of the nucleation layer region and the contact interface with the nucleation layer region 1. The content of nitrogen atoms is appropriately selected taking into account the relationship with the properties of the material.

The amount of nitrogen atoms contained in the layer region (N) is determined as desired depending on the properties required of the photoconductive member to be formed, but it is (hereinafter referred to as rT (SiGeN))" is preferably 0.001 to 50 atomic %, more preferably 0.002 to 40 atomic %, optimally 0.003 to 40 atomic %.
It is desirable that the content be 30 atomic %.

In the present invention, the one layer region (N) is the first layer LI>1
02 or the first layer (1) 102
Even if it does not occupy the entire area, the layer area (N) (7) Layer thickness To
(7) When the proportion of the first layer (I) 102 in the layer thickness T is sufficiently large, the upper limit of the content of nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value. It is desirable to

In the present invention, when the ratio of the layer thickness TO of the layer region (N) to the layer thickness T of the first layer (I>102) is two-fifths or more, the one layer region (N ) The upper limit of the amount of nitrogen atoms contained in T (SiGeN) is preferably 30 atomic % or less, more preferably 20 atomic % or less, and optimally 1O atomic % or less. is desirable.

In the present invention, the layer region (N) containing nitrogen atoms is located on the support 101 side or/and the second layer (N) as described above.
π) It is preferable to provide a localized region (B) containing nitrogen atoms at a relatively high concentration near the l.03 side; in this case, the support 101 and the first
The localized region (B) that can further improve the adhesion with the layer (I) 102 and the acceptance potential is located on the support 101 side of the first layer (I) 102 and It is desirable that the layer be provided within 5 l from the surface of the second layer (1r) 103 side.

In the present invention, the localized region (B) is formed in the first layer (
I) 102 pieces of support or second layer (X)
It may be the entire layer region (LT) from the surface on the 103 side to the final thickness of 5, 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 determined as appropriate depending on the characteristics required of the light-receiving layer 104 to be formed.

The localized region (B) is defined as the distribution state of the nitrogen atoms contained therein in the layer thickness direction, and the maximum concentration C(N) of nitrogen atoms (ficmax)
It is desirable that the layer be formed in such a manner that a distribution state can be obtained such that PJ or more, tIfL<1f is 800 atomic ppm or more, and optimally 1000 atomic ppm or more.

11tJ, in the present invention, the first layer (I) 102
The layer region (N) containing nitrogen atoms in the support 1
It is desirable that the maximum value Crnax of the distribution concentration exists within 5 in terms of layer thickness from the surface of the 01 side or the second layer (π) 103.

In the present invention, the halogen atoms contained in the first layer (I) 102 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 first layer region (G) 105 that contains germanium atoms and/or the second layer region (S) 106 that does not contain germanium atoms has a dominant conductive property. By containing the substance (D) that controls the conduction characteristics, the conduction characteristics of the layer region (G) and/or the layer region (S) can be controlled as desired.6 In the present invention, the substance that controls the conduction characteristics The layer region (P N) containing (D) may be provided in part or all of the first layer (1) 102. Alternatively, the layer region (PN) may be provided in part or all of the layer region (G) or (S).

Substances (D) that control such conductive characteristics include so-called impurities in the semiconductor field. Examples include a p-type impurity that provides a conductive property, and an n-type impurity that provides an n-type conductivity. Specifically, p-type impurities include atoms belonging to Group 1 of the periodic table (Group atoms) 1, for example, )6M element (B), aluminum (AU), gallium (Ga), and indium (In
), thallium ('I4), etc., and B and Ga are particularly preferably used. In addition, as an n-type impurity,
Atoms belonging to Group V of the periodic table (Group V atoms), such as phosphorus (P), atom (As), antimony (Sb), bismuth (Bi), etc., and are particularly used for tIf. are P and As.

In the present invention, the content of the substance (D) that controls the conductive properties contained in the first layer (I) 102 is determined by the conductive properties required for the second layer (I) 102 or The layer can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support 101 in which the second layer (I) 102 is provided in direct contact.

In addition, the substance (D) that controls the conduction characteristics described above is included in the first layer (
I) 102, the second layer (I) 10
When it is contained locally in a desired layer region of 2, particularly when it is contained in a layer region at the end of the support side of the first layer (I) 102, it is in direct contact with the layer region. The relationship between the properties of other layer regions provided and the properties at the contact interface with the nucleation layer region is also considered, and the substance (D
) content is selected appropriately.

In the final IJJ, the content of the substance (D) that controls conduction properties contained in the first layer (I) 102 is as follows:
Preferably 0. O1-5 x 104 atoms ppm, more preferably 0.5-1 x 104 atoms ppI1. Optimally, 1 to 5 x 10' atoms ppm is desirable.

In the present invention, the content of the substance (D) that controls conduction characteristics in the layer region (PN) containing the substance (D) is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more. ppm or more, optimally, 100 ppm or more, the substance (D) governing the conduction properties may be locally contained in a part of the layer region of the first layer (I) 102. It is desirable that it is unevenly distributed, particularly in the support side end layer region (E) of the first layer (I) 102.

Among the above, by containing the substance (D) that controls the conductive characteristics in the support side end layer region (E) of the first layer (1) 102 in a content that is equal to or higher than the above value, For example, if the substance (D) is the p-type impurity described above, when the free surface 107 of the photoreceptive layer 104 is charged to the polarity, it is injected into the photoreceptor layer 104 from the support 101 side. In addition, when the substance controlling the conduction characteristics is the n-type impurity, - the free surface 1 of the photoreceptive layer 104 (17 is charged to ○ polarity) When subjected to treatment, the light-receiving layer 10 is removed from the support 101 side.
The movement of holes injected into 4 can be effectively blocked.

In this way, when the support side end layer region (E) contains the substance (D) that controls the conductivity of one polarity, the remaining layer region of the first layer (I) 102, i.e. 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 may contain a substance that controls the conduction characteristics of the same polarity. The substance that controls
It may be contained in an amount much smaller than the actual amount contained in the support side end layer region (E).

In such a case, the content of the substance (D) that controls the conductive properties contained in the layer region (Z) depends on the polarity and the content of the substance contained in the support side end layer region (E). It is determined as desired depending on the content, but
Preferably o,ooi to 1ooo atoms ppm,
More preferably 0.05 to 500 atomic ppm, optimally 0.05 to 500 atomic ppm.
The content is preferably 1 to 200 atomic ppm.

In the present invention, when the support side end layer region (E) and the layer region (Z) contain the same type of substance that controls conductivity, the content of the substance in the layer region (Z) It is preferable that PPff1 be 30 atoms or less. In addition to the above-described case, in the present invention, the first layer (I) 102 includes a layer region containing a substance that controls conductivity having one polarity and a conductivity region having the other 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 controlling the properties. A blockage, e.g. in the first layer (I) 102,
The layer region containing the p-type impurity and the layer region containing the n-type impurity are provided so as to be in direct contact with each other to form a so-called p-
It is also possible to form an n-junction and provide a depletion layer.

In the present invention, the first layer region (G) 1.05 made of 4I of a-Ge (S f , H, X) is, for example,
It is formed by a vacuum deposition method that utilizes a discharge phenomenon such as a glow centering method, a sputtering method, or an ion blating method. For example, by the glow discharge method, a G
In order to form the first layer region (G) 105 composed of e (S + r H + A source gas for supplying silicon atoms capable of supplying silicon atoms, a source gas for introducing hydrogen atoms, and/or a source gas for introducing halogen atoms are introduced at a desired gas pressure into a deposition chamber whose interior can be depressurized. Then, a glow discharge is generated in the deposition chamber, and a-Ge(S i ,
A layer consisting of H, X) may be formed. Further, germanium atoms are distributed in the first layer region (G) 10 in a non-uniform distribution state.
In order to incorporate a-Ge (Si,
A layer consisting of H, X) may be formed. In addition, in the sputtering method, a target composed of silicon atoms, or a target composed of the target and germanium atoms is used in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Or use two pieces of targets.

Using a target containing a mixture of silicon atoms and germanium atoms, a raw material gas for supplying germanium atoms diluted with a diluent gas such as He or Ar as necessary, and hydrogen atoms or/and halogen atoms as necessary. A first layer region (G) 105 is formed by introducing a gas for introducing atoms smoothly into a deposition chamber for tuttering to form a plasma atmosphere of a desired gas. In this sputtering method, when the distribution of germanium atoms is made non-uniform,
The target may be sputtered while controlling the gas meteor of the raw material gas for supplying germanium atoms 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 respectively housed in a evaporation port as a 7i source, and this evaporation source is heated using a resistance heating method or an electron beam source. The first layer region (G) 105 is formed in the same manner as in the sputtering method except that the evaporated material is heated and evaporated by a beam method (CEB method) or the like and the flying evaporated material is passed through a desired gas plasma atmosphere. I can do it.

Substances that can be used as raw material gas for supplying silicon atoms used in the present invention include SiH4, S x2H (,
5t3Hp, S i, H,,! ': Silicon hydride (silanes) in a gaseous state or that can be gasified is mentioned as one that can be effectively used, especially in terms of ease of handling during layer creation work and good silicon atom supply efficiency. SiH, S
i, H6, are listed as preferred.

Substances that can be used as raw material gas for supplying germanium atoms include G e H4, G ejH6, G e, H,, G
e4Ht6,G etH,,Ge,H,4,Ge
yH4, G ePH,.

Germanium hydride in a gaseous state or capable of being gasified as G e 2 H2, # is mentioned as one that can be effectively used, especially in terms of ease of handling during layer creation work, good germanium atom supply efficiency, etc. ,GeH4,Ge,H6,Q
ejH, is preferred.

Many 7X halogen compounds are effective as the raw material gas for introducing /\ halogen atoms used in the present invention, such as halogen gas, /\ halide, interhalogen compound, /\ silane derivative substituted with halogen. Preferred examples include halogen compounds in a gaseous state or in a gas state such as halogen compounds. Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, Cu F, Br F (,
Examples include interhalogen compounds such as BrF, IF, IF, IC, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
Preferred examples include silicon halides such as i, F4, S 12F6, SiC moni, and 5iBr♦.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing halogen atoms, a raw material capable of supplying silicon atoms together with a raw material gas for supplying germanium atoms is used. Even without using silicon hydride gas as a gas, the desired support 1011 can be coated with /
A first layer region (G) 105 made of a-5iGe containing X rogen atoms can be formed.

When manufacturing the first layer region (G) 105 containing halogen atoms according to the glow discharge method, basically, for example, a silicon halide serving as a raw material gas for supplying silicon atoms and a raw material gas for supplying germanium atoms are used. The first layer region (G
) 105 on the desired support 101 by introducing a first layer region (G) 10 into a deposition chamber and generating a glow discharge to form a plasma atmosphere of these gases.
However, in order to make it easier to control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is also mixed with these gases. A layer may be formed.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

In order to introduce halogen atoms into the first layer region (G) 105 formed in both the sputtering method and the ion blating method, - the above-mentioned halogen compound or the above-mentioned silicon compound containing a halogen atom is used. It is sufficient to introduce a gas into the deposition chamber and form a plasma atmosphere B of the gas.

Further, when introducing hydrogen atoms into the first layer region (G) 105, a raw material gas for hydrogen atom introduction, such as F2,
Alternatively, gases such as the above-mentioned silanes and/or germanium hydride 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 raw material gases for introducing halogen atoms, but halogen compounds such as HF, He, HBr, and Hl are also used. hydrogen chloride.

S i H, F, Si F21s, S f HJCl
x, 5iHC, S i H2B F2, S i HB
r3, etc.+7)/”Rogen-substituted silicon hydride, and G e
HF7, GeF2F2, GeH3P, GeH
C11, G e H2CAs, G e HJC, G
e HB F3, G e HJB F2, G e H3
B r, G e HF3, G e H2L, G e H
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as jI, Ge4, GeCn
A, GeBr4. Ge14, GeF2. GeC11,.

Gaseous or gasifiable substances such as germanium halides such as G e B r, G e I2, etc. can also be mentioned as useful starting materials for forming the first layer region (G) 105 .

Among these substances, halides containing hydrogen atoms are hydrogen atoms that are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the first layer region (G) 105. Since atoms are also introduced, it is used as a suitable raw material for halogen introduction in the present invention.

In order to structurally introduce hydrogen atoms into the first layer region (G) 105, in addition to the above, F2 or S i H4,S
i, H,, S i71 (p, S is H/J c7)
Silicon hydride with germanium or a germanium compound for supplying germanium atoms, or G e H4
, G e2H4, G elHp, G e4Hto, G
e, H, 2, Ge, H, 4°G e7H, 7, Ge,
H,...,Ge,HJ' (7) This can also be carried out by causing germanium hydride and silicon or a silicon compound for supplying silicon atoms to coexist in a deposition chamber to generate a discharge.

In a preferred example of 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) is preferably 0.01 to 40 atomic %, more preferably 0.05 to 30 atomic %, most preferably 0.1 to 25 atomic %.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the first layer region (G) 105, for example, the temperature of the support and/or the amount of hydrogen atoms or halogen atoms used to contain them can be controlled. The amount of starting material introduced into the deposition 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 (starting materials for forming the second layer region (S) 106 (tile)) excluding the starting materials that serve as raw material gas for supplying germanium atoms from the starting materials (I) for forming the second layer region (S) 105
It is possible to use the same method and conditions to form 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, in order to form the second layer region (S) 106 composed of a-3t (H, Along with the raw material gas, a raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms as necessary is introduced into a deposition chamber whose inner shell can be depressurized to generate a glow discharge in the deposition chamber. What is necessary is to form a layer consisting of a-3t(H, In addition, when forming by sputtering method,
For example, silicon B in an atmosphere of an inert gas such as Ar or He or a 4'14 gas mixture based on these gases; (
When sputtering a target composed of particles, a gas for introducing hydrogen atoms and/or 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 stars of hydrogen atoms and halogen atoms (H+X) contained in the second layer region (S) 106 to be formed is preferably is 1~
To provide a layer region (N) containing the most atoms, preferably 5 to 30 atom %, the first layer (I) 1
When forming 02, the starting material for introducing nitrogen atoms is used together with the starting material for forming the first layer (I) 102 described above, and the amount thereof is controlled and contained in the layer to be formed. good.

When a glow discharge method is used to form the layer region (N), a starting material for introducing nitrogen atoms into a starting material selected as desired from among the starting materials for forming the first layer (I) 102 described above. Substances are added. As the starting material for uniformly introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms, a raw material gas containing nitrogen atoms, and a raw material gas containing hydrogen atoms and/or halogen atoms as necessary are mixed at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms and a raw material gas containing nitrogen atoms and hydrogen atoms may be mixed at a desired mixing ratio. It is possible to use a mixture of a raw material gas whose constituent atoms are , and a raw material gas whose constituent atoms are silicon atoms, nitrogen atoms, and hydrogen atoms.

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.

It becomes the raw material gas for introducing nitrogen atoms used when forming the layer region (N)1! Examples of starting materials that can be effectively used include nitrogen (NJ), ammonia (N)b), hydrazine (H,N N HJ), Hydrogen azide (HNz), ammonium azide (NH3N2
), gaseous or gasifiable nitrogen, and nitrogen compounds such as nitrides and azides. In addition to this,
In addition to introducing nitrogen atoms, halogen atoms can also be introduced, so nitrogen trifluoride (F, N) and nitrogen tetrafluoride (F
Examples include halogenated nitrogen compounds such as 4NJ).

In unreleased j, in order to further promote the effect obtained with nitrogen atoms in the layer region (N), in addition to nitrogen atoms,
Furthermore, it can contain oxygen atoms.

As the raw material gas for introducing oxygen atoms into the layer region (N), for example, oxygen (Oa), ozone (0
3), -nitric oxide (NO), nitrogen trioxide (NOJ)
, -nitrogen dioxide (N, o), nitrogen sesquioxide (NJO
), nitrogen tetroxide (NJ 04), nitrogen sesquioxide (N
JOx), nitrogen trioxide (No,) whose constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, such as disiloxane ()Ijs i OS i Hj), trisiloxane (Hjs i OS i H20S + H3), etc. Lower siloxanes and the like can be mentioned.

In order to form the layer region (N) by the sputtering method, a single crystal or polycrystalline silicon wafer or a silicon wafer or a silicon atomic layer is mixed during the formation of the first layer (I) 102. This can be carried out by using a wafer containing wafers as a target and subjecting them to wafer sintering 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 required.

The silicon wafer may be sputtered by introducing the gas into a deposition chamber for sputtering and forming a gas plasma of these gases.

Alternatively, silicon atoms and Sta% may be used as separate targets, or by using a single target containing silicon atoms and Si7%, in an atmosphere of diluted scum as a gas for sputtering 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 nitrogen atom introduction, the raw material gas 1 for nitrogen atom introduction among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming the first layer (1) 102,
When a layer region (N) containing nitrogen atoms is provided, the distribution concentration C'(N) of nitrogen atoms contained in the layer region (N)
is changed in the layer thickness direction to obtain the desired distribution state in the layer thickness direction (
layer area (N
), in the case of glow discharge, the distribution concentration C
A starting material gas for introducing nitrogen atoms to change (N) may be introduced into the deposition chamber while changing its gas flow rate appropriately according to a desired rate of change curve. For example, the opening of a predetermined needle valve provided in the gas passage system 4 may be appropriately changed by any commonly used method such as manually or by using an externally driven motor.

At this time, a desired content rate curve can be obtained by controlling the flow rate according to a pre-designed change rate curve using, for example, a microcomputer or the like.

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 (d) of nitrogen atoms in the layer thickness direction.
epth profile), first, as in the case of the glow discharge method, the starting material for introducing nitrogen atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is This can be done by appropriately changing as desired.

Second, if a target containing a mixture of silicon atoms and S or N is used as a target for subtantaring, the mixing ratio of silicon atoms and 5izN4 should be adjusted in the direction of the layer thickness of the target. This is done by changing the parameters in advance.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, to structurally introduce Group II atoms or Group V atoms, when forming one layer, a starting material for introducing Group II atoms or a starting material for introducing Group V atoms is deposited in a gaseous state. It may be introduced into the chamber together with other starting materials for forming the second region (S) 106. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Examples of starting materials for the introduction of group Ⅰ atoms include BiHt, 1341(+, BtHq, BrHr()).
, BsHra, Bt HIJ, B6H14, etc., boron halides such as BF, , BCI, , B B rj, and the like. In addition, A view C sentence 3, G e C
513, G e (CHJ), I n CM7, T
I CUj etc. can also be mentioned.

As a starting material for introducing a group V atom, in the present invention, PH7 is effectively used for introducing a phosphorus atom.
, PJH4, etc. hydrogen north neighbor, PH4I, P F,, P
Fj, P C13, P C%, P B rl, P B
r(, PI, etc.).In addition, As H3, AsFj, AsCjL), As
B rj, AsF,, S bH,, S bF,, S b
F,,SbCla,SbC! ;Lr, B i H3
, BiCl3. BiBrJ, etc. may also be mentioned as effective starting materials for the introduction of Group V atoms.

In the present invention, the layer thickness of the layer region (PN) that constitutes the first layer (I) 102 and is unevenly distributed on the support 101 and contains a substance that controls conduction characteristics is is the layer region (PN) and the first layer formed on the layer region (PN).
The lower limit is preferably determined to be 50 A or more, depending on the characteristics required for the other layer regions constituting the layer (I) 102. . Further, when the content of the substance controlling the conductive properties contained in the layer region (PN) is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region (PN) is preferably 1 oIL or less, preferably 8 oIL or less,
The optimum thickness is desirably 5μ or less.

In the photoconductive member 100 shown in FIG. 1, the second layer (π) 103 formed on the first layer (I) 102 has a free surface and mainly has moisture resistance and continuous repeated use characteristics. , is provided in order to achieve the objects 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 CI) 102 and the second layer (TL) lo3 has a common constituent element of silicon atoms, both Chemical stability is sufficiently ensured at the laminated interface of layers ('I) 102 and (1') 103.

The second layer (1) 103 in the present invention is an amorphous material (hereinafter referred to as r a -(S 1
x07-x) y(H,X)ry", however,
0<x, y<1).

a −(S i!ot −x) y(H,X)/−TQ
The second layer (1) 103 is formed by a glow discharge method, a sputtering method, an electron beam method, an ion planarization method, an ion plate ink method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be produced. The second layer (X), which is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and which contains oxygen atoms and halogen atoms together with silicon atoms.
A glow discharge method or a sputtering method, which has the advantage of being easy to introduce into the material 103, is preferably employed. Furthermore, in the present invention, a glow discharge method and a sputtering method are used together in the same system to form the second layer (X).
103 may be formed.

To form the second layer (M) lo3 by the glow discharge method, a −(S 1xO1-x)! (H,X)+
-y-forming raw material gas is mixed with dilution gas at a predetermined mixing ratio as needed, and introduced into the deposition chamber where the support 101 is installed, and the introduced gas is used to cause glow discharge. The first layer (1) 102 that has already been formed on the support 101 is coated with a −(Si*o+ −
x) y(H,X)+-y may be deposited.

In the present invention, a-(S 1xorx)y (H,
)+-y The raw material gas for forming y is silicon atoms,
Most gaseous substances or gasified substances containing at least one of oxygen atoms, hydrogen atoms, and halogen atoms can be used.

When using a raw material gas containing silicon tq-7- as one of silicon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, for example, if silicon atoms are
, a raw material gas containing atoms, a raw material gas containing oxygen atoms, and, if necessary, a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms, as desired. A raw material gas containing silicon atoms and a raw material gas containing oxygen atoms and hydrogen atoms or/and a raw material gas containing oxygen atoms and halogen atoms may be used in a mixed ratio. This is also possible by mixing at a desired mixing ratio, or by mixing a raw material gas with silicon atoms as constituent atoms and a raw material gas with three constituent atoms: silicon atoms, oxygen atoms, and hydrogen atoms, or with silicon atoms and oxygen atoms. It is possible to use a mixture of a raw material gas having three constituent atoms: atoms and /＼rogen atoms.

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

In the present invention, suitable halogen atoms contained in the second layer (ff) 103 include fluorine, chlorine, bromine,
Iodine, particularly fluorine and chlorine, are preferred.

In the present invention, raw material gases that can be effectively used to form the second layer (π) 103 include those in a gas state or substances that can easily turn into scum at Hatake temperature and normal pressure. I can do it.

When forming the second layer (1) 103 by the sputtering method, for example, it is performed as follows.

Firstly, when sputtering a target composed of silicon atoms in an atmosphere of inert gas such as Ar or He or a mixed gas based on these gases, a raw material gas for introducing oxygen atoms is used. If necessary, it may be introduced into a vacuum deposition chamber in which sputtering is performed together with a raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms.

Second, the target for sputtering is 15i.
A target composed of Oyu or a target composed of silicon atoms and S i O.

Oxygen atoms can be introduced into the second layer (ff) '103 formed by using two targets composed of silicon atoms or a target composed of silicon atoms and SiO. I can do it. At this time, if the raw material waste for introducing oxygen atoms is also used, it is easy to arbitrarily control the amount of oxygen atoms introduced into the second layer (π) 103 by controlling the flow rate. It is.

The content of oxygen atoms introduced into the second layer (ff) 103 can be determined by controlling the flow rate when the raw material gas for introducing W1 elementary atoms is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing W1 elementary atoms is introduced into the deposition chamber. The proportion of oxygen atoms contained in the gouget can be arbitrarily controlled as desired by adjusting the ratio of oxygen atoms contained in the gouget when preparing the gouget, or by both.

The starting materials used in the present invention as raw material scraps for supplying silicon atoms include 5i1(,,s, 1JH
4, SIJH51, S 1qHtO and other silicon hydrides (silanes) in a gaseous state or in a form of scum can be effectively used, and in particular, they are easy to handle in layer creation work and improve silicon atom supply efficiency. S i H4 in terms of quality etc.
, S i and H6 are preferred.

If these starting materials are used, the second layer (1) 1'03 can be formed by appropriately selecting the conditions for forming the first layer.
Hydrogen atoms may also be introduced in addition to silicon atoms.

In addition to the above-mentioned silicon hydride, effective starting materials that can be used as raw material gas for supplying silicon atoms include silicon compounds containing halogen atoms, so-called silane conductors substituted with halogen atoms, specifically, for example, 1fsiF. ,,Si,F(,5i
Cu4. Preferred examples include silicon halides such as SiBr4°. Furthermore, S i H2F
2. S i H.

I3+ S IJClz, S 1Hc9. j, S
iH, Bra.

Halogen-substituted silicon hydride such as 5iHBrj, etc. can be in a gaseous state or in a gaseous state. Hydrogen atom is one of the constituent elements
Other halides can also be mentioned as effective starting materials for supplying silicon atoms for the formation of the second layer (π) 103.

Even when using these silicon compounds containing halogen atoms, as mentioned above, by appropriately selecting the layer forming conditions,
Silicon atoms and halogen atoms can be introduced into the second layer (ff) YO3 to be formed.

Among the above-mentioned starting materials, silicon halide compounds containing hydrogen atoms are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer during the formation of the second layer (π) 1o3. Since a hydrogen atom can also be introduced, it is used as a starting material for introducing a suitable halogen atom in the present invention.

In addition to the above-mentioned materials, effective starting materials that serve as raw material residue for introducing halogen atoms used in forming the second layer (]L') 103 in the present invention include, for example, fluorine, 1! ! element, bromine, iodine, halogen gas, B r
F + Cl 'F, CQ Fi +BrF,
Interhalogen compounds such as BrFJ, IFj, IFq, ICu, IBr, HF, He, HBr.

Examples include hydrogen halides such as HI.

The starting material that can be effectively used as a raw material gas for introducing oxygen atoms used when forming the second layer ('II) 103 includes oxygen atoms as constituent atoms, or nitrogen atoms and oxygen atoms. For example, oxygen (0
λ), ozone (OJ), -nitrogen oxide (No), nitrogen dioxide (NOJ), -nitrogen dioxide (NJO), nitrogen sesquioxide (N>03), nitrogen tetroxide (N, 04), nitrogen sesquioxide (N)Ot), nitrogen trioxide (No, ), and disiloxane (H,S
iO51H3), trisiloxane (H3S iOS
Examples include lower siloxanes such as HjOS 1H)).

In the present invention, so-called rare gases such as He, Ne, Ar, etc. are preferably used as the diluting gas used when forming the second layer (π) 103 by a glow discharge method or a sputtering method. I can do it.

The second layer (In) 103 in the present invention is carefully formed to provide the desired properties.

In other words, substances whose atoms are composed of silicon atoms, oxygen atoms, hydrogen atoms and/or halogen atoms if necessary, have a structure ranging from crystalline to amorphous depending on the conditions of creation, and have different electrical properties. , exhibiting properties ranging from conductivity to semiconductivity to insulating properties, and exhibiting properties ranging from photoconductive properties to non-photoconductive properties. Therefore, in Undeveloped II, desired properties depending on the purpose are obtained. has a −(S
1xo) -x) y (H, To provide the main purpose of improving sexual performance, a-(S:xO
t −x)y (H,

In addition, when the second layer (N) 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 1xot −x )! (H,X)/-
y is created.

First layer (I) 10? ) on the surface, 6-(Si!0+-
A second layer (X)1 consisting of x)y (H,X)ly
Support 1'01 during layer formation when forming 03
The temperature of 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 tightly controlled so that the layer can be formed as desired. In the present invention, the second layer (π) 103 for effectively achieving the desired purpose
The support temperature in the optimum range is selected as appropriate in accordance with the formation method, and the formation of PJ second layer (TL) process 03 is executed.
What is the temperature of the support during layer creation?

Preferably 20-400°C, more preferably 50-35°C
The temperature is desirably 0°C, most preferably 100-300°C.

To form the second layer (π) 103, glow discharge is used to form the second layer (π) 103, since fine control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. Adoption of sputtering method or sputtering method is advantageous. When forming the second layer (π) 103 using these layer forming methods, the discharge power during layer formation is set to a −(
It is one of the important factors that influences the characteristics of S i+C)+ -x )yXl-y.

a having the characteristics for achieving the object of the present invention;
-(S 1xOl-x )tX+-y can be effectively created with good productivity as the discharge power condition is preferably lO~300W, more preferably 20~250W, and optimally 50~200W. It is desirable that the

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

In the present invention, the support temperature and discharge power for forming the second layer (π) 103 may be within the above-mentioned ranges, but these layer formation factors may be determined independently and separately. It is not determined by the desired characteristic a −(S ixO+−X) V (H,X)/−
It is desirable that the optimum value of each layer creation factor be determined based on mutual organic relationship so that the first degree layer ('n) 103 consisting of y is formed.

The amount of oxygen atoms contained in the second layer (U) 103 in the photoconductive member of the present invention is the same as the production conditions of the second layer (π) 103. This is an important factor for the formation of the resulting second layer (π) 103.

The amount of oxygen atoms contained in the second layer (M) 103 in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (Jf) 103. It is something that can be done.

That is, the general formula a-(S'i*O1-x) V(
H,X)/-! Amorphous materials shown in can be roughly divided into:
An amorphous material composed of silicon atoms and oxygen atoms (hereinafter referred to as ra-Siao/-aJ).

(p, shi, O<a<1), an amorphous material 1 (hereinafter referred to as "amorphous material") composed of silicon atoms, oxygen atoms, and hydrogen atoms.

It is written as ra-(Sibo+-b)cH+-cJ. However, 0<b, c<1), and an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as ra-(Sid0f-d)
It is written as e (H,X)l-e'J. However, 0<d, e
el).

In undeveloped IJII, the second leopard (N) l O3 is a
-S 1aO1-a, the second layer (I
11') The amount of oxygen atoms contained in 103 is a-5ia
If expressed as a in O1-a, a is preferably 0.3
3 to 0.99999, more preferably 0.5 to 0.99,
The optimum value is 0.6 to 0.9.

In the present invention, the second layer (π) 103 is a-(S i
bo 1-b) c When composed of Ht-c, the violet of fI# elementary atoms contained in the second layer (X) 103 is a
-(Sibo+ -b)c If expressed as b and C in Ht-c, b is preferably 0.33 to 0.99999
, more preferably 0.5-0,99, optimally 0.6-0.
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 (IJ) 103 is a - (S 1dOt-d
) e (H, e(H,X
) When expressed as d and e in 1-e, d is preferably 0.33 to 0.99999, more preferably 0.5 to 0.
99. Optimally, e is between 0.6 and 0.9, and e is preferably between 0.8 and 0.99. The range is one of the important factors for effectively achieving the purpose of the present invention. This P!
XyJ is appropriately determined as desired depending on the intended purpose so as to effectively achieve the purpose of the present invention. Furthermore, this layer thickness also depends on the characteristics required for each layer region in relation to the amount of oxygen atoms contained in the layer (π) 103 and the layer thickness of the first layer (I) 102. It is necessary to decide as appropriate based on the organic relationship depending on the desired situation.

In addition, it is desirable that this layer thickness is also taken into consideration from the economical point of view, taking into account productivity and mass production.

The layer thickness of the second layer ([)lo3 in the present invention is as follows:
Preferably 0.003 to 3011, more preferably 0.0
0'4 to 20 l, optimally 0.005 to 10. It is desirable that this is done.

In addition, in the present invention, raw material gases for introducing carbon atoms to obtain oxygen atoms include, for example, saturated hydrocarbons having 1 to 5 carbon atoms, saturated hydrocarbons having 1 to 5 carbon atoms, and 2 carbon atoms. ~5 ethylene hydrocarbon, carbon number 2-4
These include acetylene hydrocarbons, etc.

Specifically, as a saturated hydrocarbon, methane (CH-stopped)
, ethane (CjH6), propane (CjH,r).

n-buta 7 (n -C4H,,), penta 7 (C
, (%) , Ethylene hydrocarbons include ethylene (CHO), propylene (CjHj), butene-1 (
C4H,), butene-2 (C4HF), isobutylene (C4HP), pentene (C,H,.), and acetylene hydrocarbons include acetylene (CJa) and methylacetylene (CcoH4).

Examples include butyne (C4Ha) and the like. In addition to these, 5i (CHa) and 5i (C) are used as raw material scraps whose constituent atoms are silicon atoms, carbon atoms, and hydrogen atoms.

H) 1 class alkyl silicides can be mentioned.

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

Examples of the conductive support include NiCr, stainless steel, AIL, Cr, Mo, Au, Nb, Ta, ■, Ti,
Examples include metals such as 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, ceramics, paper, etc. are usually used. Ru.

These electrically insulating supports preferably have at least one surface conductively treated, and the electrically conductively treated surface side.
Preferably, other layers are provided.

For example, if it is glass, NiCr1. A
n, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Pt, Pd, I n, oJ, S noJ, I To (
Conductivity is imparted by providing %JN consisting of I n, O, +S no, ), etc., or if it is a synthetic resin film such as a polyester film, NiCr,
AM, Ag, Pb, Zn, Ni, Au, Cr, Mo, I
A thin film of metal such as r, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal,
Conductivity is added to the surface.

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired.1 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 101 is determined as appropriate so that a desired photoconductive member is formed. However, when flexibility is required as a photoconductive member, the thickness is made as thin as possible within a range that allows it to fully perform its function as a support. In such a case, the thickness of the support 101 is preferably l from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
It is considered to be over 0.

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

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

In the figure, gas cylinders 1102 to 1106 are sealed with raw material gases for forming the photoconductive member of the present invention. 99.999%, hereinafter S
i H4/ He (abbreviated as ) cylinder, 1103 is He
G e H4 gas diluted with (purity 99.999%,
Hereinafter referred to as G e H (abbreviated as / He) cylinder, 1104
is a N Hj gas (99.99% purity) cylinder.

1105 is He gas (99.999% purity) cylinder, 1
106 is an H gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, valves 1122 to 1126 of gas pumps 1102 to 1106,
Make sure the leak valve 1135 is closed,
Also, ili, inlet valves 1112 to 1116. Outflow valves 1117-1121, auxiliary valves 1132.1133
First, check that the main valve 11 is opened.
34 is opened to exhaust the inside of the reaction chamber 1101 and each waste pipe.The reading of the vacuum gauge 1136 is approximately 5 x 10 T.
When it becomes o r r, the auxiliary valves 1132, 11
33. Close the outflow valves 1171-1121.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137 as a support, (7) SiH1/He gas from the gas cylinder 1102,
From the gas pump 1103 (7) G e H4/He gas, the N H gas from the gas pump 1104, open the valves 1122, 1123, and 1124 to the outlet pressure gauge 1.
By adjusting the pressure at 127, 1128° 1129 to 1 kg/cm' and gradually opening the inlet valves 1112, 1113, and 1114, the mass flow controller 110
7.1108 and 1110 respectively. Pull! Then, gradually open the outflow valves 1117, 1, 118, and 1119, and the auxiliary valve 1132 to supply each gas to the reaction chamber 11.
01.

5iH4/He gas flow rate and G e H4/
The outflow valves 1117, 1118 and 1119 are adjusted so that the ratio of the He gas flow rate and the N Hj gas flow rate becomes the desired value, and the vacuum gauge 1136 is adjusted so that the pressure inside the reaction chamber 1101 becomes the desired value. Main valve 11 while checking the reading
Adjust the aperture of 34. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50° to 400°C by the heating heater 113B,
is set to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the valve is activated by applying G e H4/He gas and a method such as manual or external driver according to a pre-designed rate of change curve. 1118-112
The flow rate of N 2 H and gas is adjusted by appropriately changing the aperture of 0, thereby controlling the distribution concentration C(N) of germanium atoms and nitrogen atoms contained in the layer formed.

In the manner described above, the first layer region (G) 105 is formed on the base 1137 to a desired layer thickness by maintaining glow discharge for a desired period of time. At the stage when the first layer region (G) IO'5 is formed to the desired layer thickness, the outflow valve 1116 is completely closed, and the discharge conditions are changed as necessary.
A second layer region (S) 106 substantially free of germanium atoms can be formed on the first layer region (G) 105 by maintaining glow discharge for a desired period of time according to similar conditions and procedures.

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 B2H6 or PH3 may be added to the gas introduced into the deposition chamber 1101.

In this way, the first layer (I) 102 is formed on the base 1137.

”-first layer (I) formed to a desired layer thickness as described below.
To form the second layer (If) 103 on the layer 102, for example, each of S i H4 gas and No gas is added as necessary by the same valve operation as when forming the first layer 102 (I). The diluent may be diluted with a diluent gas such as He and supplied into the reaction chamber 1101 to cause glow discharge according to desired conditions.

In order to contain halogen atoms in the second layer (Ir) tos, for example, add S I F4 gas and No gas, or add S i J gas thereto and form the second HC layer in the same manner as above.
I) It is sufficient to form 1o3.

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 remaining in the gas piping leading from JL7 valves 1117 to 1121 into the reaction chamber 1101, close the outflow valves 1117 to 1121,
Open auxiliary valves 1132 and 1133 and open main valve 1.
134 will be fully opened and the prefecture will be evacuated to high vacuum if necessary.

The amount of oxygen atoms contained in the second layer (n') 103 can be determined by, for example, changing the flow rate ratio of S i H4 gas and No gas introduced into the reaction chamber 1101 in the case of glow discharge as desired. Alternatively, when forming a layer by sputtering, the sputtering area ratio of the silicon wafer and the SfO wafer is changed when forming the target, or the target is formed by changing the mixing ratio of the silicon powder and the SiO powder. By molding, it can be controlled as desired. Second layer (π)! The amount of halogen atoms contained in 03 is determined by the amount of M material gas for introducing halogen atoms,
For example 'Sr F4. This is accomplished by adjusting the flow rate when the gas is introduced into the reaction chamber 11 (11).

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.

Using the manufacturing apparatus shown in FIG. 15, a sample (sample No. 11-1-17-4) as an electrophotographic image forming member was prepared on a cylindrical An substrate as a support under the conditions shown in Table 1.
) were created 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 obtained in this way was placed in a heavy exposure experiment device and +5. Corona charging was performed for 0.3 seconds (sec) using OKV, and a light image was immediately irradiated.

The light image uses a tungsten lamp light source.
The light amount of S'e C was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the sample (imaging member) surface by cascading the sample (imaging member) surface with a charged developer (including toner and carrier). The toner image on the sample is +5
．． When transferred onto transfer paper using OKV's corona charging, clear, high-density images with excellent resolution and good gradation reproducibility were obtained in all samples.

In the above, each sample was subjected to the same toner image forming conditions except that an 810 nm GaAs semiconductor laser (LOMW) was used instead of a tungsten lamp as a light source to form an electrostatic image. When the image quality of the toner transfer images was evaluated, it was found that in all samples, clear, high-quality images with excellent resolution and good gradation reproducibility were obtained.

Example 2 Cylindrical AJI was manufactured using the manufacturing equipment shown in Fig. 15.
Samples (sample Nos. 21-1 to 27-4) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 3 (Table 4).

The content distribution concentration of germanium atoms in each sample is the first
The θ diagram and the nitrogen atom content distribution concentration are shown in FIG. 17.

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. In addition, for each sample, 38℃, 8
When a repeated use test was conducted 200,000 times in an environment of 0% RH, no deterioration in image quality was observed in any of the samples.

Example 3 The sample preparation of Example 1, 11-1.12-
Each of the electrophotographic image forming members (No. 11-1-1 to 11-1-
8.12-1-1 to 12-1-8, 13-1-1 to 1
3-1-8) were created. Each of the electrophotographic image forming members 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 We evaluated the overall image quality of the transferred image and evaluated its durability through 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 When forming the second layer (π) 103, silicon sea urchin /\ and 3
Each of the image forming members was prepared in exactly the same manner as Samples +b and 11-1 of Example 1, except that the target area ratio of i01 was changed and the content ratio of silicon atoms and oxygen atoms in layer (II) was changed. It was created. 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 the image Jf value was measured, and the results shown in Table 7 were obtained. .

Example 5 Second layer (II) When forming the layer 103, the flow rate ratio of SiH4 gas and No gas was changed to change the content ratio of silicon atoms and oxygen atoms in the layer (, ]f). Each of the image forming members was created in exactly the same manner as in Example 1 Sample No. 12-1.

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 the second layer (π) 103, SiH4 gas, S
i By changing the flow rate ratio of F4 gas and No gas, the layer (ff
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 i) was changed. After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 8 were obtained. .

Example 7 Example 1 except for changing the layer thickness of the second layer (π) 103
Each of the image forming members was prepared in exactly the same manner as Sample No. 111. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 10.

The layer forming conditions in the embodiments of the present invention shown in Table 2, Table 4, and Table N5to are shown below.

Substrate temperature: germanium atom (Ge) containing layer...approximately 2
00℃ Germanium atom (Ge)-free layer...approx. 250℃ Discharge frequency: 13.56MHz Reaction chamber pressure during reaction: 0.3Torr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the leading member of the present invention, and FIGS. 2 to 10 respectively show the distribution state of germanium atoms in the first layer (I). The explanatory drawings for explanation, FIGS. 11 to 14, respectively show the first layer (1
), FIG. 15 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 16 and 17 are respectively applicable to the embodiments of the present invention. FIG. 3 is a distribution state diagram showing the content distribution concentration state of each atom. 100... Photoconductive member 101... Support 102... First layer (I) 103... Second layer (II) 104... Photoreceptive layer Applicant Canon Co., Ltd. Attorney Yoshi Tani - Figure 1 +07 1o. c Figure 5 C C -1111-C C Figure 11 Figure 12 C (N) Figure 13 Figure 14 C (N)

Claims (2)

[Claims] (1) A support for a photoconductive member, a first layer region (G) formed of an amorphous material containing germanium atoms and provided on the support, and an amorphous material containing silicon atoms. (a first layer having a second layer region (S) that is composed of four materials and exhibits photoconductivity and is provided on the first layer region (G); and
(It has a photoreceptive layer consisting of a second layer made of an amorphous material containing five keratinized silicon atoms and oxygen atoms,
6 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 within the layer (7-). Features of photoconductive materials. (2) First layer region (G) and second layer region (8(S)
2. The photoconductive member according to claim 1, wherein at least one of the components (a) contains a hydrogen atom. ) The photoconductive member according to claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. 2.) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform. ) The photoconductive member according to claim 1, wherein the germanium source 7 is uniformly distributed in the first layer region (G). ) The photoconductive member according to claim 6, wherein the substance that controls conductivity is an atom belonging to group m of the periodic table. ) The photoconductive member according to claim 6, wherein the substance controlling conductivity is an atom belonging to Group V of the periodic table.