JPS60140250A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member superior in photosensitivity, etc., by forming a photoconductive layer made of amorphous Si and Ge and contg. C in a nonuniform concn. distribution in the layer thickness direction, and an amorphous layer made of Si and N in succession on a substrate. CONSTITUTION:The objective photoconductive member 100 is obtained by successively forming on a substrate 101 the first photoconductive layer 102 made of amorphous Si and Ge and the second amorphous layer 103 made of Si and N. The first layer 102 contains C in a concn. distribution in the layer thickness direction having concn. C1 in the first region 104, C3 in the third region 106, and C2 in the second region 105 formed in this order from the side of the substrate 101, and C3 is never highest alone, and when one of the three is 0, the other two are not 0 and not equal to each other.

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.

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 high sensitivity and a high signal-to-noise ratio [photocurrent (Ip)].
/dark current (Id)), have absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated, have fast photoresponsiveness, have a desired dark resistance value, and be resistant to the human body during use. 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, 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,
DE 2933411 describes an application to a photoelectric conversion reader.

Hyakuen et al., a photoconductive member having a photoconductive layer composed of conventional A-3T has a dark resistance value and a 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 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 repeatedly used for a long period of time, fatigue due to repeated use accumulates, resulting in so-called ghost development in which an afterimage occurs. Alternatively, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur.

Furthermore, a-5i 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. Stay.

When a commonly used halogen lamp or light lamp is used as a 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 transmitted through the photoconductive layer, interference due to multiple reflections will occur within the photoconductive layer, which is one of the causes of "poke" 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 a 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 Elementary 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 in the formed photoconductive layer by light irradiation is not sufficient, or the prevention of charge columnarization from the support side in a dark area is not sufficient. This occurs in many cases.

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 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-St material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and the present invention focuses on the applicability of a-3i 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 developed a sulfur amorphous material that uses silicon atoms and germanium atoms as a matrix and contains at least either a hydrogen atom or a halogen atom, so-called hydrogenated amorphous silicon germanium, and halogenated amorphous silicon. Germanium or halogen-containing hydrogenated amorphous silicon germanium (hereinafter referred to as RA-5i)
Ge (H, The conductive material not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, especially as a photoconductive material for electrophotography. The present invention is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side.

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

Another object of the present invention is to 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 the support and between each layer of laminated layers, and to have a dense and stable structural arrangement; An object of the present invention is to provide a photoconductive member with 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 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 comprises a support for the photoconductive member, and a first layer exhibiting photoconductivity provided on the support and made of an amorphous material containing silicon atoms and germanium electrons. , a photoreceptive layer is provided on the second layer and includes a second layer made of an amorphous material containing silicon atoms and nitrogen atoms, and the first layer is made of an amorphous material containing silicon atoms and nitrogen atoms. The distribution concentration of carbon atoms in the layer thickness is C(1),
It is characterized by having a first region, a third region, and a second region each having a value of f'J and C(2) in this order from the support side (however, carbon The distribution concentration of atoms C(3) alone will not reach the maximum, and if any one of the distribution concentrations C(z), c(2), and C(3) becomes O, the other two are not 0 and are not equal).

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, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

In addition, the photoconductive member of the present invention has a photoreceptive layer formed on the support, which has a strength of 1N, and has excellent adhesion to the support, and can be continuously and repeatedly applied at high speed for a long time. can be used.

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

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

FIG. 1 is a schematic configuration diagram 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 (
1) 102 consists of a-5i Ge (H,X),
Contains carbon atoms and has photoconductivity. First layer (I)
102 and the second layer (■) 103 form the photoreceptive layer 10.
8.

The germanium atoms may be contained in the first layer (I) 10'2 so as to be evenly distributed in the first layer (I) 102, or evenly distributed in the layer thickness direction. However, the temperature distribution may be non-uniform. Hyakunen et al.
In either case, in the first layer (I) 102,
In the in-plane direction parallel to the surface of the support, it is necessary that germanium atoms be contained in a uniform distribution in an amount of 10,000 M in order to make the properties uniform in the in-plane direction.

In particular, it is contained evenly in the layer thickness direction of the first layer CI) 102, and is contained on the side opposite to the side where the support 101 is provided (the free surface 107 side of the photoreceptive layer 108). )
The distribution state is such that the number of the particles is distributed more toward the support 101 side (the interface side between the photoreceptive layer 108 and the support lO1), or vice versa. Germanium atoms are contained in the first layer (I) 102.

In the photoconductive member of the present invention, as described above, the distribution state of the germanium atoms contained in the first layer (I) 102 takes the above-mentioned distribution state in the layer thickness direction, and In the in-plane direction parallel to the surface of 101, it is desirable to have a uniform distribution state.

First layer (I) 1 of photoconductive member 100 shown in FIG.
02 contains carbon atoms, and the distribution concentration in the layer thickness direction is c(1), the first region (1) 1
04, a second region (2) with a value of C(2) 105,
and a third region (3) 106 having a value of C(3).

In the present invention, the above-mentioned item 1. Second. And each of the third regions 104 to 106 does not necessarily need to contain carbon atoms. However, if one region does not contain carbon atoms, the other two regions always contain carbon atoms, and the thickness of the carbon atoms in those regions is The distribution concentrations must be different. Clogging, distribution concentration of carbon atoms C(1), C
(2), C(3) It is necessary to form each region 104 to 106 so that when one of the noise deviations is 0, the other two are not 0 and are not equal. By doing so, it is possible to effectively prevent charges from being injected into the photoreceptive layer 108 from the free surface 107 side or the support 101 side when subjected to charging treatment, and at the same time, it is possible to It is possible to improve the dark resistance of the layer 108 itself and the adhesion between the support 101 and the light-receiving layer 108.

The first layer CI) 102 has practically sufficient photosensitivity and dark resistance, and the first layer (r)i.

The third region ( 3)1
It is necessary to design the first layer (I) 102 so that the distribution concentration C(3) of carbon atoms of 06 does not become maximum by itself. In this case, preferably the third region (3) 106
It is desirable to design the first layer (I) 102 so that the layer thickness of the third region (3) 102 is sufficiently thicker than that of the other two regions 104 and 105.
It is desirable to design the first layer (I) 102 so that the six-layer thickness occupies one-fifth or more of the layer thickness of the first layer (I) 102.

In the present invention, the layer thickness of the first region (I) 104 and the second region (2) J105 is preferably 0.00.
3-30#1. , more preferably 0.004 to 20 JL, most preferably 0.005 to 10 JL. or,
The layer thickness of the third region (3) 106 is preferably 1
~1ooIi, more preferably 1-80g, optimally 2
It is desirable to set it to 50. First area (1) 1
04 and the first layer (I) 10 in the second region (2) 105
The first layer (I) 1.02 is designed to primarily function as a so-called charge injection blocking layer that blocks charge injection into the first layer (I) 1.02.
When designing the first region (1) 104 and the second region (1) 104,
It is desirable that the layer thickness of each region (2) 105 is at most 10 μl.

When designing the photoreceptive layer so that the third region (3) 106 mainly functions as a charge generation layer, the layer thickness of the third region (3) 106 depends on the light source used. It can be determined as desired depending on the absorption coefficient of light. In this case, if a light source normally used in the field of electrophotography is used, the layer thickness of the third region (3) 106 is at most 10
It is good if it is about 1. In order for the third region (3) 106 to primarily function as a charge transport layer, it is desirable that the layer thickness be at least 5 IL.

In the present invention, the carbon atom content distribution concentration C(1), C
The maximum value of (2) and C(3) is preferably 67 at%, more preferably 50 at%, and optimally 40 at%, based on the sum of silicon raw material, germanium atoms, and carbon atoms. It is desirable that Moreover, the distribution concentration C
When (1), C(2), and C(3) are not O, the minimum value is preferably 1 atom ppm, more preferably 50 atoms ppm, based on the sum of silicon atoms, germanium atoms, and carbon atoms. The optimum content is preferably 100 atomic ppm.

III - FIGS. 2 to 10 show typical examples where the distribution state of germanium atoms contained in the first layer (I) 102 in the layer thickness direction is non-uniform.

In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer (I) exhibiting photoconductivity.
102 layer thickness, t8 is the position of the layer surface on the support 101 side, and tl is the first layer (I) on the opposite side from the support side.
The position of the surface of 102 is shown. That is, the first layer (I) 102 containing germanium atoms is formed from the t8 side toward the t and T sides.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer (I) 102 in the layer thickness direction.

In the example shown in FIG. 2, the surface on which the first layer (I) 102 containing germanium atoms is formed and the support to
From the interface position t, where it contacts the surface of i, to the position t, the distribution concentration C of germanium atoms takes a constant value C1 and is contained in the first layer (I), and from the position t1 to the interface position 1. The distribution concentration gradually and continuously decreases from C2 until reaching C2. At the interface position □, the distribution concentration C of germanium atoms is C3.

゛In the example shown in FIG. 3, the first layer (I) 10
The distribution concentration C of germanium atoms contained in 2 is at the position t
, a distribution state is formed in which the concentration gradually and continuously decreases from C1 until reaching position 1, and becomes e Ii Cs at position 〇.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is from position tB to position t2.
The distribution concentration C is set to a constant value up to C4, and is gradually and continuously decreased between position t2 and position ta, and at position T, the distribution concentration C is substantially zero (here, the distribution concentration C is substantially zero). Generally speaking, zero means that the amount is below the detection limit).

In the case of FIG. 5, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is from position tB to position tT.
The concentration gradually decreases continuously from C2 until reaching , and becomes substantially zero at the 5th position tT.

In the example shown in FIG. 6, the distribution concentration C of germanium atoms contained in the first layer (1) 102 is between the position t and the position t3, the concentration C? is a constant value, and the concentration C is relaxed at position ta. Between the positions t and ta, the one-distribution concentration C is decreased in terms of time difference from the position 1j to the position tT.

In the example shown in FIG. 7, the first layer (I) 102
The distribution concentration C of germanium atoms contained in is at the position t,
The concentration C11 takes a constant value up to position t+, and
From 4 to position tT, the concentration is C1, and the distribution decreases linearly to concentration CI5.

In the example shown in FIG. 8, the distribution concentration C of germanium atoms contained in the first layer (I) 102 is linear from position t8 to position tT such that the concentration C5 becomes substantially zero. It is decreasing functionally.

In the to9 diagram, the distribution concentration C of germanium atoms contained in the first layer (I) 102 decreases linearly from the concentration CIG to the concentration CI& from the position t until the position t-y. t and MtT, an example is shown in which the concentration CI6 is kept at a constant value.

In the example shown in Fig. 1θ, the distribution concentration C of germanium atoms contained in the first layer (i) is a concentration C,7 at a position t, and from this concentration C17 until a position t6 is reached. is slowly decreased, and around the position t6, it is rapidly decreased, and at the position t, the concentration C7f
1! : To be done.

Between position t6 and position t7, the concentration decreases rapidly at first, and then slowly decreases to C1 at position t7, and between position t7 and position t, the concentration decreases extremely slowly. and gradually decreased to position 1. At this point, the concentration reaches a certain level. Position 1. and the position t□, the density is reduced from 02a to substantially zero according to a curve shaped as shown in the figure.

As described above, from FIG. 2 to FIG. 1θ, the first layer (1) 10
As described above with reference to some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention, the support 101 side has a portion with a high distribution concentration C of germanium atoms. , on the interface t1 side, the distribution state of germanium atoms has a portion where the distribution concentration -C is considerably lower than that on the support 101 side.
) 102 is one preferred example.

First layer (I) 1 constituting the photoconductive member in the present invention
02 preferably has a localized region (A) containing germanium atoms at a relatively high concentration on the support 101 side or, conversely, on the free surface 107 side, as described above. is desirable.

For example, if the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (A) be provided within 5IL in the layer thickness direction from the interface position tI3.

The localized region (A) may be the entire layer region (L□) up to a thickness of 5 μm from the interface position t6, or may be a part of the layer region (LT).

Whether the localized region (A) is a part or all of the layer region (Lr) is determined as appropriate depending on the characteristics required of the first layer (1) 102 to be formed.

In the localized region (A), as the distribution state of the germanium atoms contained therein in the layer thickness direction, the maximum value Cmai of the distribution concentration of germanium atoms is the sum with silicon atoms,
Preferably 1000 atoms ppo+ or more, more preferably 5
000 atomic ppm or more, optimally I
It is desirable that the layers be formed so that a distribution state of m or more can be achieved.

That is, in the present invention, the first layer (I) 1'02 containing germanium atoms has a distributed concentration within 5 layers in thickness from the support 101 side (a layer region of 5 layers thick from tB). It is preferable that the maximum value Cwax exists.

In the present invention, the content of germanium atoms contained in the first layer (I) 102 is appropriately determined as desired so as to effectively achieve the object of the present invention. Preferably 1 to 9 for the sum of
5 X 10s atomic ppm, more preferably 100-8X
10 atomic ppm, optimally 500-7×lO atomic ppm
It is desirable to set it as pm.

The distribution state of germanium atoms in the first layer (I) 102 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 determined by light from the support lot side. If a decreasing change or vice versa is applied towards the free surface 107 of the receiving layer 108, the rate of change curve of the distributed concentration C can be arbitrarily designed as desired. Accordingly, the first layer (I) 102 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer (1) 102 should be sufficiently increased on the support 101 side, and should be as low as possible on the free surface 107 of the photoreceptive layer 108. By applying changes in the IrJ 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 prevent interference with coherent light such as laser light.

Furthermore, as will be described later, by extremely increasing the distribution concentration C of germanium atoms at the end of the first layer (I) 102 on the side of the support 101, it is possible to , it is possible to substantially completely absorb light on the long wavelength side that cannot be sufficiently absorbed on the laser irradiation surface side of the photoreceptive layer 108 in the end layer region of the photoreceptive layer 108 on the support 101 side. Therefore, interference due to reflection from the support surface can be effectively prevented.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and increasing dark resistance, and further improving the adhesion between the support 101 and the first layer (I) LO2, First layer (I) 1
02 contains a carbon atom. First layer (I)
The carbon atoms contained in C) 2 may be evenly contained in the entire layer area of the first layer (1) 102 satisfying the above conditions, or the carbon atoms contained in the first layer (I) It may be contained only in a part of the layer region of 102 and unevenly distributed.

In the present invention, the distribution state of carbon atoms is determined in the first layer (I
) 102 as a whole is non-uniform in the layer thickness direction as described above, but in each of the first, 1lS2° and third regions, it is uniform in the layer thickness direction.

11 to 15 show typical examples of the distribution of carbon atoms in the entire first layer (I) 102. FIG. still,
Symbols used throughout these descriptions have the same meanings as used in FIGS. 2 through 10.

In the example shown in the figure, the position t9 is lower than the position tB.
The distribution concentration C (C) of carbon atoms is assumed to be a constant value of Cz + χ, and from position t9 to position Mt□ the distribution concentration C of carbon atoms is
(C) is assumed to be constant at C22.

In the example shown in FIG. 12, from position t to position t10, the distribution concentration of carbon atoms C(C) is a constant value of C23. From position t10 to position t11, the distribution concentration of carbon atoms C(C) ) is taken as Cr2, and from position tI+ to position tT
Until now, the distribution concentration C (C) of carbon atoms was assumed to be 02g,
The distribution concentration C (C) of carbon atoms is reduced in three stages.

In the example of the pfS13 diagram, from position t to position 12, the distribution concentration C (C) of carbon atoms is 02G, and at position t12
From the position to the position, the distribution concentration of carbon atoms C (C) is C2
It is said to be 7.

In the example of FIG. 14, from position tB to position t1. From position t13 to position t, the distribution concentration C (C) of carbon atoms is CZa, and from position t13 to position t, the distribution concentration C (C) of carbon atoms is C2,
The distribution concentration C (C) of carbon atoms from position t to position tT is CBD-.

In this way, the distribution concentration C (C) of carbon atoms is increased in three stages. In the example in Fig. 15, from position t to position t15, the distribution concentration C (C) of carbon atoms is C31, From position tIs to position g:t, the distribution concentration C(C) of carbon atoms is C32, and from position t16 to position t, the distribution concentration C(C) of carbon atoms is C33. in this way,
The distribution concentration C (C) of carbon atoms is made to be high on the support body 101 side and the free surface 107 side.

In the present invention, the layer region (C) containing carbon atoms provided in the first layer (I) 102 (the above-described first layer region (C)) is provided in the first layer (I) 102.
Second. The third region (consisting of at least two layer regions 104 to 106) occupies the entire layer region of the first layer (I) 102 when the main purpose is to improve photosensitivity and dark resistance. the free surface 10 of the photoreceptive layer 108
To prevent charge injection from the free surface 10
Provided near the interface on the 7 side, the support 101 and the first layer (
When the main purpose is to strengthen the adhesion between the first layer (I) 102 and the first layer (I) 102, the support io
It is provided so as to occupy the t-side end layer region (E).

The content of carbon atoms contained in the layer region (C) is made relatively small in order to maintain high photosensitivity as described above, and is To prevent charge injection, a relatively large amount of
Furthermore, in order to ensure the reinforcement of the adhesion between the support body 101 and the first layer (I) 102, it is desirable that the amount be relatively large.

In addition, in order to achieve these three things at the same time, the support 101
A relatively high concentration of carbon atoms is distributed on the sides, a relatively low concentration is distributed in the center, and a distribution state of carbon atoms with a larger number of carbon atoms is formed in the interface layer region on the free surface 107 side. It may be formed in region (C).

In the present invention, the carbon atom content in the carbon atom-containing layer region (C) provided in the first layer (I) 102 depends on the characteristics required for the layer region (C) itself or the layer region (C). When the region (C) is provided in direct contact with the support lot, it may be selected as appropriate in terms of organic relationship, such as the relationship with the characteristics at the contact interface with the support 101. I can do it.

In addition, when another layer region is provided in direct contact with the layer region (C), 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. Consideration: The content of carbon atoms is selected accordingly.

The amount of carbon atoms included in the layer region (C) is determined as desired depending on the properties required of the photoconductive member to be formed, but it is On the other hand, it is preferably o,oot to 50 atom%, more preferably 0.002 to 40w, and most preferably 0.003 to 30 atom%.

In the present invention, the layer region (C) 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 pressure TO of the layer region (C) to the layer pressure T of the first layer (I) 102 is sufficient. When the amount of carbon atoms is large, it is desirable that the upper limit of the content of carbon atoms contained in the layer region (C) is sufficiently smaller than the above value.

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

If the ratio of carbon atoms to the layer thickness T of the first layer (I) 102 is two-fifths or more, the upper limit of the carbon atoms contained in the layer region (C) is , silicon atom,
With respect to the sum of the three atoms, germanium atoms and carbon atoms, it is preferably 30 atom % or less, more preferably 20 atom % or less, and optimally 1O atom % or less.

In the present invention, the layer region CC) containing carbon atoms is formed on the support lO1 side or/and the second layer (I
I) It is preferable to provide a localized region (B) containing a relatively high concentration of carbon atoms near the 103 side, and in this case, the support lot and the first layer (I ) 102 and the acceptance potential can be further improved.

The localized region (B) is desirably provided within 5 l in the layer thickness direction from the interface position t or tT, as described using the symbols shown in FIGS. 11 to 15.

In the present invention, the localized region (B) is located at the interface position t
It may be the entire layer area (LT) from 13 or 70 to 5 l thick, or it may be a part of the layer area (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 first layer (I) 102 to be formed.

In the localized region (B), the maximum value Cmax of the distribution concentration C (C) of carbon atoms as the distribution state of the carbon atoms contained therein in the layer thickness direction is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more. Atomic ppm or more, optimally 1000
It is desirable that the layer be formed in such a manner that a distribution state of atomic ppm or more can be obtained.

That is, in the present invention, in the first layer (Z) 102,
The layer region (C) containing carbon atoms has a layer thickness of 5 from the support 101 side or from the surface side of the second layer (II) 103.
It is preferable that the maximum value Cmax of the distributed concentration C (C) exists within the range 1 (layer region with a thickness of 5 iL from position t or tl).

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 CI) 102
By containing therein a substance (D) that controls the conductive properties, the conductive properties of the first layer (I) 102 can be arbitrarily controlled as desired.

As the substance (D) that controls such conductive characteristics, there can be mentioned so-called impurities in the semiconductor field, and in the present invention, the substance (D) that constitutes the first layer (I) 102 to be formed can be mentioned. For a-3iGe (H, Specifically, the P-type impurity is an atom belonging to Group Ⅰ of the periodic table (Group Ⅰ atom), for example, boron (B).

Examples include aluminum (All), gallium (Ga), indium (In), and thallium (Tl), among which B and Ga are particularly preferably used. In addition, n-type impurities include atoms belonging to group V of the periodic table (group II atoms),
For example, phosphorus (P), arsenic (As), antimony (sb)
.

Bismuth (Bi), etc., and particularly preferably used 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, in order to contain the substance controlling the conductive properties in the first layer (I) 102, the second layer (I)
When locally contained in 102 desired layer regions,
In particular, when it is contained in the support side end layer region of the first layer (I) 102, the characteristics of the other layer region provided in direct contact with the layer region and the relationship between the layer region and the other layer region are particularly important. 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.

In the present invention, the content of the substance (D) that controls conduction properties contained in the first layer (I) 102 is preferably 0. 1 to 5 x lO atoms ppm, more preferably 0.5 to 1 x 104 atoms ppm, optimally 1 to 5 x 1
011; It is desirable that the content be J ppm.

In the present invention, the content of the substance (D) in the layer region containing the substance (D) that controls conduction properties is preferably 30 atomic ppm or more, more preferably 50 atomic ppm.
+ or more, optimally 100 atomic ppm or more,
The substance (D) that controls the conductive properties is the first layer (I)
It is desirable to locally contain it in a part of the layer region of the first layer (I) 102, and it is particularly desirable to make it unevenly distributed in the end layer region (E) on the support side 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 (I) 102 in a content equal to or higher than the above value, 1 For example, if the substance (D) is the p-type impurity, it is injected into the photoreceptive layer i08 from the support lO1 side when the free surface 107 of the photoreceptive layer 10g is charged to the polarity of When the substance that can effectively block the movement of electrons and controls the conduction characteristics is the n-type impurity, the free surface 107 of the photoreceptive layer 108 is charged to e-polarity. At this time, the movement of holes injected from the support lO1 side into the photoreceptive layer 108 can be effectively prevented.

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 tooo atomic ppm, more preferably 0.05 to 500 atomic ppm, optimally 0
．． 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 material in the layer region (Z) The amount of 44 is preferably 30 atomic ppm or less. In addition to the above-mentioned case, in the present invention, a layer region containing a substance controlling conductivity having one polarity in the first layer (1) 102 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-
A depletion layer can be provided by forming an n-junction.

In the present invention, the first layer (I)-102 composed of a-S iGe (H,
It is formed by a vacuum deposition method that utilizes a discharge phenomenon such as a sputtering method or an ion blating method. For example, a-5i Ge (H,
X) To form the first layer (I) 102 composed of A source gas and 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, thereby generating a glow discharge within the deposition chamber. a-5iG on the surface of a predetermined support, which
A layer consisting of e (H,X) may be formed. Further, germanium atoms are formed in the first layer (I) 10 in a non-uniformly distributed state.
In order to incorporate a-3iGe(H,
What is necessary is to form a layer consisting of X).

In addition, in the sputtering method, for example, an inert gas such as Ar or He or a gas such as
Using a target composed of silicon atoms in an atmosphere of M gas, or a target composed of the target and germanium atoms, or a mixed target of silicon atoms and germanium atoms. If necessary, a raw material gas for supplying germanium atoms diluted with a diluent gas such as He or 'Ar, and a gas for introducing hydrogen atoms or/and halogen atoms are introduced into the deposition chamber for sputtering. Then, a first layer (I) 102 is formed by forming a plasma atmosphere of a desired gas.

In this sputtering method, if the distribution of germanium atoms is to be made uniform, the target may be sputtered while controlling the gas flow rate 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 housed in a deposition port as evaporation sources, and the evaporation sources are heated using a resistance heating method or an electron beam. Except for heating and evaporating by method (EB method) etc. and passing the flying evaporated material through the desired gas plasma atmosphere,
The first layer (I) 102 can be formed in the same manner as in the case of sputtering.

Substances that can be used as a raw material gas for supplying silicon atoms used in the present invention include:

S i H4, S l2) (G, S i, H8, 5i4
H,,'iminocous or gasifiable silicon hydride (
Silanes) can be effectively used, and S i H4 and S 12H4 are particularly preferred in terms of ease of handling during layer formation work and good silicon atom supply efficiency.

Substances that can serve as raw material scraps for supplying germanium atoms include G e H4, G e2H,, G e3H,, G
e,H,,,G e5H,7,G e,H,,,G
e7H,6,G e,H,f.

Geranium hydride in the gaseous state or gasifiable in Ge, H2, $ is mentioned as being usefully used;
In particular, GeH4, G e2H,, G
e, H-< preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, and halogen-substituted silane derivatives. Or a halogen compound that can be gasified is preferably mentioned. 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, CuF, CRI3, BrF5. BrF
Examples include interhalogen compounds such as 3, I I8, I F, ICM, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, 5
The characteristic photoconductive member of the present invention is formed by a glow discharge method using silicon halides such as 12F4.5i2F, SiO4, SiBr, etc., and silicon compounds containing such halogen atoms. In this case, a-S containing halogen atoms can be formed on the desired support 101 without using silicon hydride gas as a source gas capable of supplying silicon atoms together with a source gas for supplying germanium atoms.
A first layer (I) 102 made of iGe can be formed.

According to the glow discharge method, the first layer containing halogen atoms (
I) When manufacturing 102, basically, for example, silicon halide is used as a raw material gas for supplying silicon atoms, germanium hydride is used as a raw material gas for germanium atoms, and gases such as Ar, I2, He, etc. are introduced into a deposition chamber in which a photoreceptive layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases, thereby depositing them on a desired support 101. However, in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or silicon containing hydrogen atoms may be added to these gases. The compound gas may also be added in a desired amount to form a layer.

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

In order to introduce halogen atoms into the first layer CI) 102 formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is deposited. The gas may be introduced into the chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms into the first layer (I) 102, a raw material gas for introducing hydrogen atoms, such as I2, or the above-mentioned silanes and/or gases such as germanium hydride, is used. The gas may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gas.

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;
In addition, hydrogen halides such as HF, HCu, HBr, HI, S i I2F2.5iH2I2.5iI2C,
.

Halogen-substituted silicon hydride such as 5iHC Mi3, S i H2B r2.5iHBr, and G e HI3゜G
e I2F2, G e H, F, G e HCl,,
G e H, Cn.

, GeHCJI GeHBr, GeHBr, GeH,B
r, GeHI, ,GeH,I, ,GeH,I and other halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides, GeF, 10GeCfL4, GeBr4, GeI4,G
e F,, G e Cl,, G e B r2, GeI
Gaseous or gasifiable substances such as germanium halides such as 2, etc. may also be mentioned as useful starting materials for forming the first layer (I) 102.

Among these substances, halides containing hydrogen atoms are extremely effective for controlling electrical or optical properties at the same time as introducing halogen atoms into the layer when forming the first layer (I) 102. Since hydrogen 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 (I) 102, in addition to the above, H2, S i H4, S i2
H,, Si3H, Si4H-protected silicon hydride with germanium or germanium compound for supplying germanium atoms, or G e H4, Ge2H,, G
e3Hr, G e+H,,,G esH,2,G
e, H, +, G e, H, 4, G e, H,,, G C
9H, Rating c7) 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, the amount of halogen atoms, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the first layer (I) 102 of the photoconductive member to be formed is preferably 0.01 to 40 atom%, more preferably 0.05 to 30 atom%, optimally O81-2
It is desirable that the content be 5 at.%.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the first layer CI) 102, it is possible to control, for example, the temperature of the support or/and the starting materials used for containing hydrogen atoms or halogen atoms. clay to be introduced into the deposition system of
All you have to do is control the discharge force, etc.

In the present invention, in order to provide the layer region (C) containing carbon atoms in the first layer (I) 102, the above-mentioned starting material for introducing carbon atoms is added during the formation of the first layer 102. In the first layer (I), it may be used together with a starting material for forming LO2, and may be contained in the formed layer while controlling its amount.

When a glow discharge method is used to form the layer region (C), a starting material for introducing carbon 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 introducing carbon atoms, most of the gaseous substances having at least carbon 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 carbon atoms, and a raw material gas containing hydrogen atoms 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 carbon atoms and hydrogen atoms may be mixed at a desired mixing ratio, or silicon atoms may be mixed with a raw material gas containing silicon atoms as constituent atoms. It is possible to use a mixture of a raw material gas having three constituent atoms: a silicon atom, a carbon atom, and a hydrogen atom.

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

Effective raw material gases for introducing carbon atoms include:
Examples include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene-based hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 4 carbon atoms.

Specifically, the saturated hydrocarbon is methane (CH,)
, Ethane (C2H□, Propane (03H1) I
n-butane (nC4H,6), pentane (C.

H,, ), ethylene hydrocarbons include ethylene (
C2H4), propylene (C,H,), butene-1
(C+Hr), butene-2(rimachi)inbutylene CC
Examples of the acetylene hydrocarbons include acetylene (C and H2), methylacetylene (C3H,), and butyne (C4H,).

In addition to these, Si(CH,)4. S
Examples include alkyl silicides such as i (C, H, etc.).

In the present invention, the one-layer region (C) may further contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms in order to further enhance the effect obtained by carbon atoms.

Acid-resistant nitrogen (N, 0), nitrogen sesquioxide (N.

O8), trinitrogen tetraoxide (N304) *Nitrogen sesquioxide (
N20. )', Nitrogen trifluoride (No, ), whose constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, for example, disiloxane (H, S i OS i HJ), ) resiloxane (H3S i OS i H2O5i H,
) and other lower siloxanes.

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms used when forming the layer region (C) include nitrogen atoms as constituent atoms or nitrogen atoms and hydrogen atoms as constituent atoms. Atoms such as nitrogen (N), ammonia (NH6), hydrazine (H2NNH,), hydrogen azide (HNρ, ammonium azide (NH,Nρ)
Mention may be made of gaseous or gasifiable 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), nitrogen tetrafluoride (
Examples include halogenated nitrogen compounds such as F+NYU).

To form the first layer (I) 1o2* containing carbon atoms by a sputtering method, use a single crystal or polycrystalline silicon wafer or a graphite wafer, or a wafer containing a mixture of silicon atoms and carbon atoms. This can be done by sputtering them in various gas atmospheres using as a target.

For example, if a silicon wafer is used as a target, the raw material gas for introducing carbon 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 gases.

Alternatively, silicon atoms and carbon atoms can be used as separate targets, or by using a single target with a mixture of silicon atoms and carbon atoms, in an atmosphere of diluent gas as a sputtering gas, or at least This is accomplished by sputtering in a gas atmosphere containing hydrogen atoms and/or halogen atoms as constituent atoms. As a raw material gas for introducing carbon atoms,
The raw material gas for introducing carbon atoms in the raw material gas shown in the glow discharge example described above can also be used as an effective gas in the case of sputtering.

In the present invention, when forming the first layer (I) 102,
When providing a layer region (C) containing carbon atoms, the distribution concentration C (C) of carbon atoms contained in the layer region (C) is changed in the layer thickness direction to obtain a desired distribution in the layer thickness direction. Condition '8
(depth profile), in the case of glow discharge, the distribution concentration C (C
) is introduced into the deposition chamber while the gas flow rate of the starting material for introduction of carbon atoms to be changed is appropriately changed according to a desired rate of change curve.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change of the flow rate does not need to be linear; for example, a pre-designed rate of change curve can be obtained using a microcomputer or the like.

When forming the layer region (C) by a sputtering method, the distribution concentration C (C) of carbon atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (d) of carbon atoms in the layer thickness direction.
epth profile), first, as in the case of the glow discharge method, a starting material for introducing carbon atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is adjusted. This can be done by appropriately changing as desired.

Second, if a target for sputtering is used, for example, a target containing a mixture of silicon atoms and carbon atoms, the mixing ratio of silicon atoms and carbon atoms should be changed in advance in the layer thickness direction of the target. It is achieved by letting it happen.

In the first layer (I) 102, a substance that controls the conduction properties;
For example, in order to structurally introduce a group II atom or a group V atom, a starting material for introducing a group II atom or a starting material for introducing a group V atom is deposited in a gaseous state during layer formation. It may be introduced into the chamber together with other starting materials for forming the first layer (I) 102. 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 introducing such Group I atoms include B2H, B4H, and B4H for boron atom introduction. , B, H9, BjHll, B.C.
Boron hydride such as H+D, B, H12, Bg H+4, B
Examples include boron halides such as F3, B CfL3, and BBrl.

In addition, A J2. CM,,G e Cn,,Ge(
CHj), I n CD, , T u CfL5, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PHP,
Hydrogen phosphorus monolide, PHI, P F3, P F5, P C phosphorus, P C
Examples include phosphorus halides such as i, , PBrJ, PBr, PI, and the like. In addition, As H,, As F,, As
Cf)-,.

AsBrJ, AsF,, SbH,, S b F,, S
b F,,s b c,c,,S b C,Q,,B
i H,, B i CfL, B i B r, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the layer thickness of the layer region constituting the first layer (I) 102 and containing a substance that controls conduction properties and provided unevenly on the support 101 side is as follows: and the other layer regions forming the first layer (I) 102 formed on the layer region. Preferably 30λ or more, more preferably 40A or more, optimally 50A or more
It is desirable that it be λ or more. Further, the content of the substance controlling the conductive properties contained in the layer region is 30 atomic pp.
m or more, the upper limit of the layer thickness of the layer region is preferably 10 g or less, preferably 8 tiles or less, and optimally 5 p or less.

In the photoconductive member 100 shown in FIG. 1, a second layer (IL) 103 formed on a first layer (I) 102
has free blood loss 107, and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

Further, in the present invention, each of the amorphous materials constituting the first layer (I) 102 and the second layer (1) 103 has a common constituent element, silicon atoms.
Both layers CI) 10213 yo 0'(X) 103 (7) Chemical stability is sufficiently ensured at the laminated interface.

The second layer (II) 103 in the present invention is an amorphous material (hereinafter referred to as ' a-(
SlxNl-x), (HlX)1-7''. However, 0<x, y<1).

The second layer (II) 103 composed of a-(S+x)L-x)y(H+X)1-z is formed by a glow discharge method, a sputtering method, an electron beam method, or the like.

These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. A second layer (and) 10 in which it is relatively easy to control the creation conditions for manufacturing the conductive member and in which nitrogen atoms and halogen atoms are created together with silicon atoms.
A glow discharge method or a sputtering method is preferably employed, which has the advantage that it can be easily introduced into the liquid.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same device system to form the second layer (11) 1
03 may be formed.

To form the second layer (]I) 103 by the glow discharge method, a-(SixN, J (H, The gas is mixed and introduced into the vacuum deposition chamber where the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, so that the gas already formed on the support 101 is On the first layer (I) 102, a-
(SixN+-x)7 (u, x),-, may be deposited.

In the present invention, a-(SiyN+-x)y (H,X
The raw material gas for forming the film may be a gaseous substance whose constituent atoms are at least one of silicon atoms, nitrogen atoms, hydrogen atoms, and halogen atoms, or most of the gasified substances that can be gasified. can be used.

When using a raw material gas containing a silicon atom as one of silicon atoms, nitrogen atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas containing silicon atoms and a nitrogen atom may be used. A raw material gas containing silicon atoms and a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms as necessary in a desired mixing ratio are used, or silicon atoms are used. A raw material gas having constituent atoms and a raw material gas having nitrogen atoms and hydrogen atoms or/and a raw material gas having nitrogen atoms and halogen atoms are also mixed at a desired mixing ratio. Or, a raw material gas containing silicon atoms as constituent atoms, and a raw material gas containing three constituent atoms: silicon atoms, nitrogen atoms, and hydrogen atoms, or three constituent atoms: silicon atoms, nitrogen atoms, and halogen atoms.
It can be used in combination with a raw material gas having two constituent atoms.

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

In the present invention, fluorine and chlorine are preferable as the halogen atoms contained in the second layer (x) 103.

Bromine and iodine are preferred, with fluorine and chlorine being particularly preferred.

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

When the second layer (n) 103 is made of the above-mentioned amorphous material, the layer forming method may be a glow discharge method, a sputtering method, an ion implantation method, an ioj brating method, an electron beam method, etc. can be mentioned. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing photoconductive members, and in addition to silicon atoms, nitrogen atoms,
A glow discharge method or a sputtering method is preferably employed, which has advantages such as easy introduction of hydrogen atoms and halogen atoms into the second layer (][) t03.

Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same device system to form the second layer (11) 1
03 may be formed.

In order to form the second layer (IL) 103 composed of a-9iN (H, A source gas for introducing atoms and, if necessary, a source gas for introducing hydrogen atoms and/or a source gas for introducing halogen atoms are introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. , a-S on a predetermined first layer (I) 102 which has been placed in a predetermined position in advance.
A second layer (II) 103 made of iN (H,X) may be formed.

Further, when forming the second layer (I) 103 by sputtering, the process is performed as follows, for example.

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

Secondly, S i as a target for sputtering
A target composed of 3N4, or a target composed of silicon atoms and a target composed of 5ijN4, or a target composed of silicon atoms and Si, N4.
Nitrogen atoms can be introduced into the second layer (1) 103 formed by using a target composed of the following. At this time, if the aforementioned raw material gas for introducing nitrogen atoms is also used, the second layer (
1) It is easy to arbitrarily control the amount of nitrogen atoms introduced into 103.

The content of nitrogen atoms introduced into the second layer (rL) 1 (13) can be determined by controlling the flow rate when the raw material gas for introducing nitrogen atoms is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing nitrogen atoms is introduced into the deposition chamber. The proportion of nitrogen atoms contained in the target can be arbitrarily controlled as desired by adjusting the proportion of nitrogen atoms contained in the target when the target is produced, or by doing both.

The starting material used in the present invention as a raw material gas for supplying silicon atoms is SiH.

Gaseous or gasifiable arsenic hydride (silanes) such as S i, H,, S i, H,, S i, Hto, etc. are used. In terms of silicon atom supply efficiency, SiH4,
Preferred examples include Si and H. By using these starting materials, it is possible to introduce hydrogen atoms as well as silicon atoms into the second layer (I) 103 formed by appropriately selecting layer forming conditions.

In addition to the above-mentioned hydrocarbons, effective starting materials that can be used as raw material gas for supplying silicon atoms include 41-element compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, For example, SiF,,Si,F,,
5ICn. Preferred examples include silicon halides such as , 5iBr+, and the like.

Furthermore, SiH2F2, 5iH2I,, SiHyoC21 SiuC! ;Lx +5iH2Br,, 5i
Silicon atoms for forming the second layer (x) 103, which is also effective with halogen-substituted hydrogen fossil main fibers such as HBr, etc., and halides that have hydrogen atoms as one of their constituents, which are in a gaseous state or can be gasified. It can be mentioned as a starting material for supply.

Even when these silicon compounds containing halogen atoms are used, it is possible to introduce halogen atoms together with silicon atoms into the second layer (U 103) to be formed by appropriately selecting the layer forming conditions as described above. be able to.

Among the above-mentioned starting materials, a halogenated compound containing a hydrogen atom is used during the formation of the second layer (IL) 103.
Hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer, so they are used as a suitable starting material for introducing halogen atoms in the present invention.

In addition to the above-mentioned materials, effective starting materials that serve as raw material gases for introducing halogen atoms used when forming the second layer (1) 103 in the present invention include, for example, fluorine, chlorine, bromine, and iodine. Halogen gas, BrF, C
Also, interhalogen compounds such as F, CJlj F BrF BrF3゜J"S' LF, TF7, ICU, IBr, HF.

Examples include X halides such as HGfL, HBr, and old.

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms used when forming the second layer (II) 103 is one that has nitrogen atoms as a constituent atom or contains nitrogen atoms, For example, nitrogen (N2), ammonia (NH), hydrazine (
Mention may be made of gaseous or gasifiable nitrogen, such as hydrogen azide (uNi), ammonium azide (NH4N, ), nitrogen compounds such as nitrides and azides. In addition to this, nitrogen trifluoride (F, N) is also used as a starting material because it can introduce halogen atoms in addition to nitrogen atoms.

Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F4N).

In the present invention, the diluent gas used when forming the second layer (I) 103 by a glow discharge method or a sputtering method is a so-called rare gas, such as He, Ne, A
Preferred examples include r.

The second layer (I) 103 in the present invention is carefully formed so that its required properties are provided as desired.

In other words, substances whose constituent atoms are silicon atoms, nitrogen atoms, hydrogen atoms and/or halogen atoms if necessary, can 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 the present invention, a-
(St XNl-4(H,

For example, in order to provide the second layer (J) 103 with the main purpose of improving electrical voltage resistance, a-(St, N, -,)
y(HIX)t-7 is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the second layer (1) 103 is provided for the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the degree of electrical insulation mentioned above is relaxed to some extent, and it becomes less resistant to the irradiated light. As amorphous materials having a certain degree of sensitivity, a-(Si, N, A), (H, X)1. −, is created.

On the surface of the first layer (I) 102 (7), a-(s;yN
The second scrap (1) consisting of +-x)y (HIX)l-7
When forming 103, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. In the present invention, it is desirable that the temperature of the support during layer formation be strictly controlled so that a-(SixN+-y); (H9X)-7 having the desired properties can be formed as desired. In order to effectively achieve the desired purpose in the present invention, the second layer (x) 103 is formed by selecting an optimal range of support temperature and forming the second layer (n). ) 103 is carried out, the support temperature during layer formation is preferably between 20 and 400° C.
More preferably 50-350°C1 optimally 100-30°C
It is desirable that the temperature be 0°C.

To form the second layer (x) 103, glow discharge is used to form the second layer (x) 103, since delicate control of the composition ratio of atoms constituting the layer and control of layer density are relatively easy compared to other methods. However, when forming the second layer (1) 103 using these layer forming methods, the discharge power during layer formation as well as the support temperature described above must be adjusted. , is one of the important factors that influences the characteristics of the produced als+yNI-)y(H2X)1-7.

a having the characteristics for achieving the object of the present invention
-(SiN1Ωy ('l + It is desirable that the power be 250W, most preferably 5.0 to 200W.

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 preferable numerical ranges of the support temperature and discharge power for creating the second layer (x>103) include the values in the above-mentioned ranges.

However, these layer creation factors cannot be determined independently and separately, but are based on the desired characteristics a − (S ix
N1-X), (H+

The amount of nitrogen atoms contained in the second layer 103 in the photoconductive member of the present invention is the same as the second M2O3 production conditions.
Therefore, the amount of nitrogen atoms contained in this second layer (n) 103 is an important factor in the formation of the second layer (11) 103 that achieves the desired properties that achieve the object of the present invention. is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (1) 103.

That is, the general formula a-(Si, N, -x)y (H
The amorphous material represented by 9X)+-y can be roughly divided into an amorphous material composed of silicon atoms and nitrogen atoms (hereinafter referred to as r a-3i, 1 N, -WJ. However, 0
<a<1), an amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms (hereinafter referred to as ' a -(S I
b N+-b) Written as cH, -cJ. However, 0<b, c
<1), an amorphous material composed of silicon atoms, nitrogen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as '
It is written as a-(S'b'+4)e(H2X)1-eJ. However, they are classified into 0<d, e<1).

In the present invention, the second layer (1) 103 is a-SiN
14, the amount of nitrogen atoms contained in the second layer (X) 103 is preferably 1xlO to 80 at%, more preferably 1 to 50 at%, optimally 10 to 45
It is desirable to set it as M%. That is, if we use the above a-sraka display, 8 is preferably 0.
4-0.9i3999, more preferably 0.5-0.8
9, optimally between 0.55 and 0.9.

In the present invention, the second direct 3 is a − (S i b N
+-b) When composed of c n, c, the second layer (IL
) The amount of nitrogen atoms contained in 103 is preferably l
It is desirable that Xl be 0 to 55 atom %, more preferably 1 to 55 atom %, and optimally 1O to 50 atom %.

Furthermore, the content of hydrogen atoms is preferably 1 to 4
0 at%, more preferably 2 to 35 at%, optimally 5
It is desirable that the hydrogen atom content be in the range of 30 to 30 at.

That is, the previous "-("' lb "1-b) cHl
- If we do this in b and C representation of c, b is preferably 0.4
5-0. H998, preferably 0.45 to 0.38,
Optimally 0.45 to 0.9, with C preferably 0.45 to 0.9.
Desirably, it is between 8 and 0.98, more preferably between 0.65 and 0.98, most preferably between 0.7 and 0.85.

Second layer (II) 103 is a-(Si, 1NI-4)
e (n, x), -, the content of nitrogen atoms contained in the second layer (1) 103 is preferably l is desirably 1 to 60 atomic %, most preferably 10 to 55 atomic %. Furthermore, the content of halogen atoms is preferably 1 to 20 at%, more preferably 1
-18 atom%, optimally 2 to 15 atom%, and photoconductive members made with halogen atom content in this range can be sufficiently applied in practice. be. Furthermore, the content of hydrogen atoms, which may be included as necessary, is preferably 18 atomic % or less, more preferably 13 atomic % or less.

That is, first) a-(Si, INIJ (H,X), -
, d is preferably 0.4 to e.
0.8999!9, more preferably 0.4 to 0.88, optimally 0.45 to 0.9, and e is preferably 0.8
~O,l1ll#, more preferably 0.82-0.99,
The optimum value is 0.85 to 0.98.

The range of layer thickness of the second layer (and) 103 in the present invention is as follows:
This is one of the important factors for effectively achieving the purpose of the present invention. The layer thickness 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, including the amount of nitrogen atoms contained in the layer (JL) 103 and the layer thickness of the first layer (I) 102. It is necessary to appropriately decide according to the desired organic relationship. In addition, it is desirable that this layer thickness is also taken into account from the economic point of view, taking into account productivity and mass production.

The layer thickness of the second layer (and) i03 in the present invention is as follows:
Preferably 0. o 03-3Jt, more preferably 0
．． It is desirable that the tiles be 004-20, most preferably 0-005-10.

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

Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo, Au, Nb, Ta, V, Ti, P
Examples include metals such as T, Pd, and alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate-1, 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 conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr1. A
l, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Pt, Pd, I n, O,, SnO,, I To
Conductivity is imparted by providing a thin film consisting of (I n, O, + S n Q,), etc., or if it is a synthetic resin film such as a polyester film, NiCr
, An, Ag, Pb.

Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta,
Conductivity is imparted to the surface by providing a thin film of metal such as V, Ti, or Pt on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminating the surface with the metal.

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. 1 may be used as an electrophotographic image forming member. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape.

The thickness of the support 101 is appropriately determined so as to form a desired photoconductive member, but when the photoconductive member is required to have high performance, the thickness of the support 101 is determined so that it can sufficiently function as a support. It is made as thin as possible within the range. Hyakunen et al.
In such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness of the support 101 is preferably 10
It is considered to be more than μ.

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

FIG. 16 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 H, / He is abbreviated as ) cylinder, 1103 is He
1104 is a GeH+ gas (purity 99.999%, hereinafter abbreviated as GeH4/He) diluted with He gas (purity 99.999%, hereinafter referred to as S
i F4/He, abbreviated as) cylinder, 1105 is C,
H4 gas (99.999% purity) cylinder, 110B is H
2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1101, gas pumps 1102-1106 (1) At-fu 1122-1
126, confirm that the leak valve 1135 is closed, and also check the inflow valves 1112 to 1116, the outflow valves 1117 to 1121, and the auxiliary valves 1132 and 1133.
First, check that the main valve 11 is opened.
34 is opened to exhaust the reaction chamber 1101 and each gas pipe.The reading on the vacuum gauge 1136 is approximately 5XlOtorr.
When the auxiliary valves 1132, 1133. Close outflow valves 1117-1121.

Next, to give an example of forming a photoreceptive layer on the cylindrical substrate 1137 as a support, Si H4/He gas from the gas cylinder 1102,
The G e H4/He gas from the gas pump 1103 and the CaH gas from the gas pump 1105 are supplied to the valve 112.
2,1123.Open 1125 and outlet pressure gauge 1127
．． Adjust the pressure of 1128°l13'o to 1kg/C, and then open the inlet valve 1112. By gradually increasing the mass flow controller 1107.1
108 and 1110 respectively. Subsequently, outflow valve 1117°1118.1120, auxiliary valve 11
32 is gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, the outflow valve 1117°111 is adjusted so that the ratio of the S i H4/He gas flow rate, the Q e H4/He gas flow rate, and the C2H4 gas flow rate becomes a desired value.
8. Adjust the opening of the main valve 1134 while checking the reading of the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. and base 1
The temperature of 137 is set to 50 to 40 by the overheating heater 1138.
After confirming that the temperature is set in the range of 0℃,
The power source 1140 is set to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time, the opening of the valve 1120 is changed accordingly according to a pre-designed rate of change curve by applying a method such as manual or external drive motor. The operation is performed to adjust the flow rate of the CxHf gas, thereby controlling the distribution concentration C (C) of carbon atoms contained in the layer formed. Thus, the first (7) 7# (I
) 102 is formed.

First layer (I) 1 formed to a desired layer thickness as described above
02 upper GC second no J! ? (II) To form 103, for example, each of S f H4 gas, NH, and gas such as He etc. is added as necessary by the same valve operation as in the case of forming the first layer 102 (I). It is sufficient to dilute it with a diluent gas and supply it into the reaction chamber 11O1, and to generate glow discharge according to desired conditions.

To impregnate halogen atoms in the second layer (■) 103, for example, add S i F4 gas and NH gas, or add S i H gas to this, and form the second layer (■) in the same manner as above. (2) 103 may be formed.

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 the valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed.

If necessary, the auxiliary hulls 7' 1132 and 1133 are opened, the main valve 1134 is fully opened, and the system is once evacuated to a high vacuum.

The amount of nitrogen atoms contained in the second layer (II) 103 can be determined, for example, by changing the flow rate ratio of S i H4 gas and NHj gas introduced into the reaction chamber 1101 as desired in the case of glow discharge, or Alternatively, when forming a layer by sputtering, the desired layer can be formed by changing the sputter area ratio of the silicon wafer and silicon nitride wafer when forming the target, or by changing the mixing ratio of silicon powder and modified silicon powder. It can be controlled accordingly.

The amount of halogen atoms contained in the second layer (II) 103 is determined by the raw material gas for introducing halogen atoms.

For example, this can be done by adjusting the flow rate when S i F4 gas is introduced into the reaction chamber 11 (jl).

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

Examples will be described below.

Example 1 Using the manufacturing apparatus shown in FIG. 16, samples as electrophotographic image forming members (Samples 8011-1 to 8011-13-
6) were prepared respectively (Table 2).

The content distribution concentration of germanium atoms in each sample is the first
7, and the distribution concentration of carbon atoms is shown in FIG. 18.

Each sample obtained in this way was placed in a charging exposure experimental device 1))5, corona charging was performed for 0.3 seconds (sec) using OKV, and a light image was immediately irradiated.

The light image uses a Dungesten lamp light source.

A light intensity of 21 ux*sec was irradiated through a transmission type test chart.

Immediately thereafter, the surface of the sample (imaging member) was cassgated with an e-chargeable developer (containing toner and carrier) to obtain a good toner image on the surface of the sample (imaging member). 5. The toner image on the sample.
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 used under the same toner image forming conditions, except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a Dungesten lamp as a light source to form an electrostatic image. When the image quality of the toner-transferred images was evaluated, all samples yielded fresh, high-quality images with excellent resolution and good gradation reproducibility.

Example 2 Using the manufacturing apparatus shown in FIG. 16, samples (sample Nos. 21-1 to 21-2) as electrophotographic image forming members were prepared on an AM substrate on a cylinder as a support under the conditions shown in Table 3.
3-fi) were prepared respectively (the 4th cloth density is shown in Figure 17,
Further, the distribution concentration of carbon atoms is shown in FIG.

When each of these samples was subjected to the same image evaluation test as in Example 1, all of the samples provided high quality toner transfer images. In addition, each sample was heated at 38°C and 80% R.
When a repeated use test was conducted 200,000 times in an environment of H, no deterioration in image quality was observed in any of the samples.

Example 3 Material No. 11-1.12 of Example 1 except that the conditions for creating the second layer (II) 103 were as shown in Table 5.
-1 and 13-1, each of the electrophotographic image forming members (sample No. 11-1-1 to 11-1
-8.12-1-1~12-1-8.13-1-1~1
3-1-8) were created.

Each of the electrophotographic image forming members thus obtained 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 (II) 103, the target area ratio between the silicon wafer and silicon nitride was changed, or the content ratio of silicon atoms and nitrogen atoms in the second fi(II) 103 was changed. Each of the image forming members was produced in a completely different manner from that of Sample No. 11-1 of Example 1, except that the sample No. 11-1 was used in Example 1. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated about 50,000 times, and then image evaluation was performed, and the results shown in Table 7 were obtained. Ta.

Example 5 When forming the second layer (II) 103, Si
Sample No. 1 of Example 1 except that the flow rate ratio of H4 gas and NH gas was changed or the content ratio of silicon atoms and nitrogen atoms in the second layer (II) 103 was changed.
Each of the image forming members was created by the same method as in 2-1.

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,
Image evaluation was performed.

The results shown in Table 8 were obtained.

Example 6 When forming the second layer (II) 10.3, Si
Example 1 except that the flow rate ratios of H gas, SiF gas, and NH3 gas were changed, or the content ratio of silicon atoms and nitrogen atoms in the second layer (11) 103 was changed.
Each of the image forming members was prepared in exactly the same manner as Sample No. 13-1. 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 9 were obtained.

Example 7 Each of the image forming members was created in exactly the same manner as in Sample No. 11-1 of Example 1, except that the layer thickness of the second layer (II) was changed to 1.03. 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 2 and Table 10 are shown below.

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

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 9510 each show the distribution state of germanium atoms in the first layer (I). 11 to 15 are explanatory diagrams for explaining the distribution state of carbon atoms in the first layer (I), and FIG. 16 is an explanatory diagram for explaining the distribution state of carbon atoms in the first layer (I). FIGS. 17 and 18, which are schematic illustrations of the apparatus shown in FIG. 100...Photoconductive member 101...Support 102...First layer (I) 103...Second layer (II) 108...・・・
...Photoreceptive layer Fig. 1 Fig. 2 C -C C C (C) Fig. 14 Fig. 15 C<C+ (R+%) (1'702) (1703)

Claims (8)

[Claims] (1) A support for a photoconductive member and an amorphous material containing silicon atoms and germanium atoms were provided on the support. It has a photoreceptive layer consisting of a first layer exhibiting photoconductivity and a second layer provided on the second layer and made of an amorphous material containing silicon atoms and nitrogen atoms. , the first layer contains carbon atoms, and the distribution concentration of carbon atoms in the layer thickness direction is C(1), C(3).
, and a photoconductive member having a first region, a third region, and a second region having values of C(2) in this order from the support side (provided that the distribution concentration C( 3) will not reach the maximum by itself, and if any one of the distribution concentrations C(1), C(2), and C(3) becomes O, the other two are not 0, and are not equal.) (2) The photoconductive member according to claim 1, wherein the first layer contains hydrogen atoms. (3) The photoconductive member according to claims 1 and 2, wherein the first layer contains halogen atoms. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness direction. (5) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer is uniform in the layer thickness direction. (6) The photoconductive member according to claim 1, wherein the first layer contains a substance that controls conductivity. (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 element that controls conductivity is an atom belonging to Group V of the periodic table.