JPS60121453A - Photoconductive member - Google Patents

Abstract

PURPOSE:To stabilize performance, to enhance photosensitivity to a longer wavelength side, and to improve durability by forming a light receiving layer composed of the first photoconductive layer made of a-SiGe contg. O in a specified concn. distribution in the layer thickness direction, and the second layer made of a-SiN. CONSTITUTION:A light receiving layer 104 formed on a substrate 101 consists of the first layer 102 made of a-SiGe and the second layer 103 made of a-SiN. The layer 102 has an layer region O contg. O element nonuniformly and it has a smooth O concn. distribution in the layer thickness direction and it has its max. concn. distribution in the inside of the layer 102. The layer 102 contains H or halogen element and further, a conductivity governing material, such as an element of group III or V. It may contain Ge in a uniform concn. distribution or in a nonuniform concn. distribution. The use of the light receiving layer made of such a-SiGe(H, X) always stabilizes electrical, optical, and photoconductive characteristics, and it can enhance photosensitive characteristics in the long wavelength region, and improve durability.

Description

[Detailed description of the invention] The present invention is based on light (here, light in a broad sense, ultraviolet rays).

The present invention relates to photoconductive members that are sensitive to electromagnetic waves such as visible light, infrared light, X-rays, gamma rays, etc.

Photoconductive materials forming photoconductive QA layers in solid-state imaging devices, electrophotographic image forming members in the image forming field, and document reading devices have high sensitivity and low signal-to-noise ratio [
High photocurrent (,I,)/dark current (Id): ], absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, fast photoresponsiveness, and desired dark resistance value, when used. Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body, 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 this point, amorphous silicon (hereinafter referred to as a-8i) is a photoconductive material that has recently attracted attention.
No. 55718 describes its application as an electrophotographic image forming member, and DE 2933411 describes its application to a photoelectric conversion/reading device.

A photoconductive member having a conventional photoconductive layer composed of A-81 has excellent electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and moisture resistance. The reality is that there are points that can be further improved in terms of usage environment characteristics and furthermore, stability over time, which requires comprehensive improvement of 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 was often observed that residual potential remained during use, and When a conductive member is repeatedly used for a long period of time, fatigue due to repeated use accumulates, and a so-called male strike phenomenon occurs in which an afterimage occurs. Alternatively, when used repeatedly at high speeds, inconveniences such as a gradual decrease in responsiveness often occur.

Furthermore, a-8t has a relatively small absorption coefficient in the long wavelength region compared to the short wavelength region in the visible light region, making it difficult to match with semiconductor lasers currently in practical use. In this case, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there is still room for improvement in that the light on the long wavelength side 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 "decashed" images.

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 forming a photoconductive layer using a-81 material, in order to improve its electrical and photoconductive properties, hydrogen atoms, fluorine atoms, chlorine atoms, etc., and/or rogen atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the type, or other atoms are included in order to improve properties, but how these constituent atoms are contained is determined. In some cases, problems may arise with the electrical or photoconductive properties of the formed layer.

(5) That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer is not sufficient, or the injection of charge from the support side is not sufficiently prevented in the dark area. etc. often occur.

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

Therefore, while efforts are being made to improve the properties of the A-81 material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and provides (6) Applicability of A-8I 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 the viewpoint of applicability, we have found that a silicon atom (sB) and germanium atom (Ge) are the base materials, and contains at least either a hydrogen atom (b) or a halogen atom (3). Amorphous materials, so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium,
A hydrogenated amorphous silicon germanium containing halogen [hereinafter referred to as [a-5iG]
e(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. This is based on the discovery that it has excellent absorption spectrum characteristics on the long wavelength side.

The present invention has stable electrical, optical, and photoconductive properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent photosensitivity on the long wavelength side and is 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 provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer weight.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has sufficient performance and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere.

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

Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support.

The photoconductive member of the present invention includes a support for the photoconductive member, a photoconductive first layer composed of an amorphous material containing silicon atoms and germanium atoms, and a photoconductive first layer composed of an amorphous material containing silicon atoms and germanium atoms. and a light-receiving layer consisting of a second layer made of an amorphous material containing, the first layer having a layer region (0) containing oxygen atoms non-uniformly in the layer thickness direction. , the layer area (
0) is characterized in that the oxygen atom distribution concentration curve in the layer thickness direction is smooth and the maximum distribution concentration is within the first layer.

The photoconductive member of the present invention designed to have the layer structure described above can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties (9). , shows electrical voltage resistance and operating environment characteristics.

In particular, when applied as an electrophotographic image forming member, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. As a result, high-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained with excellent light fatigue resistance and repeated use characteristics.

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

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

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

FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention.

C10) The photoconductive member 100 shown in FIG. The first layer (
1) 102 and a second layer @) 103.

And the first layer (I) 102 and the second layer (IQ
103 forms a light-receiving layer 104.

The germanium atoms contained in the 10th layer (I) 102 may be contained in the first layer (i) i 02 so as to be uniformly distributed, or may be contained in the layer thickness direction. Although it is contained evenly, the distribution concentration may be non-uniform. In any case, the content is uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the support, from the point of view of making the properties uniform in the in-plane direction. is necessary. In particular, it is evenly contained in the layer thickness direction of the first layer (1) 102, and the side opposite to the side where the support 101 is provided (the side of the first layer (1) 102) or the second layer (II) 103 side) so that it is more distributed on the support side (the interface side between the first layer (1) 102 and the support 101), or Or,
Said first layer (1) 10 so as to have this reverse distribution state.
Contained in 2.

In the photoconductive member of the present invention, as described above, the distribution state of the germanium atoms contained in the first layer (1) 102 takes the above-mentioned distribution state in the layer thickness direction, and It is desirable that the distribution be non-uniform in the in-plane direction parallel to the surface of the surface.

2 to 10 show typical examples in which the distribution state of germanium atoms contained in the first layer (1) 102 of the photoconductive member in the present invention is non-uniform in the layer thickness direction. It will be done.

In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer (1) exhibiting photoconductivity.
102, and tB is the layer thickness of the first layer on the support side (1
) 102, and tT indicates the position of the interface of the first layer (1) 102 on the side opposite to the support side. That is,
First layer containing germanium atoms (1) 102
A layer is formed from the tB side toward the tT side.

FIG. 2 shows a first typical example of the distribution state of germanium atoms contained in the first layer (1) 102 in the layer thickness direction.

In the example shown in FIG. 2, the interface position tB where the surface on which the first layer (1) 102 containing germanium atoms is formed contacts the surface of the second layer (I) 102! ! lt
Up to the position 1, the distribution concentration C of germanium atoms is 01
Germanium atoms are contained in the first layer (1) 1o2 formed while maintaining a constant value, and the distribution concentration C2 gradually decreases continuously until reaching the position t, or rather, the interface position tT. has been done. At the interface position 1T, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the multiple positions tT, and reaches the concentration C5 at the position tT. forming a state.

In the case of Fig. 4, the distribution concentration C of germanium atoms is constant at the concentration C6 from position tB to position t2, and gradually decreases continuously between position t2 and position tA. At position t, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms is gradually decreased from the concentration C8 in a multi-continuous manner from position tB to multiple positions t, and becomes substantially zero at the position t. .

In the example shown in FIG. 6, the distribution concentration C of germanium atoms is a constant value of concentration C2 between position tB and position t3, and is set to concentration C1o at position tT. Between the position t3 and the position tT, the distribution density C is linearly decreased from the position t3 to the multiple positions t.

In the example shown in FIG. 7, the distribution concentration C is at the position tB.
The concentration C11 is kept at a constant value until the position t4.
From position 4 to position t, the distribution state decreases linearly from the concentration C1□ to the concentration C13.

In the example shown in FIG. 8, position tB! ,! lJ position t
, the distribution concentration C of germanium atoms is the concentration C
(14) decreases in a linear function so that it virtually reaches zero.

In FIG. 9, from position tB to multiple positions t5, the distribution concentration C of germanium atoms decreases linearly from concentration C15 to concentration C16, and from position t5 to position tT.
An example is shown in which the density C16 is set to a constant value between .

In the example shown in FIG. 10, the distribution concentration C of germanium atoms is C47 at position 1B, and is gradually decreased from this concentration CI7 until reaching position t6, and near position t6. is rapidly decreased to a concentration C18 at position t6.

Between position t6 and position t7, the concentration decreases rapidly at first, and then gradually decreases until reaching C19 at position t7, and between position t7 and position t8, the concentration υ decreases very slowly. The concentration is gradually decreased until the concentration C2o is reached at position t8. Between position t8 and position 1T,
The concentration C2o is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above, according to FIGS. 2 to 10, the first layer (D102
As described above, some typical examples of the distribution state of germanium atoms contained in the layer thickness direction, in the present invention,
On the support side, there is a part with a high distribution concentration C of germanium atoms, and on the interface tT side, the distribution concentration C is high.
One preferred example is the case where the first layer (1) 102 is provided with a germanium atom distribution having a portion that is considerably lower than that on the support side.

First layer (1) constituting the photoconductive member in the present invention
102 is preferably a localized region (containing germanium atoms at a relatively high concentration) on the support side as described above or, conversely, on the second layer (II) 103 side. It is desirable to have A).

For example, if the localized region (4) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (4) be provided within 5 μ from the interface position tB.

The above-mentioned localized region (4) may be the entire layer region (L,) from the interface position tB to a thickness of 5 μm, or the layer region (
LT).

Whether the localized region (A) is a part or all of the layer region (LT) is appropriately determined according to the characteristics required of the photoreceptive layer to be formed.

In the localized region (A), the distribution state of germanium atoms contained therein in the layer thickness direction is such that the maximum distribution concentration Crt+ax of germanium atoms is preferably 1000 atomic ppm or more with respect to the sum with silicon atoms, It is desirable that the layer be formed in such a manner that a distribution state can be obtained, preferably 5000 atomic ppm or more, most preferably I x 10' atomic ppm or more.

That is, in the present invention, the first layer (1) 102 containing germanium atoms has a layer thickness of 5 from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within μ (layer region with a thickness of 5 μ from tB).

In the present invention, the content of germanium atoms contained in the first layer (1) 102 is appropriately determined as desired so as to effectively achieve the object of the present invention, but preferably 1 to 9.5
X 10' atomic ppm % Good (1
7) Shikke 100~8 X 10' atomic ppm
, optimally 500-7 X 10' atomic
It is desirable to set it as ppm.

The distribution state of germanium atoms in the first layer (( ) 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 from the support side to the first layer. Layer (T) 102 second layer (II) 1
If a decreasing change is given toward 03 or vice versa, the distribution concentration C
By arbitrarily designing the rate of change curve as desired, the photoreceptive layer 104 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium in the first layer (1) 102 is sufficiently increased on the support side, and on the second layer (II) 103 side of the first layer (1) 102. In this case, by giving the distribution concentration curve of germanium atoms a change in the distribution concentration C that can be visualized as much as possible, light of wavelengths in the entire range from relatively short wavelengths to relatively short wavelengths including the visible light region can be obtained. On the other hand, it is possible to increase the photosensitivity (/111+), and it is also 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 (1) 102 on the support side, it is possible to , first layer (1) I The first layer (1
In the support side end layer region 102, it is possible to substantially completely absorb the light, and interference due to reflection from the support surface can be effectively prevented.

In the photoconductive member of the present invention, high photosensitivity and high dark resistance are achieved, and furthermore, the first layer Q) 102 and the second layer ω) 10
For the purpose of preventing charge injection from 3, the first layer (
T) 102 contains an oxygen atom. The oxygen atoms contained in the first layer (1) 102 are
It may be uniformly contained in the entire layer region of the first layer (1) 102, or it may be contained only in a part of the layer region of the first layer (1) 102 so that it is omnipresent.

The distribution state of oxygen atoms in the layer region 0) containing oxygen atoms is such that the distribution concentration C(O) is uniform in the in-plane direction parallel to the surface of the support of the first layer (D102). However, it is non-uniform in the layer thickness direction.

In the present invention, in order to more effectively achieve the object of the present invention, the distribution concentration curve of oxygen atoms in the layer thickness direction in the layer region (0) is smooth in the entire region. Oxygen atoms are contained in the layer region (0) so as to be present and continuous. Further, the distribution concentration curve has a maximum distribution concentration Cm
By designing the aX fc to be present inside the first layer (1) 102, the effects described below are significantly exhibited.

In the present invention, the maximum distribution concentration Cmax is preferably determined at the interface of the first layer (r) 102 opposite to the support (the second layer (It) 103 side in FIG. 1). It is desirable that it be installed nearby. In this case, the maximum distribution concentration Cm
By appropriately selecting ax, when the second layer Ql) 103 is charged from the free surface side, the first layer Ql) 103 is charged from the surface side.
It is possible to effectively prevent charges from being injected into the inside of the transistor 102.

In addition, near the interface with the second layer (ff) 103,
Oxygen atoms are contained in the first layer (1) 102 so that the distribution concentration of oxygen atoms decreases sharply from the maximum distribution concentration Cmax toward the interface with the second layer (U) 103, Durability in a humid atmosphere can be further improved.

In the present invention, the oxygen atom distribution concentration curve has the maximum distribution concentration Cmax inside the first layer (1) 102, but the distribution concentration is further adjusted so that the maximum value of the distribution concentration exists toward the support side. The curve can be designed to include oxygen atoms to improve the adhesion between the υ support and the first layer (t) 102 and to prevent charge injection.

In the present invention, oxygen atoms are desirably contained in the central layer region of the first layer (1) 102 in an amount that does not reduce photosensitivity even though it strives to increase dark resistance. .

In the present invention, the maximum distribution concentration Cmax of oxygen atoms is defined as the sum of silicon atoms, germanium atoms, and oxygen atoms (hereinafter referred to as r T (5iGeO) J):
Preferably 67 atomic% or less, more preferably 50 atomic% or less, optimally 40 atomic%
It is desirable that it be less than mlc%.

11 to 14 show typical examples of the distribution of oxygen atoms throughout the first layer (1) 102. FIG.

In the description of these figures, the symbols used without exception have the same meanings as used in FIGS. 2 to 10.

In the example shown in FIG. 11, position tB! b The oxygen atom concentration is C21 up to position t, and from position t to position t10
”, and at position t1o, the oxygen atom concentration reaches the peak value C2.
It becomes 2. The oxygen atom concentration decreases from the position t1o to the position t11, and reaches the oxygen atom concentration c21 at the position tT.

In the example shown in FIG. 12, the oxygen atom concentration is C23 from position tB to position t1□, and from position t, 2 to position t1
At position t15, where the oxygen atom concentration rapidly increases to 3, the oxygen atom concentration reaches a peak value C24, and from multiple positions t13 to position t.

until the oxygen atomic concentration decreases to almost zero.

In the example shown in FIG. 13, from position tB to position t14t
The oxygen atom concentration is 026 from C25 (22
), and the oxygen atom concentration reaches the peak value C2 at position t14.
It becomes 6. The oxygen atom concentration rapidly decreases from position t14 to position tT, and at position tT, the oxygen atom concentration becomes C25.

In the example shown in FIG. 14, the oxygen atom concentration C at position tB
At step 27, the oxygen atom concentration decreases to position t15 and reaches oxygen atom concentration C28.From position t15 to position t, the oxygen atom concentration remains constant at C28. The oxygen atom concentration increases from position t16 to position t17, and at position t17, the oxygen atom concentration reaches a peak value C2. The oxygen atom concentration decreases from the position t17 to the position tT, and reaches the oxygen atom concentration C28 at the position tT.

In the present invention, when the main purpose of the layer region (0) containing oxygen atoms provided in the first layer ([) 102 is to improve photosensitivity and dark resistance, the layer region (0) provided in the first layer ([) 102 is Layer (1
) 102, and in order to prevent charge injection from the first layer (1) 102 second layer (II) 103 side, the second layer ω) 103 is provided. When the main purpose is to strengthen the adhesion between the support and the first layer (1) 102, the support side edge of the first layer (T) 102 is provided near the interface with the support. It is provided so as to occupy the sublayer area.

In the former case, the content of oxygen atoms contained in the layer region (0) is kept relatively low in order to maintain high photosensitivity;
In the second case, the first layer Q) 102 and the second layer ω) are relatively large in order to prevent injection of charge from the 103 side, and in the latter case, to ensure strengthening of adhesion to the support. Therefore, it is desirable to have a relatively large amount.

In addition, in order to simultaneously achieve the above-mentioned advantages, the first layer ([) 1 is distributed at a relatively high concentration on the support side.
The first layer 0), the second layer (II) of 102, and the interface layer region on the 1.03 side are distributed with a relatively low concentration in the center of 02. The distribution state may be formed in the layer region (0).

In order to prevent the injection of charges from the second layer (ff) 103 side, a shingle layer region (0) is formed with a high distribution concentration of oxygen atoms on the second layer (II) 103 side.

In the present invention, the content of oxygen atoms contained in the layer region (0) provided in the first layer (I) 102 is determined based on the characteristics required for the layer region (0) itself, or the content of oxygen atoms contained in the layer region (0) provided in the first layer (I) 102. ) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the core support.

In addition, when another layer region is provided in direct contact with the layer region (0), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of oxygen atoms is appropriately selected taking into account the following.

The amount of oxygen atoms contained in the layer region (0) is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably 0. It is desirable that the content be 0.001 to 50 atomic %, more preferably 0.002 to 40 atomic %, and optimally 0.003 to 30 atomic %.

In the present invention, the layer region (0) is the first layer (1) 10
2 or the first layer (I) 102
Even if the entire area is old-fashioned, if the ratio of the first layer (1) 102 of the layer thickness To of the layer region (0) to the layer thickness T is large enough, it will not be contained in the layer region (0). (25) The upper limit of the content of oxygen atoms in the layer region (0) is desirably set to be sufficiently higher than the above value. In the case where the ratio of oxygen atoms to T(SiG@O) is two-fifths or more, the upper limit of the amount of oxygen atoms contained in the layer region (0) is preferably:
30 atomia or less, preferably 20 atomia
atomic% or less, preferably 10 atomIe% or less.

In the present invention, the layer region (0) containing oxygen atoms constituting the first layer Q) 102 has oxygen atoms on the support side and near the interface with the second layer (1) 103, as described above. It is preferable to provide a localized region (B) containing atoms at a relatively high concentration; in the former case, the adhesion between the support and the first layer (1) 102 can be further improved and the acceptance potential can be improved.

The localized region (B) can be explained using the symbols shown in FIGS. 11 to 14 at interface position tB or t,
It is desirable that it be provided within μ.

C26) In the present invention, the localized region (B) is located at interface position 1.
It may be the entire layer region (LT) of B or 1T up to a thickness of υ5μ, or it may be a part of the layer region (LT).

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

The localized region (B) has the maximum distribution concentration Cma of oxygen atoms as the distribution state of the oxygen atoms contained therein in the layer thickness direction.
x is preferably 500 atomic ppm or more,
It is desirable to form a layer so as to obtain a distribution state of preferably 800 atomic ppm or more, most preferably 1000 atomic ppm.

That is, in the present invention, the layer region (0) containing oxygen atoms is within 5 μm in layer thickness from the support side or the first layer (I) 102 (a layer region with a thickness of 5 μm from 1, or t). ) is preferably formed so that the maximum value Cm1LX of the distribution concentration exists.

In the present invention, specific examples of the halogen atoms contained in the first layer ([) 102 as necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as something.

In the photoconductive member of the present invention, the first layer (1) 102
By containing therein a substance that controls the conductive properties, the conductive properties of the first layer (1) 102 can be controlled as desired.

Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-5iGe(
With respect to H, Specifically, P-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), At
(aluminum).

Ga (gallium) + rn (indium), Tt (thallium), etc., especially '! HmK is used: B,
It is Ga.

Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus), As (arsenic), and Sb (
Antimony LB1 (bismuth), etc., and particularly preferably used are P and All.

In the present invention, the content of the substance that controls conduction properties contained in the first layer (1) 102 is determined by
) 102 or the conduction properties required for the second layer Q)
It can be selected as appropriate based on the organic relationship, such as the relationship with the characteristics of the contact interface with the support in which 102 is provided in direct contact.

In addition, the substance controlling the conduction properties is included in the 10th layer (1).
When it is contained locally in a desired layer region of the -0th layer (1) 1o2, especially in the support side end layer region of the first layer (I) 102. When containing O layer, the characteristics of other O layer regions provided in direct contact with the layer region and the relationship with the characteristics at the contact interface with the other layer region are also taken into consideration to improve conduction properties. The content of the substance to be controlled is selected as appropriate.

In the present invention, the content of the substance that controls conduction properties contained in the first layer (1) 102 is preferably 0. O1~5 X 10' atomioppm
, more preferably 0.5 to I x 10' atoms
e ppm, optimally 1-5 X 10” atoms
It is preferable that the amount is lc ppm.

In the present invention, the content of the substance controlling conduction properties in the layer region containing the substance is preferably 30 at.
omic ppm or more, preferably 50 atoms
ic ppm or more, optimally 100 atomic
9711 or more, the substance is 1 in the first layer.
It is desirable to locally contain it in a part of the layer region of 02, and it is particularly desirable to have it unevenly distributed in the end layer region of the first layer (I) 102 on the side of the support.

Among the above, by containing the substance controlling the conductive properties in the support side end layer region (g) of the first layer (I) 102 in a content equal to or higher than the above value, for example, When the substance to be contained is the above-mentioned P-type impurity, when the free surface of the photoreceptive layer 104 is subjected to polar charging treatment, electron injection from the support side into the photoreceptor layer 104 can be effectively prevented. If the substance to be contained is the n-type impurity described above, when the free surface of the photoreceptive layer 104 is charged to e polarity, K, from the support side into the photoreceptor layer 104. This can effectively prevent the injection of holes into.

In this way, when the end layer region (G) contains a substance that controls conduction characteristics of one polarity, the 10th layer (I
) The remaining layer region of 102, i.e., the end layer region (■)
The layer region 2) excluding the part may contain a substance that controls the conduction characteristics of the other polarity, or the material that controls the conduction characteristics of the same polarity may be added to the end layer region 2). It may be contained in a much smaller amount than the actual amount contained in the.

In such a case, the content of the substance controlling the conduction properties contained in the layer region (1) is as follows:
It is determined as desired depending on the polarity and content of the substance contained in the substance, but preferably 0.0
01 to 1000 atomic ppm, more preferably 0.05 to 500 atomic ppm, most preferably 0.1 to 200 atomic ppm.

In the present invention, when the end layer region (g) and the layer region (a) contain the same kind of substance governing conductivity, the content in the layer region (a) is preferably・3
It is desirable that the amount be less than 0 atomla ppm. In addition to the above-described case, in the present invention, the first layer (1) 102 includes a layer region containing a substance controlling 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 region by directly contacting a layer region containing a substance controlling the properties. Clogging, e.g. first layer (I) 102
Inside, 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 to form a so-called p-n junction, thereby providing a depletion layer. I can do it.

In the present invention, the first layer (I) 102 composed of a-5IGe (H, It is done by a deposition method. For example, a-8iGe(H
,
A raw material gas for Ge supply that can supply germanium atoms (Go), and a raw material gas for introducing hydrogen atoms or/and halogen atoms (3
) A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and the source gas is introduced onto the surface of a predetermined support, which has been set in advance at a predetermined position. A layer made of a-5iGe(H,X) may be formed on the surface. In addition, in order to contain germanium atoms in a non-uniform distribution state, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve, and a-5iGe(H,X
) may be formed. In addition, when forming by sputtering method, for example, a target composed of 81 in an atmosphere of a mixed gas with an inert gas such as Ar or Ha, or a gas such as acetic acid, or the target and G@ Ge diluted with a diluent gas such as He or Ar, if necessary, using two of the configured targets or a mixed target of Sl and Go.
By introducing the raw material gas for supply and, if necessary, the gas for introducing hydrogen atoms (6) or halogen atoms (a) into the deposition chamber for sputtering to form a plasma atmosphere of the desired gas. will be accomplished. When the distribution of germanium atoms is made non-uniform, the gas flow rate of the raw material gas for supplying Ge is controlled according to a desired rate of change curve;
The target described above may be sputtered.

In the case of the ion blating method, for example, polycrystalline silicon or black crystalline silicon and polycrystalline germanium or black crystal germanium are housed in a deposition date as evaporation sources, and the evaporation sources are heated by resistance heating or electron beam. Except for heating and evaporating by a method such as the εB method and passing the flying evaporated material through a desired gas plasma atmosphere,
This can be done in the same manner as in the sputtering method.

Substances that can be used as the raw material gas for S1 supply used in the present invention include SiH4, 512H6, Si, H8
゜Si4H10 and other gaseous or gasifiable silicon hydrides (silanes) can be effectively used, especially in terms of ease of handling during layer creation work and good St supply efficiency. Preferred examples include 5IH4 and 5t2H6.

GeH is a substance that can be used as the raw material gas for supplying Go.
4+ Ge 2Hb + Ge 5Hs! G64
H101Ge 5H12r Ge6H+ 41Ge7H
Germanium hydride in a gaseous state or that can be gasified, such as 16+ Ge5H+ a + GeyHzo, is cited as one that can be effectively used. In particular, Gem4 is easy to handle during layer creation work, and has good Ge supply efficiency. ．． Ge2
H6+G.3H8 is 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, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Iodine halogen gas, BrFr CI-F + C
4F3 r BrF51BrFs, IF5, I
Interhalogen compounds such as F7, ICt, and IBr can be mentioned.

As silicon compounds containing halogen gas, so-called silane derivatives substituted with halogen atoms, specifically, for example, 5
IF4,81. , H6, 51ct4. Silicon halides such as SiBr4 are preferred.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying 81 along with a raw material gas for supplying Go. a-5iGe containing halogen atoms on a desired support without using silicon oxide gas
A first layer (1) 102 consisting of:

According to the glow discharge method, the first layer containing halogen atoms (
1) When manufacturing 102, basically, for example, silicon halide is used as a raw material gas for sub-supply, germanium hydride is used as a raw material gas for Go supply, and Ar l H2,H
Gases such as No. 6 are introduced into the deposition chamber for forming the first layer (1) 102 at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. Then the first layer (1) is deposited on the desired support.
102, but in order to make it easier to control the ratio of hydrogen atoms introduced, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is also mixed with these gases 2. A layer may also be formed.

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

In order to introduce halogen atoms into the layer formed in either the sulfur silating method or the ion silating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into the deposition chamber for snow settering to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCL, HBr.

[etc. (D Hydrogen halide, 5IH2F2.5IH2I
2.5In2ct2゜S 1HcZ S IHBr S
Halogen-substituted hydrogen such as 1HBr s! +221 silicon oxide, and GeHF, , GeH2F2, Ga
H, F, GeHCl, .

GeH2CL2. GsH, Ct, GeHBr, ,
GeH2Br2. GeI (, Br.

GeHI, , GeH2I2. Get (halides containing hydrogen atoms as one of their constituents, such as hydrogenated germanium halides such as 3I, GeF4. GaCl2.
GeBr4. GeI4. GeF2゜GeC12,
GeBr2. Gaseous or gasifiable substances such as germanium oxides such as GeI2 may also be mentioned as useful starting materials for forming the first layer (1) 102.

Among these substances, logenides containing hydrogen atoms are
First layer (1) When forming IO2, hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced simultaneously with the introduction of halogen atoms into the layer. Used as raw material for rogens introduction.

Luniha, in which hydrogen atoms are structurally introduced into the first layer (1) 102, in addition to the above, H2, or SiH4, 81□H6
゜81, H8,5t4H, o and other silicon hydrides with germanium or germanium compounds for supplying Go, or G6H4, Gs 2H6, Go sHs r G
o 4H10y G115H12*G@6H14+ G
This can also be done by causing germanium hydride such as 8H181Ge9H20 and silicon or a silicon compound for supplying hydrogen to coexist in the deposition chamber to generate discharge.

In a preferred example of the present invention, hydrogen atoms (b) contained in the first layer (1) 102 of the photoconductive member to be formed
The amount of halogen atoms (a) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 0.01 to 4.
0 atomlo%, more preferably 0.05-30
atomla q6, optimally 0.1-25 ato
It is desirable to set it as mic %.

10th layer (I) Hydrogen atoms contained in 102 (B)
Or/and to control the amount of halogen atoms (a), for example, the temperature of the support and/or the amount of hydrogen atoms introduced into the deposition system of the starting material used to contain the halogen atoms. , the discharge force, etc. may be controlled.

The layer thickness of the first layer (1) 102 in the photoconductive member of the present invention is adjusted as desired so that the photocarriers generated in the first layer (1) 102 are efficiently transported. preferably 1 to 100μ, more preferably 1
It is desirable that the thickness be ~80μ, most preferably 2~50μ.

In the present invention, in order to provide the layer region (0) containing oxygen atoms in the first layer (I) 102, the first layer (1)
When forming 102, a starting material for introducing oxygen atoms is used together with the above-mentioned starting material for forming first layer (I) 102, and the amount thereof is controlled and contained in the layer to be formed. good.

When the glow discharge method is used to form the layer region (0), a starting material for introducing oxygen atoms is added to the starting material selected as desired from among the starting materials for forming the 10th layer (D102) described above. As the starting material for such oxygen atom introduction, most of the gaseous substances or gasified substances having at least oxygen atoms as a constituent atom can be used.

For example, a raw material gas containing silicon atoms (Sl) as constituent atoms, a raw material gas containing oxygen atoms (0) as constituent atoms, and hydrogen atoms (6) or halogen atoms (a) as necessary. Either a raw material gas is mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (st) and a raw material gas whose constituent atoms are oxygen atoms (fo) and hydrogen atoms (b) are used. are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (ST) and silicon atoms (ST) and oxygen atoms)
and hydrogen atoms (6) can be mixed and used.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (b) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (0) as constituent atoms.

Specifically, for example, oxygen (0□), ozone (03), -
Nitric oxide (No), nitrogen dioxide (N02), -dioxide (
41) Nitrogen (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N205), nitrogen trioxide (No, 'l, silicon atom (81) and oxygen atom (
For example, disiloxane (H5SIO8iI(,), tridioki?
Examples include lower siloxanes such as 7 (H, 5tO8iH20SH(, )).

In order to form the layer region (0) containing oxygen atoms by the sputtering method, a wafer containing St and 5tO2 mixed therein is used as a target. etc., by sputtering in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms may be diluted with a diluent gas as necessary for sputtering. The St wafer is sputtered by introducing the St wafer into a deposition chamber to form a gas plasma of these gases.

Additionally, 81 and StO□ are separate targets (A
By using a single target mixed with St and 810□, hydrogen atoms (6
) or/and halogen atoms (3) in a gas atmosphere containing them as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when a layer region 0) containing oxygen atoms is provided when forming the first layer (1) 102, the distribution concentration C of oxygen atoms contained in the layer region (0) is (0) in the layer thickness direction to obtain the desired distribution state (d
In order to form a layer region 0) having a epth profile ), in the case of a glow discharge, a starting material gas for introducing oxygen atoms whose distribution concentration CI) is to be changed is introduced, and its gas flow rate is adjusted to the desired rate of change curve. This is accomplished by introducing the material into the deposition chamber while changing it accordingly.

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 in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

When forming the layer region (0) by sputtering, the distribution concentration C(O) of oxygen atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (d) of oxygen atoms in the layer thickness direction.
epth profile'), firstly, as in the case of the glow discharge method, the starting material for introducing oxygen atoms is used in a gaseous state, and the gas when introduced into the deposition chamber is This is accomplished by appropriately changing the flow rate as desired.

If the target for the second Niha, S, zottle ring is a mixture of Si and 8102, for example, the mixing ratio of St and 5102 can be changed in advance in the layer thickness direction of the target. It is achieved by letting it happen.

In order to structurally introduce a substance that controls conduction characteristics, such as a group (I) atom or a group V atom, into the first layer (I) 102, during layer formation, a substance for introducing a group (I) atom must be prepared. The starting material or the starting material for introducing Group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the first layer (1) 102. As the starting material for the introduction of the 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. Specifically, starting materials for introducing such group (Ⅰ) atoms include B2H6, B4H, and the like for introducing boron atoms. , B5H,, B5H,1
,B6H,. .

Boron hydride such as B6H121B6H14, BF3. B
Cl3. Examples include boron halides such as BBr3. In addition, ktct3. GILC13,Ga(CH3
')3. InCl2. TtCl, etc. can also be mentioned.

In the present invention, effective starting materials for introducing Group V atoms include PH3,
Hydrogen north neighbors such as P2H4, PH4I, PF, .

PF5, PCl5, PCl5 r P Br
3, PBr 5 + PI 3 and other halogen north neighbors. In addition, AsH3, AsF, , A
sCl2゜A-mBr AgF, 8bHSbF Sb
F 8bCt5,5bCts.

31 5 5 + 51 51 BiI (3, BiCl3. B1Br, etc. can 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 constituting the first layer (r) 102 and containing a substance that controls conduction characteristics and provided unevenly on the support side is defined as the thickness of the layer region and the layer region. It is determined as desired depending on the characteristics required of the first layer (1) formed on the region and the other layer regions constituting the region 102, but the lower limit is preferably 3.
0X or more, more preferably 40i or more, optimally 5o
It is desirable that it be X or more.

Further, when the content of the substance controlling the conductive properties contained in the layer region is 30 atomlc ppm or more, the upper limit of the layer thickness of the layer region is preferably 10 μm or less, more preferably is desirably 8μ or less, optimally 5μ or less.

In the photoconductive member 100 shown in FIG. This is provided in order to achieve the objectives of the present invention in terms of physical pressure resistance, use environment characteristics, and durability.

Furthermore, in the present invention, since each of the amorphous materials forming the first layer (I) 102 and the second layer (If) 103 has a common constituent element of silicon atoms,
Chemical stability is sufficiently ensured at the laminated interface.

The second layer (If) 103 in the present invention is an amorphous material (hereinafter referred to as ra-(818N,-x)y(...X),□"However, 0
<X, 7<1).

The second layer Q[) 103 composed of 1-(81XN, done by.

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. Advantages include that it is relatively easy to control the manufacturing conditions for manufacturing the conductive member, and that it is easy to introduce nitrogen atoms and halogen atoms together with silicon atoms into the second layer Ql) 103 to be manufactured. Glow discharge method or S/l! The Tuttering method is preferably employed.

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

To form the second layer (g) 103 by the glow discharge method, a - (81xN, -,) y (1 (, x), -
The raw material gas for y formation is mixed with a dilution gas at a predetermined mixing ratio as needed, and introduced into a deposition chamber for vacuum deposition where a support is installed, and the introduced gas is used as a glow discharge. The first layer (1) 102, which has already been formed on the support, is turned into a gas plasma by generating
81xN1-x)y(H,X), -y may be deposited.

In the present invention, a −(st XN1-x )y(
The raw material gas for forming L Most substances or gasified versions of gasifiable substances can be used.

When using a raw material gas having Sl as a constituent atom as one of Sl, N, H, and X, for example, a raw material gas having 81 as a constituent atom, a raw material gas having N as a constituent atom, and Depending on the situation, a raw material gas containing ■ as a constituent atom and/or a raw material gas containing
A thick gas having constituent atoms of and/or a raw material gas having X having constituent atoms are also mixed at a desired mixing ratio, or a raw material gas having constituent atoms of
and H as constituent atoms, or 81. N
and a raw material gas having three constituent atoms of X can be used in combination.

Separately, N is added to the raw material gas containing St and H as constituent atoms.
A raw material gas having constituent atoms may be mixed and used, or a raw material gas having N as constituent atoms may be mixed and used with a raw material gas having Sl and X as constituent atoms.

In the present invention, the halogen atoms contained in the second layer Qr) 103 are preferably F, C1, Br, I
In particular, F and C1 are preferable.

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

In the present invention, 5IH4,812I (6,8S3H8,814H1) containing St and H as constituent atoms is effectively used as the raw material gas for forming the second layer ω)103.
o Silicon hydride gas such as silanes (811ano), examples where N is the constituent atom or N and H are the constituent atoms t H nitrogen (N2''), ammonia (N■, ) l hydrazine (H2NNH2 ') + Hydrogen azide (H'N3)
, gaseous or gasifiable nitrogen such as ammonium azide (NH4N), nitrogen compounds such as nitrides and azides. In addition to this, halogenated nitrogen compounds such as nitrogen trifluoride (F, N) and nitrogen tetrafluoride (F4N2) can be used, since in addition to introducing nitrogen atoms (2), halogen atoms (1) can also be introduced. I can list them.

Effective starting materials that serve as raw material gases for introducing halogen atoms (3) include, for example, interhalogenation of fluorine, chlorine, bromine, and iodine, BrF, CIF, C4F6.
BrF5. .

BrF IF r IF7 + rcz l Interhalogenated 3v3 compounds such as IBr, HF, HCl, HBr, HI, etc.
・Hydrogen chloride can be mentioned.

These second layer Ql) 103 forming substances contain silicon atoms, nitrogen atoms, I/Rogen atoms, and optionally hydrogen atoms in a predetermined composition ratio in the second layer ω) 103 to be formed. is selected and used as desired when forming the second layer Q[) 103 so that it contains.

For example, by introducing into a deposition chamber a raw material gas for introducing silicon atoms, nitrogen atoms, and, if necessary, a raw material gas for introducing hydrogen atoms and/or halogen atoms, and causing a glow discharge. -(S IXN, -,
)y(H,x), -y can form a second layer Q[)103.

S) To form the second layer (I) 103 by the R tuttering method, a phosphor crystal or polycrystalline Si wafer or a S 1 , N4 wafer or a mixture of st and Si , N 4 is contained. Sputtering may be carried out by using a wafer as a target in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements as necessary.

For example, if you use 61 wafer as a target,
813N4 and raw material gas to introduce H or/and X are required! The St wafer may be sputtered by diluting the St wafer with a diluting gas according to the conditions, introducing it into a deposition chamber for snow and tar, and forming a gas plasma of these gases.

Also, separately, Sl and 81. As a separate target from N4 or st,! : This is accomplished by using a single target mixed with 5t3N4 and carrying out sulfur ringing in a gas atmosphere containing hydrogen atoms and/or halogen atoms as required. N,H
As for the material serving as the raw material gas for introducing X, the material for forming the second layer ω) 103 shown in the glow discharge example described above is also used as an effective material in the snow tuttering method. obtain.

In the present invention, the diluent gas used when forming the second layer Qr) 103 by the glow discharge method or the sottering method is a so-called rare gas, such as He, Na, etc.
, Ar, etc. can be cited as suitable examples.

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

That is, 81. Substances containing N, optionally H or/and
In the present invention, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties, so in the present invention, it has desired properties depending on the purpose. The preparation conditions are strictly selected as desired so that a-(SlxN1□)y(H9X)1-y is formed.

For example, if the second layer 1) 103 is provided with the main purpose of improving electrical voltage resistance, U a -(S 1 xN, -x
')y(H+

In addition, when the second layer (ff) 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 a certain extent, and the resistance to the irradiated light is reduced to some extent. A-(SiXN1-x)a(HlX)1-y is prepared as an amorphous material having a sensitivity of .

First layer (1) a −(Sip+−x
)y(■rX)1-y second layer (II)10
3, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer, and in the present invention, &-(S1xN
It is desirable that the temperature of the support during layer formation be strictly controlled so that 1-x)y(HlX)1-3' can be formed as desired.

In the present invention, the formation of the second layer (II) 103 is carried out by selecting an optimal range as appropriate in accordance with the method of forming the second layer (II) 103 in order to effectively achieve the desired purpose. However, the temperature is preferably 20 to 400°C, more preferably 50 to 350°C, most preferably 100 to 300°C. The glow discharge method is used to form the second layer (6) 103 because it is relatively easy to finely control the composition ratio of atoms constituting the layer and control the layer thickness compared to other methods. However, when forming the second layer (If) 103 using these layer forming methods, the discharge power during layer formation, as well as the support temperature described above, is advantageous. Created a-(SIXN, -x)yXl-
This is one of the important factors that influences the characteristics of y.

a- having the characteristics for achieving the object of the present invention;
The discharge power conditions for (8txN1-x)yXl-a to be produced effectively with good productivity are preferably 10~
300W, preferably 20-250W, optimally 50W
A value of ~200W is desirable.

The gas pressure in the deposition chamber is preferably about 0.01 to 1 Torr, and more preferably about 0.1 to 0.5 Torr.

In the present invention, the support temperature and discharge power for forming the second layer (II) 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 characteristics &-(SIXN,-x)y(H,X''l,-).

It is desirable that the optimum value of each layer creation factor be determined based on mutual organic relationship so that the second layer (1) 103 consisting of the following is formed.

The amount of carbon atoms contained in the second layer (I[) 103 in the photoconductive member of the present invention is determined to have the desired characteristics to achieve the object of the present invention, similar to the conditions for creating the 20th layer Ql) 103. This is an important factor in the shape of the resulting second layer Qr) 103. The amount of carbon atoms contained in the second layer (II) 103 in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer ω) 103. It is something.

That is, the general formula a-(SIxN, -X)y(H2X)
, -y can be broadly classified as an amorphous material composed of silicon atoms and nitrogen atoms (hereinafter referred to as [
It is written as a-Sl aNl-aj. However, 0(a
(1), an amorphous material composed of silicon atoms, nitrogen atoms, and hydrogen atoms (hereinafter r a −(st bNl
-b) c horse-0".

However, 0〈b, C〈1), an amorphous material composed of silicon atoms, nitrogen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter ra-(StdNl,'), (H, X'
11-, written as J. However, it is classified as 0(d, e(1')).

In the present invention, the second layer (n) 103 is a-81aN
, 1, the amount of nitrogen atoms contained in the second layer Ql) 103 is preferably 1×10 to 90ato
mic%, preferably 1-80 atomic%
, and the optimum value is preferably 10 to 75 atomic%. That is, a-81, N, C)
If expressed as a, 1 is preferably 0.1 to 0.99
999, more preferably 0.2 to 0.99, optimally 0.999, more preferably 0.2 to 0.99, optimally 0.
25 to 0.9.

In the present invention, the second layer Q[) 103 is a-(si,
N,-,). When composed of mountain-8, the second layer Q[)
The amount of nitrogen atoms contained in 103 is preferably I
10"" to 90 atomia%, more preferably 1 to 90 atomlc%, most preferably 10"
-80 atomic% is desirable. The content of hydrogen atoms is preferably 1 to 40
atomlc%, more preferably 2-35 atoml
o %, preferably 5 to 3° atomic %, and photoconductive members formed when the hydrogen content is in this range are excellent in practical applications. It is something.

That is, in the above representation of a-(81,N,-6), H4-0, b is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, and optimally is 0.15 to 0.9,
C is preferably 0.6 to 0.99, more preferably 0.6
5 to 0.98, most preferably 0.7 to 0.95.

The 20th layer Ql) 103 is a-(SidN, -d), C
I(, X'l, -0, the second layer Q
[) The content of nitrogen atoms contained in 103 is as follows:
Preferably I x 10-3 to 90 atoms,
More preferably 1 to 90 atomic %, optimally 1
The content of halogen atoms is preferably 1 to 20 atomic c%, more preferably 1 to 1%.
8 atomic%, optimally 2-15 atomic%
It is preferable that the halogen atom content be within this range, so that photoconductive members produced when the halogen atom content is in this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19 atoms.
It is desirable that the content be ie % or less, more preferably 13 atomic % or less.

That is, the previous a-(stdN,-,'), (a, x')1
- If expressed as d and e of e, d is preferably 0.1 to
0.99999, preferably 0.1 to 0.99. Optimally 0.15-0.9, e preferably 0.8-0.9
9, preferably 0.82 to 0.99, optimally 0.8
The number range of the layer thickness of the second layer (II) 103 in the present invention is one of the important factors for effectively achieving the object of the present invention. .

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

Also, the layer thickness of the second layer (11) 103 is the layer (■) 10
The amount of nitrogen atoms contained in 3 and the 10th layer (I) 10
The relationship with layer thickness No. 2 also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region.

In addition, it is desirable to consider the economical aspects including productivity and mass production.

The layer thickness of the second layer Ql) 103 in the present invention is as follows:
Preferably 0.003 to 30 μ, more preferably 0.00
It is desirable that the thickness be 4 to 20μ, most preferably 0.005 to 10μ.

Further, in the present invention, in order to further enhance the effect obtained by nitrogen atoms, carbon atoms may be included together with nitrogen atoms in the second layer ω) 103.

Carbon atoms and the raw material gas for introducing carbon atoms into the second layer (II) 103 include C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 5 carbon atoms, and 2 carbon atoms.
-5 ethylene hydrocarbons, C2-4 acetylene hydrocarbons, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), gulo A (c5a8), n
-Butane (n-C4H4゜)l Pentane (C5H12)
l Ethylene hydrocarbons include ethylene (C2■4
), propylene (C3H6), butene-1 (C4H8)
, butene-2 (C4H8), isobutylene (C4) I8
), pentene (C5H1o).

Examples of acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C3H4), butyne (C4
H6) and the like.

In addition to these, alkyl silicides such as 5l(CH5)4, 51(C2H5)4 and the like can be cited as raw material gases containing St, C, and H as constituent atoms.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NlCr, stainless steel, and At.

Cr, Mo, Au, Nb, Ta, V, TI
, Pt, Pd, or alloys thereof.

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

For example, if it is glass, NiCr is applied to its surface.

AA, Cr, Mo, Au, Ir, Nb, Ta, V, TI
, Pt, Pd.

In2O,,5n02, ITO(In20.+5n
Conductivity is imparted by providing a thin film consisting of O2), etc., or if it is a synthetic resin film such as a polyester film, NiCr, At, Ag, Pd, Z
n, Ni, Au, Cr, Mo.

A thin film of metal such as Ir, Nb, Ta, V, TI, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, taring, etc., or the surface is laminated with the above metal to make the surface conductive. gender is given. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired.
If the photoconductive member 100 of FIG. 1 is to be used as a frame forming member for electrophotography, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying. The thickness of the support is appropriately determined so as to form a photoconductive member of a desired thickness, but if flexibility is required as a photoconductive member,
It is made as thin as possible within the range where it can fully function as a support. In the case of both years and others, the thickness is preferably 10μ or more from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.

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. Gases 1102 to 1106 in the figure are sealed with raw material gases for forming the photoconductive member of the present invention. is SiH4 gas diluted with He (99.999% purity).

Hereinafter, it will be abbreviated as SIH4/He. ) Zenpe, 1103 is Gs H4 Ga2 diluted with Ha (99.999% purity)
, hereinafter abbreviated as G@H4/He. )Impe, 1104
is diluted with He and becomes 95IF4 gas (99.99% purity,
Hereinafter, it will be abbreviated as 81F4/H. ) Zembe, 1105 is He
1106 is H2 gas (99.999% purity).

In order to flow these gases into the reaction chamber 1101, gas valves 1122 to 1126 (1102 to 1106) are used.
, make sure that the leak valve 1135 is closed, and also check that the inlet valves 1112 to 1116 and the outlet valve 11 are closed.
After confirming that 17 to 1121, auxiliary valves 1132, and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.

Next, the reading on the vacuum gauge 1136 is approximately 5 x 10 = tor
When the temperature reaches r, the auxiliary valves 1132, 1133 and the outflow valves 1117 to 1121 are closed.

Next, a first layer (1) 10 is placed on the cylindrical substrate 1137.
To give an example of forming 2, Gas Zenpe 110
From 2 81 H4/ He gas, gas exchange 11o3
) GeH4/He gas, Gas Zempe 1105, 9 N.

Open the gas valves 1122, 1123, 1124 and check the pressure of the outlet pressure gauges 1127, 1128, 1129 to IKf
/ Adjust the inlet valve 1112 to 2.

1113 and 1114 are gradually opened to allow flow into mass flow controllers 1107, 1108, and 1109, respectively. Subsequently, the outflow valve 1117°1118.1119
, the auxiliary valve 1132 is gradually opened to allow each gas to flow into the reaction chamber 1101. 5IH4/He at this time
Outflow valve 1117, so that the ratio between the gas flow rate and the G11H4/He gas flow rate and the No gas flow rate becomes a desired value.
1118 and 1119, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. Then, the temperature of the base 1137 is increased by the heating heater 1138.
After confirming that the temperature is set in the range of ~400°C, the power supply 1140 is set to the desired power and the reaction chamber 1 is turned on.
101 and at the same time generate No gas or/and GeH according to a pre-designed rate of change curve.
4/ The distribution concentration of germanium atoms contained in the formed layer is controlled by controlling the flow rate of the H gas to gradually close the opening of the valve 1118 manually or by using an externally driven motor.

First layer (1) formed to a desired layer thickness as described above
To form the second layer (II) 103 on 102,
Using the same valve operation (65) as in the formation of the first layer (I) 102, for example, each of the 5IH4 gas and NH3 gas is diluted with a diluent gas such as He as necessary, and according to desired conditions, This is accomplished by generating a glow discharge.

In order to contain ~rogen atoms in the second layer ω) 103, for example, 5IF4 gas and NH gas, or Si
Add H2 gas and prepare the second layer (II) 1 in the same manner as above.
This is accomplished by forming 03.

It goes without saying that all outflow valves other than those required for gas when forming each layer are closed, and when forming each layer, 1. In order to avoid that the gas used to form the spinning layer remains in the reaction chamber 1101 and in the gas piping from the outflow valves 1117 to 1121 to the reaction chamber 11o1, the outflow z4hi1117 to 1121 are closed and the auxiliary valves 1132 and 1133 are closed. Open main valve 113
4 is fully opened and the system is once evacuated to a high vacuum, as necessary.

For example, in the case of glow discharge, the amount of nitrogen atoms contained in the second layer (If) 103 is 5l) I4 gas and r
66) The flow rate ratio of the gas introduced into the reaction chamber 1101 can be changed as desired, or in the case of layer formation by sputtering, the sputter area ratio of the silicon wafer and the Si 3N4 wafer can be changed when forming the target. It can be controlled as desired by changing the mixing ratio of silicon powder and 813N4 powder and molding the target. The amount of halogen atoms contained in the second layer (If) 103 can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, for example, SiF4 gas, is introduced into the reaction chamber 1101. will be accomplished.

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 A cylinder-shaped At
Samples (samples Al1-1 to 13-4'1) as electrophotographic image forming members were prepared on a substrate under the conditions shown in Table 1 (Table 2).

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

Place each sample obtained in this way in a charging exposure experiment device.■5. Corona charging was performed with OKV for 0.3 hours, and a light image was immediately irradiated. The optical image uses a tungsten lamp light source,
A light intensity of 21 ux-sec was irradiated through a transmission type test chart.

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

In the above, the light source is replaced by a tungsten lamp81
The image quality of the toner transfer image was evaluated for each sample under the same toner image forming conditions as above, except that an electrostatic image was formed using a 0 nm 0 GaA semiconductor laser (10 mW). All samples had excellent resolution, and clear, high-quality images with good gradation reproducibility were obtained.

Example 2 In the manufacturing apparatus shown in FIG. 15, a cylinder-shaped At
Samples (samples A21-1 to 423-4) 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
FIG. 6 shows the content distribution concentration of oxygen atoms, and FIG. 17 shows the oxygen atom content distribution concentration.

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

Example 3 Sample Al1-1°12-1. of Example 1 was used, except that the conditions for forming the second layer (I) 103 were as shown in Table 5.
Each of the electrophotographic image forming members (Samples Al1-1-1 to (69) 11-1-8.12-1-1 to 12-1-8.13-1
-] to 13-1-8) 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 conducted an overall image quality evaluation of the transferred image and evaluated its durability through repeated and continuous use.

Table 6 shows the results of the overall image quality evaluation of the transferred image of each sample and the evaluation of durability through repeated and continuous use.

Example 4 When the chroma of the 20th layer (■) 103 is reached, the target area ratio of silicon wafer and graphite is changed, and the layer ([) 10
Each of the image forming members was produced in exactly the same manner as in Sample Al1-1 of Example 1, except that the content ratio of silicon atoms and nitrogen atoms in Example 3 was changed. For each of the imaging members thus obtained, as described in Example 1,
After repeating the steps of image formation, development, and cleaning about 50,000 times, image evaluation was performed, and the results shown in Table 7 were obtained.

(70) Example 5 Second layer (when forming layer 103, 81) f4 gas and N
By changing the flow rate ratio of H and gas, the 20th layer (It) 103
Each of the image forming members was produced in exactly the same manner as Sample 412-1 of Example 1, except that the content ratio of silicon atoms to nitrogen atoms was changed.

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 Ql) 103, 81H4 gas, 8
1 By changing the flow rate ratio of F4 gas and NH3 gas, layer (II)
Each of the image forming members was created in exactly the same manner as in Sample Al 3-1 of Example 1, except that the content ratio of silicon atoms to nitrogen atoms in No. 103 was changed.

After repeating the image forming, developing, and cleaning steps as described in Example 1 approximately 50,000 times for each image forming member thus obtained, image evaluation was performed, and the results shown in Table 9 were obtained. .

(71) Example 7 Second layer (II) IO30 Each of the imaging members was prepared in exactly the same manner as in Example 1, except that the thickness of the O30 layer was changed. The steps of image formation, development, and printing as described for sample All°-1 of Example 1 were repeated to obtain the results shown in Table 10.

(72) Table 2 (74) 426- Table 6 (78) Common layer forming conditions in the above embodiments of the present invention are shown below.

Substrate temperature:) 1' Rumanium atom (Go) containing layer...
...About 200°C Germanium atom (Go)-free layer...About 250°C Discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3 Torr

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 respectively show the first layer (
FIGS. 11 to 14 are explanatory diagrams for explaining the distribution state of r-rumanium atoms in the first layer (1), respectively. FIG. 15 is a schematic explanatory diagram of the apparatus used in the present invention, and FIGS. 16 and 17 are distribution state diagrams showing the distribution state of each atom in the embodiment of the present invention, respectively. 100... Photoconductive member 101... Support body 102-
...First 01m (1) 103 ...Second tv r@
(II) 104... Photoreceptive layer (81) 00 / -1111011--→-C 431-

Claims (8)

[Claims] (1) A support for a photoconductive member, a first layer exhibiting photoconductivity made of an amorphous material containing silicon atoms and germanium atoms, and an amorphous material containing silicon atoms and nitrogen atoms. the first layer has a layer region (0) containing oxygen atoms non-uniformly in the layer thickness direction; 0) A photoconductive member characterized in that the oxygen atom distribution concentration curve in the layer thickness direction is smooth and the maximum distribution concentration is within the first layer. (2) The photoconductive member according to claim 1, wherein the first layer contains hydrogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein the first layer contains halogen atoms. (4) Distribution of germanium atoms in the first layer (1) Claim 1 in which the cloth state is non-uniform in the layer thickness direction
The photoconductive member described in . (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) Photoconductive member 0 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 substance that controls conductivity is an atom belonging to Group V of the periodic table.