JPS60140248A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member superior in photosensitivity, etc., by forming a layer composed of a layer region made of amorphous Ge and a photoconductive layer region made of amorphous Si, and contg. N in a nonuniform concn. distribution in the layer thickness direction and an amorphous layer made of Si and O in succession on a substrate. CONSTITUTION:The objective photoconductive member 100 is obtained by successively forming on a substrate 101 the first layer 102 composed of an amorphous layer region 105 made of Ge and a photoconductive layer region 106 made of amorphous si, and the second amorphous layer 103 made of Si and O. The first layer 102 contains N in a concn. distribution in the layer thickness direction having concn. C1 in the first region, C3 in the third region, and C2 in the second region 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 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 harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. Particularly in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as a-9i) 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.

Hyakunen et al., a photoconductive member having a photoconductive layer composed of conventional A-3I 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 used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in so-called ghost development, which causes afterimages, or when used repeatedly at high speeds, responsiveness gradually decreases. There were many cases where spots appeared.

Furthermore, a-3i has a relatively smaller absorption coefficient in the long wavelength region than in the short wavelength region of the visible light region, which makes it difficult to match with semiconductor lasers currently in practical use. However, when a commonly used halogen lamp or fluorescent lamp is used as a light source, there remains room for improvement in that the light on the longer 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 "blurring" in the image. Become.

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-5i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms and chlorine atoms, and electrically conductive Boron atoms, phosphorus atoms, etc. are included for control purposes, and other atoms are included as constituent atoms in the photoconductive layer for the purpose of improving other properties, but depending on how these constituent atoms are contained, However, problems may arise in the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charge from the support side may not be sufficiently prevented in dark areas. There are many cases.

Furthermore, when the layer thickness exceeds the thickness of the support, the layer may lift or peel off from the surface of the support, or cracks may occur in the layer as 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-Si material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above-mentioned points, and is characterized by the applicability and applicability of a-St as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has silicon atoms, germanium atoms, and at least one of hydrogen atoms or halogen atoms, so-called hydrogenated amorphous silicon germanium, and halogenated amorphous. Silicon germanium or halogen-containing hydrogenated amorphous silicon germanium [hereinafter referred to as generic notation ra
-5iGa(H, The photoconductive material not only shows extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in every respect, especially as a photoconductive material for electrophotography. The present invention is based on the discovery that it has the same properties and has excellent absorption spectrum characteristics on the long wavelength side.

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

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

Still another object of the present invention is to provide excellent adhesion between a layer provided on a support and a support, and between each laminated layer, and to provide a dense and stable structural arrangement. It is an object of the present invention to provide a high quality photoconductive member.

Still another object of the present invention is to provide a charge control system for electrostatic image formation to the extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has sufficient retention ability and excellent electrophotographic properties with almost no deterioration in its properties observed even in a humid atmosphere.

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

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

The photoconductive member of the present invention is composed of a support for the photoconductive member, an amorphous material containing germanium atoms, and a second layer region (G) provided on the support, and a second layer region (G) containing silicon atoms. a first layer comprising an amorphous material and a second layer region (S) exhibiting photoconductivity provided on the first layer region (G); and a second layer region (S) provided on the first layer region (G); has a photoreceptive layer consisting of a second layer made of an amorphous material containing silicon atoms and oxygen atoms, and the first layer contains nitrogen atoms and has A tokki characterized by having a first region, a third region, and a second region having atomic distribution concentrations of C(1), C(3), and C(2), respectively, in this order from the support side. Sakai's thoughts (However, the distribution concentration C(3) alone will not reach the maximum, and any one of the distribution concentrations c(i), C(2), and (3)
is O, then the other two are not O 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.

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

Further, the photoconductive member of the present invention has high photosensitivity in the entire 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 described 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. It has a second layer (,11) 103. First layer (
I) 102 and the second layer (■) 103 constitute a light-receiving layer 104.

The first layer (I) 102 is made of an amorphous material (hereinafter ra-Ge) containing germanium atoms and, if necessary, at least one of silicon atoms, hydrogen atoms, and halogen atoms.
(bj, H, (hereinafter referred to as ra-3i (H, X)
a photoconductive second layer region (S) 106 provided on the first layer region (G) 105;
and has.

The germanium atoms are distributed evenly and uniformly in the first layer region (G) 105.
It may be contained in the layer, or it may be contained evenly in the layer thickness direction, but the distribution concentration may be non-uniform.

In each case, in the first layer region (G) 105, with respect to the in-plane direction parallel to the surface of the support,
Germanium atoms are required to be contained in a uniform distribution and a universal focus in order to make the properties uniform in the in-plane direction.

In particular, it is evenly contained in the layer thickness direction of the first layer (rI) 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 104). )
The support 101 side (the photoreceptive layer and the support 1
The germanium atoms are contained in the first layer region (G) 105 so that they are distributed more toward the interface side with the first layer region (G) 105 or vice versa.

In the photoconductive member of the present invention, as described above, it is desirable that the ridges contained in the first layer region (G) 105 be uniformly distributed in the in-plane direction parallel to the surface.

In the present invention, germanium atoms are not contained in the second layer region (S) 106 provided on the first layer region (G) 105, and the first layer region (G) 105 does not contain germanium atoms. By forming the layer (I) 102, it is possible to obtain a photoconductive member that has excellent photosensitivity to light in the entire wavelength range from relatively short and long wavelengths to relatively short wavelengths, including the visible light region. I can do it.

Further, in one of the preferred embodiments, the distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously and evenly distributed throughout the entire layer region, and germanium atoms are evenly distributed throughout the layer region. Since the distribution concentration C of atoms in the layer thickness direction decreases from the support 101 side toward the second layer region (S) 106, the first layer region (G) 1
05 and the second layer region (s)ioe, and by extremely increasing the distribution concentration C of germanium atoms at the end of the support lot side as described later, When a semiconductor laser or the like is used, the light on the longer wavelength side that is almost completely absorbed by the second layer region (S) 106 is substantially completely absorbed in the first layer region (CG) 105. be able to,
Interference due to reflection from the surface of the support 101 can be prevented.

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

2 to 10, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer region (G) 105 exhibiting photoconductivity, and t represents the support 101. tT indicates the position of the surface of the first layer region (G) 105 on the side opposite to the support side. That is, in the first layer region (G) 105 containing germanium atoms, layers are formed from the t8 side toward the t□ side.

In the example shown in FIG. 2, in the first layer region (G) 105, the surface on which the first layer region (G) 105 containing germanium atoms is formed and the support 101 From the interface position t, which is in contact with the surface of
, the distribution density is gradually and continuously decreased from C2. At the interface position t□, the distribution concentration C of germanium atoms is C3.

In the example shown in FIG. 3, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 gradually and continuously decreases from the concentration C4 from the position tB to the position t□, forming a distribution state in which the concentration C6 is reached at the position t.

In the case of FIG. 4, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is set to a constant value from position t to concentration CI up to position t2, and from position t2 to position t □, gradually and continuously decreased to 1 position t
At T, the 1-distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is continuously and gradually decreased from the concentration C6 from the position t6 to the position 1T. is considered to be essentially zero.

In the example shown in FIG. 6, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at position 1
．． and position t3, the concentration is a constant value C1,
At position 1T, the concentration C is present. position t, and position tT
, the distribution concentration C decreases in a linear manner from the position t3 to the position 1T.

In the example shown in FIG. 7, the first layer region (G) 1
The distribution concentration C of germanium atoms contained in 05 takes a constant value of concentration C11 from position t to position t4, and from position t4 to position t from concentration C1 It is said that the distribution state is decreasing.

In the example shown in FIG. 8, the first layer region (G) 105
The distribution concentration C of germanium atoms contained in is at the position t,
From there, until the position meter 〇 is reached, the concentration decreases in a linear manner so that the concentration reaches 01 and reaches substantially zero.

In FIG. 9, the distribution concentration C of germanium atoms contained in the first layer region (G) 105 is linearly decreased from the concentration car to the concentration CIG from the position t to the position t5, position t.

An example is shown in which the density CI6 is set to a constant value between and one position.

In the example shown in FIG. 10, the first layer region (G)
The distribution concentration C of germanium atoms contained in 105 is the concentration C1 at position t, and the concentration C1 at position 1. The concentration CI7 is initially slowly decreased until t,
In the vicinity of the position t, the concentration is rapidly decreased to a concentration CI8 at the position t.

Between position t6 and position t7, the concentration decreases rapidly at first, and then gradually decreases to reach the concentration C 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 C2°. Between position 11r and position 1T,
The concentration C is reduced to substantially zero according to the curve shown in the figure.

As described above, from FIG. 2 to FIG. 1θ, the first layer region (G)
As described in some of the typical examples of the distribution state of the germanium atoms contained in the support 105 in the layer thickness direction, in the present invention, the support 101 has a portion with a high distribution concentration C of germanium atoms. It is preferable that the first layer region (G) 105 is provided with a distribution state of germanium atoms having a portion where the distribution concentration C is considerably lower than that on the support 101 side when the interface is on the side. This is one of the most important examples.

The first layer region (G
) 105 is preferably a localized region containing germanium atoms at a relatively high concentration (
It is desirable to have A).

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

The localized region (A) may be the entire layer region (L-r) from the interface position t to the final thickness of 5, or...
It may also be part of the layer region (LT).

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

In the localized region (A), the distribution state of the germanium atoms contained therein in the layer thickness direction is such that the maximum value Cmax of the distribution concentration of germanium atoms is the sum of the distribution concentration of germanium atoms and silicon atoms.
Preferably 1000 atomic ppm or more, more preferably 50
It is desirable that the layer be formed in such a manner that a distribution state of 00 atomic ppm or more, optimally txio atomic ppm or more can be achieved.

That is, in the present invention, the first layer region (G) 105 containing germanium atoms has a maximum distribution concentration within 5 IL (layer region with a thickness of 1 to 5 IL) from the support 101 side. Preferably, it is formed such that there is a value Cwax.

In the present invention, the content of germanium atoms contained in the first layer region (G) 105 is appropriately determined as desired so as to effectively achieve the object of the present invention. Preferably l-10 for the sum of
XIO atomic ppm more preferably lOO~9.5×10
5 atomic ppm, optimally 500 to 8 XlO atomic ppm
It is desirable to set it to m.

The distribution state of germanium atoms in the first layer region (G) 105 is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction is small when exposed to light from the support 101 side. If a decreasing change is given toward the free surface 107 side of the receptor layer 104 or vice versa, the rate of change curve of the distribution concentration C can be arbitrarily designed as desired. Accordingly, the first layer region (G) 105 having the required characteristics can be realized as desired.

For example, the distribution concentration C of germanium atoms in the first layer region (G) 105 is sufficiently increased on the support 101 side, and as low as possible on the free surface 107 side of the photoreceptive layer 104. By giving a change in the distribution concentration C to the distribution concentration curve of germanium atoms, high photosensitivity can be achieved for light in the entire range of wavelengths from relatively short wavelengths to relatively short 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.

In the present invention, the layer thickness T of the first layer region (G) 105 is preferably 30A to 50L, more preferably 40λ to
40 liters, most preferably 50A to 30 liters.

Further, the layer thickness T of the second layer region (s)tos is preferably 0.5 to 90 IL, more preferably 1 to 80 IL, and optimally 2 to 50 IL.

The layer thickness T of the first layer region (G) 105 and the second layer region (
S) The sum of the layer thicknesses T (T8+T) of 106 is determined based on the organic relationship between the properties required for both layer regions and the properties required for the entire photoreceptive layer, of the photoconductive member. It is appropriately determined according to the requirements during layer laying.

In the photoconductive member of the present invention, the numerical range of (TB+T) is preferably 1 to 100 pL, more preferably 1 to 80 pL, and most preferably 2 to 50 IL.

In a more preferred embodiment of the present invention, the above layer thickness T
It is desirable that appropriate numerical values be selected for each of n and layer thickness T so as to preferably satisfy the relationship Tm/T≦1.

In selecting the numerical values of layer thickness TB and layer thickness T in the above case, more preferably the relationship TB/T≦0.9, optimally T s /T≦0.8 is satisfied. It is desirable that the values of the layer thickness Ts and the layer thickness ↑ are determined as follows.

In the present invention, when the content of germanium atoms contained in the first layer region (G) 105 is lXlOs atoms ppm or more, the layer thickness of the first layer region (G) 105 It is desirable that Tn be fairly thin, preferably 30 pL or less, more preferably 25 IL or less, and optimally 20 IL or less.

In the present invention, the layer thickness of the first layer region (G) 105 and the second layer region (G) 105 are
Since the layer thickness of the layer region (s)tos is one of the important factors for effectively achieving the object of the present invention, it is important to ensure that the formed photoconductive member has sufficient desired characteristics. , due care must be taken in designing the photoconductive member.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the first layer (I) 102, In the first layer (I) 102, a layer region (N) containing nitrogen atoms is provided.

As shown in FIG. 11, the first layer (I) 102 contains nitrogen atoms, and the distribution concentration in the layer thickness direction is as follows:
The first region (1) 108, which has the value C(1), C(2
), the second region (2) 109 and C (3)
and a third region (3) 110 having a value of .

In the present invention, the above-mentioned 1. Second. And each of the third regions 1O8 to 11O does not necessarily need to contain nitrogen atoms, but if any one region does not contain nitrogen atoms, the other two regions do not necessarily contain nitrogen atoms. must necessarily contain nitrogen atoms, and the distribution concentration of nitrogen atoms in the layer thickness direction in these regions must be different. Clogging, distribution concentration of nitrogen atoms C(1), C(2)
, C(3) becomes 0, the other 2
Each area 108~
110 needs to be formed. By doing so, it is possible to effectively prevent charges from being injected into the photoreceptive layer 104 from the free surface 107 side or the support body 101 side when subjected to charging treatment, and at the same time Receptive layer 1
The dark resistance of 04 itself and the adhesion between the support 10J and the light-receiving layer 104 can be improved.

The first layer ('I) 102 has practically sufficient photosensitivity and dark resistance, and can sufficiently prevent charge injection into the first layer ('I) 102, and In order to effectively transport the photocarriers generated in (1) and 102, the distribution concentration C(3) of nitrogen atoms in the third region (3) 110 must not be the maximum alone. It is necessary to design the first layer (1) 102 so that the third region (3) 110 does not become thicker than the other two regions 108 to 110. It is desirable to design the first layer (1) 102 so that it is sufficiently thick,
More preferably, the first layer (1) 102 is designed such that the layer thickness of the third region (3) 110 occupies one-fifth or more of the layer thickness of the first layer (I) 102. desirable.

In the present invention, the layer thickness of the first region (1) 108 and the second region (2) 109 is preferably 0.00
It is desirable to set it to 3 to 30 IL, more preferably 0.004 to 20 IL, and optimally 0.005 to 10 IL. Further, the layer thickness of the third region (3) 110 is preferably 1-iooIL, more preferably 1-80IL, and optimally 2-50g.

First area (1) 108 and second area (2) 109
preventing charge injection into the first layer (I) 102;
When designing the first layer (1) 102 to mainly function as a so-called charge injection blocking layer, the layer thicknesses of the first region (1) 108 and the second region (2) 109 teeth,
It is desirable that each of them has a maximum of 1 OIL.

When designing the photoreceptive layer so that the third region (3) 110 mainly functions as a charge generation layer, the layer thickness of the third region (3) 110 depends on the light source used. It can be determined as desired depending on the absorption coefficient of light. in this case,
Normally, if a light source used in the field of electrophotography is used, the layer thickness of the third region (3) 110 is at most 1
In order for the third region (3) 110 to mainly function as a charge transport layer, it is preferable that the layer thickness is at least 5 mm.

In the present invention, the nitrogen 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 atoms, germanium atoms, and nitrogen atoms. It is desirable to Furthermore, when the distribution concentrations C(1), C(2), and C(3) are not O, the minimum value is preferably 1 atom ppm with respect to the sum of silicon atoms, germanium atoms, and nitrogen atoms.
, more preferably 50 atomic ppm, most preferably 100 atomic ppm.

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

12 to 16 show typical examples of the distribution of nitrogen atoms in the entire first layer (I) 102. It should be noted that symbols used throughout the description of these figures have the same meanings as used in FIGS. 2 to 1O. Note that tB in the figure indicates the surface position of the first layer (I) 102 on the support 101 side, and tT indicates the surface position of the first layer (I) 102 on the support 101 side.
The surface position of the first layer (I) 102 on the opposite side from 1 is shown.

In the example shown in FIG. 12, the distribution concentration C(N) of nitrogen atoms is constant at C21 from position t to position t9, and the distribution concentration C(N) of nitrogen atoms from position t9 to position t1 is
N) is assumed to be constant at C20.

In the example shown in FIG. 13, the distribution concentration C(N) of nitrogen atoms is a constant value C23 from position t-to position tlo, and the distribution concentration C(N) of nitrogen atoms from position tto to position tI+. is set to C2, and the distribution concentration C(N) of nitrogen atoms is set to Cu from position t11 to position D, and the distribution concentration C(N) of nitrogen atoms is decreased in three stages.

In the example of FIG. 14, the distribution concentration C(N) of nitrogen atoms from position tB to position t12 is C2t, and the distribution concentration C(N) of nitrogen atoms from position t12 to position tT is C2□. .

In the example of FIG. 15, the distribution concentration C(N) of nitrogen atoms is C2 from position t to position t13, and from position t17 to position t5. Until then, the distribution concentration C(N') of nitrogen atoms is C
29, and the distribution concentration C(N) of nitrogen atoms from position t, 4 to position ta is C1o.

In this way, the distribution concentration C(N) of nitrogen atoms is increased in three stages.

In the example of FIG. 16, from position tB to position tIff,
The distribution concentration C(N) of nitrogen atoms is C71, and the position t15
From position tl&, the distribution concentration C(N) of nitrogen atoms is C32, and from position t14 to position tT, the distribution concentration C(N) of nitrogen atoms is C33. in this way,
The distribution concentration C(N) of nitrogen atoms is set to be high on the support body 101 side and on the free surface 107 side.

In the present invention, the layer region (N) containing nitrogen atoms provided in the first layer (I) 102 (the above-described first layer region (N)) is provided in the first layer (I) 102.
Second. If the main purpose is to improve the photosensitivity and dark resistance, the third region 108 to 110 (consisting of at least two layer regions) should cover the entire layer region of the first layer (I) 102. In order to prevent charge injection from the free surface 107 of the first layer (1) 102, the first layer (1) is provided near the interface on the free surface 107 side. When the main purpose is to strengthen the adhesion between the first layer (I) 102 and the first layer (I) 102, it is provided so as to occupy the end layer region (E) of the first layer (I) 102 on the side of the support 101.

The content of nitrogen atoms contained in the layer region (N) is made relatively small in order to maintain high photosensitivity as described above, and the content of nitrogen atoms contained in the first layer (1) 10
In order to prevent charge injection from the free surface of 2, the support 101 and the first layer (1) 102 are relatively large.
It is desirable that the amount be relatively large for the main purpose of reliably reinforcing the adhesion with the material.

In addition, in order to achieve these advantages at the same time, support l
Nitrogen atoms are distributed in a layer region (N ).

In the present invention, the nitrogen atom content in the nitrogen atom-containing layer region (N) provided in the first layer CI) 102 depends on the characteristics required of the layer region (N) itself or the layer region (N). ) is provided in direct contact with the support 101, it can be appropriately selected based on organic relationships such as the relationship with the properties at the contact interface with the support 101.

In addition, when another layer region is provided in direct contact with the layer region (N), the characteristics of the other layer region and the relationship with the characteristics at the contact interface with the other layer region are also taken into consideration. and the nitrogen atom content is appropriately selected.

The amount of nitrogen atoms contained in the layer region (N) is determined as desired depending on the characteristics required of the photoconductive member to be formed, but it is On the other hand, it is preferably 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 (N) is the first layer (1) 102
Or, even if it does not occupy the entire area of the first layer (I) 102, the ratio of the layer thickness T0 of the layer region (N) to the layer thickness T of the first layer (1) 102 is sufficient. If the amount of nitrogen atoms is large, it is desirable that the upper limit of the content of nitrogen atoms contained in the layer region (N) is sufficiently smaller than the above value.

In the present invention, when the ratio of the layer thickness T0 of the layer region (N) to the layer thickness T of the first layer (1) 102 is two-fifths or more, the layer region (N) ) is preferably 30 at% or less, more preferably 20 at% or less, optimally It is desirable that the content be 10 atomic % or less.

In the present invention, the layer region (N) containing nitrogen atoms is formed on the support 101 side and the second layer (and) as described above.
It is preferable to provide a localized region (B) in which nitrogen atoms are contained at a relatively high concentration near the support 101 and the first layer (103).
) 102 and the acceptance potential can be further improved.

The localized region CB) is desirably provided within 51L in the layer thickness direction from the interface position t8 or t□, if explained using the symbols shown in FIGS. 12 to 16.

In the present invention, the localized region (B) is located at the interface position t
Fj or t7 to 511. It may be the entire layer region (LT) up to the thickness, or it may be a part of the layer region (LT).

Whether the localized region (B) is to be a part or all of the layer region (L) 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(N) of nitrogen atoms is preferably 500 atomic ppm or more, more preferably 800 atomic ppm, as the distribution state of nitrogen atoms contained therein in the layer thickness direction. Above, optimally 1000 atomic pp
It is desirable that the layers be formed so that a distribution state of m or more can be obtained.

That is, in the present invention, the layer region (N) containing nitrogen atoms in the first layer (1) t02 is
So that the maximum value Cmax of the distribution concentration C(N) exists within 5 ml of layer thickness from the side or the second layer (1) 103 (layer area 51L thick from position 1B or 1T). preferably formed.

In the present invention, the halogen atoms contained in the first layer (I) 102 as necessary include fluorine,
Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred.

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

Substances (D) that control such conductive characteristics include so-called impurities in the semiconductor field. Examples include a p-type impurity that provides a conductive property, and an n-type impurity that provides an n-type conductivity. Specifically, pffi impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as boron (B), aluminum (All), gallium (ba), and indium (In).
), thallium (T-1), etc., and B and Ga are particularly preferably used. In addition, n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as phosphorus (P), arsenic (As), antimony (s b),
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, the substance (D) that controls the conduction characteristics described above is included in the first layer (
I) 102, the second layer (I) IO
When it is contained locally in a desired layer region of the first layer (I) 102, especially when it is contained in the end layer region on the support side of the first layer (I) 102, it comes into direct contact with the layer region. The relationship between the properties of other layer regions provided in the layer and the properties at the contact interface with the other layer regions is also considered, and the substance (D
) content is selected appropriately.

In the present invention, the content of the substance (D) that controls conduction properties contained in the first layer (I) 102 is preferably o, o, i to 5X1041' ppm,
J: ! It is preferable that the amount of the compound is 5 to 104 atoms ppm, optimally 1 to 5 X 103 atoms ppm.

In the present invention, the content of the substance (D) in the layer region (PN) containing the substance (D) that governs the conduction properties is preferably 3 ow, ppff1 or more, more preferably 50 In the case of atomic ppm or more, optimally 100 atomic ppm or more, the substance (D) governing the conduction properties is locally contained in a part of the layer region of the first layer (I) 102. It is desirable that the first layer (I) 102 is unevenly distributed in the end layer region (E) on the side of the support.

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, For example, if the substance (D) is the p-type impurity described above, it is injected into the photoreceptive layer 104 from the support 101 side when the free surface lO7 of the photoreceptive layer 104 is subjected to polar charging treatment. When the substance that can effectively block the movement of electrons and controls the conduction characteristics is the n-type impurity, the free surface TO7 of the photoreceptive layer 104 is charged to e polarity. At this time, the movement of holes injected into the light-receiving layer 104 from the support 101 side 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, oot-too atomic ppm, more preferably 0.05 to 500,500 atomic ppm, o, i to
It is desirable that the content be 200 atomic ppm.

In the present invention, when the support side end layer region (E) and the layer region (Z) contain the same type of substance that controls conductivity, the content of the substance in the layer region (Z) In addition to the above-mentioned cases, in the present invention, the first layer (
I) In 102, a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are brought into direct contact. It is also possible to provide a so-called depletion layer in the contact layer region. For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the first layer (I) 102 so as to be in direct contact with each other, so that the so-called p-n A junction can be formed to provide a depletion layer.

In the present invention, the first layer region (G) 105 composed of a-Ge (S i , H, For example, a-Ge(S) is formed by a vacuum deposition method using a glow discharge method.
i, H, X) first layer region (G) 105
To form, basically, a raw material gas for supplying germanium atoms that can supply germanium atoms, a raw material gas for supplying silicon atoms that can supply silicon atoms, and a raw material gas for introducing hydrogen atoms as necessary. or/and a raw material gas for introducing halogen atoms is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, and is previously installed at a predetermined position. A layer made of a-Ge (S i , H, X) may be formed on the surface of a predetermined support. Further, in order to contain germanium atoms in the first layer region (G) 105 in a non-uniform distribution state, the distribution concentration of germanium atoms is controlled according to a desired rate of change curve, and aG e (S i + H *X
) may be formed. In addition, in the sputtering method, a target composed of silicon atoms, or a target composed of the target and germanium atoms is used in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using two targets or a mixed target of silicon atoms and germanium atoms, He, A
A source gas for supplying germanium atoms diluted with diluent gas such as By this, a first layer region (G) 105 is formed. In this sputtering method, if the distribution of germanium atoms is to be made non-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 region (G) 105 can be formed in the same manner as in the sputtering method.

Substances that can be used as raw material gas for supplying silicon atoms used in the present invention include S i ) L, S i, H
Silicon hydride (silanes) in a gaseous state or which can be gasified in the form of , Si3H, Si4H, etc. can be effectively used, especially for ease of handling during layer formation work, silicon S i H, in terms of good atom supply efficiency, etc.
, S i, H, are listed as preferred.

Substances that can be used as raw material gas for supplying germanium atoms include GeH4, Ge, Ht, Ge, and Hr.

G e4H,,,G ekH,,,Ge,H,4,G
Germanium hydride in a gaseous state or gasifiable in the form of e7H, , G e, H, , G e9HJ is mentioned as one that can be effectively used, especially for ease of handling during layer creation work and germanium atom supply. Ge
H4, Ge, H,, Ge3H- (preferred examples include).

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 halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CfLF, CIFBrF, Br.
F,, IF, IF7,? Interhalogen compounds such as 1 1(, fL, IBr, etc.) can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
Preferred examples include silicon halides such as iF, SiF, Si0, and 4 SiBr.

When a photoconductive member characteristic of the present invention is formed by a glow discharge method using such a silicon compound containing halogen atoms, a raw material gas capable of supplying silicon atoms together with a raw material gas for supplying germanium atoms is used. The first layer region (G) made of a-3iGe containing halogen atoms can be formed on the desired support 101 without using silicon hydride gas.
105 can be formed.

When manufacturing the first layer region (G) 105 containing halogen atoms according to the glow discharge method, basically 1, for example, a silicon halide serving as a raw material gas for supplying silicon atoms, and a raw material gas for supplying germanium atoms. Germanium hydride and gas such as Ar, F2, He, etc. are mixed at a predetermined mixing ratio and gas flow rate to form a first layer region (G) 105.
The first layer region (G) 105 can be formed on the desired support 101 by introducing the gas into a deposition chamber for forming a gas and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer.

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

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

Further, when introducing hydrogen atoms into the first layer region (G) 105, a raw material gas for hydrogen atom introduction, such as F2,
Alternatively, gases such as the above-mentioned silanes and/or germanium hydride may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but halogenated compounds such as HF, HCIL, HBr, and HI are also used. Hydrogen, S i H, F□, S i H, I, SiH, C
Also, 5iHCfL,, S i H, B r2. Si
HB r, etc. (7) Halogen-substituted silicon hydride, and G
e HF, , G e H, F2. G e H3P,
G e HCl,, G e H, CfL,, G e H
, Cn, G e HB r3. G eH, B r,,
G e H, Br, G e HI,, G e H, I
2. Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as GeH and I, GeF
4. GeC1+, G e B r4, G e I,, G
eF4,GeCn,,GeBr,,GeI2
Gaseous or gasifiable substances such as germanium halides, etc., can also be mentioned as useful substances for forming the first layer region (G) 105.

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

In order to structurally introduce hydrogen atoms into the first layer region (G) 105, in addition to the above, H U or S i H4,S
i2H,, Si, Tsuru, Si4H,, $ silicon hydride with germanium or a germanium compound for supplying germanium atoms, or GeHlG e, H,,
G e, H,, G e, H,, G, e, H,,,
Ge, H14, G e7H,,,G e,H,,,G
It is also possible to cause a discharge by coexisting germanium hydride with silicon or a silicon compound for supplying silicon atoms in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms or the amount of halogen atoms contained in the first layer region (G) 105 to be formed, or the sum of the amounts of hydrogen atoms and halogen atoms (
H+X) is preferably 0. O1-40 at%, more preferably 0.05-30 at%, optimally 0.1-25
It is preferable to express it in atomic percent.

In order to control the amount of hydrogen atoms and/or halogen atoms contained in the first layer region (G) 105, for example, the support temperature or/and the amount of hydrogen atoms or halogen atoms used to contain them can be controlled. The amount of starting material introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the second
The layer region (S) 106 is the first layer region (G) described above.
105 (starting material (II) for forming the second layer region (S)) excluding the starting material that becomes the raw material gas for supplying germanium atoms from the starting material (CI) for forming the second layer region (S)
) wo use 1. -c,, tl layer region (G) 10
It can be formed according to the same method and conditions as in the case of forming No. 5.

That is, in the present invention, the second layer region (ts) 106 composed of a-3i (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, in order to form the second layer region (S) 106 composed of a-3t (H, Along with the raw material gas, a raw material gas for introducing hydrogen atoms and/or for introducing halogen atoms as necessary is introduced into a deposition chamber whose interior can be depressurized, and a glow discharge is generated in the deposition chamber to generate a predetermined amount. A layer consisting of a-3i(H,X) may be formed on the surface of a predetermined support. In addition, when forming by a sputtering method, for example, when sputtering a target composed of silicon atoms in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms or / and a gas for introducing halogen atoms may be introduced into the deposition chamber for sputtering.

In the present invention, the second layer region (S) 106 formed
The amount of hydrogen atoms or the amount of halogen atoms contained in
Or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 at%, more preferably 5 to 30 at%
The optimum content is preferably 5 to 25 atomic %.

In the present invention, in order to provide the layer region (N) containing nitrogen atoms in the first layer (I) 102, the first layer (I) 10
2, using the starting material for introducing nitrogen atoms together with the starting material for forming the first layer (I) 102,
It may be contained in the formed layer while controlling its amount.

When the glow discharge method is used to form the layer region (N), the desired starting material for the first layer (I) 102 type is selected from the starting materials for nitrogen atom introduction. starting materials are added. As the starting material for introducing nitrogen atoms, most of the gaseous substances containing at least nitrogen atoms or gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms, a raw material gas containing nitrogen atoms, and a raw material gas containing hydrogen atoms and/or halogen atoms as necessary are mixed at a desired mixing ratio. Alternatively, a raw material gas containing silicon atoms and a raw material gas containing nitrogen atoms and hydrogen atoms may be mixed at a desired mixing ratio, or A raw material gas having constituent atoms and a raw material gas having three constituent atoms, silicon atoms, nitrogen atoms, and hydrogen atoms, can be mixed and used.

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

A starting material that can be effectively used as a raw material gas for introducing nitrogen atoms used when forming the layer region (N) has nitrogen as a constituent atom, or has nitrogen and hydrogen as constituent atoms. For example, nitrogen (1'jz), ammonia (N
Nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and azides, such as H,), hydrazine (H,N N H,), hydrogen azide (HN, ), ammonium azide (NH), etc. In addition, nitrogen trifluoride (F, N), nitrogen tetrafluoride (F, N,
) and other halogenated nitrogen compounds.

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

As the raw material gas for introducing oxygen atoms into the layer region (N), for example, oxygen (0,), ozone (0,
3), -nitrogen oxide (NO), nitrogen dioxide (No, ),
-Nitrogen dioxide (N, O), nitrogen sesquioxide (Nyoq), trinitrogen tetraoxide (N, 04), nitrogen sesquioxide (Nyu06),
For example, disiloxane (HjS) whose constituent atoms are nitrogen dioxide (No), silicon atoms, oxygen atoms, and hydrogen atoms
i OSiH, ), trisiloxane (H,5iO5iH
, 09iHj) and the like.

To form the layer region (N) by the sputtering method, when forming the first layer (I) 102, a single crystal or polycrystalline silicon wafer or a Si3N4 wafer, or silicon atoms and Si, N4 This can be carried out by sputtering these materials in various gas atmospheres using a mixture of wafers as a target.

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

Alternatively, silicon atoms and SisN+ can be used as separate targets, or by using a single target containing a mixture of silicon atoms, Si, and N4, in an atmosphere of dilution gas as a sputtering gas, or Sputtering may be performed in a gas atmosphere containing at least hydrogen atoms and/or halogen atoms as constituent atoms.

As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, when forming the first layer (I) 102,
When providing a layer region (N) containing nitrogen atoms, the distribution concentration C(N) of nitrogen atoms contained in the layer region (N) is changed in the layer thickness direction to obtain a desired distribution in the layer thickness direction. state (d
In order to form a layer region (N) having an epth profile), in the case of a glow discharge, a starting material gas for introducing nitrogen atoms whose distribution concentration C(N) is to be changed is adjusted by adjusting the gas flow rate to a desired rate of change. It may be introduced into the deposition chamber while changing it appropriately according to the curve. For example, the opening of a predetermined needle valve provided in the coating of the gas flow path system may be appropriately changed by any commonly used method such as manually or by using an externally driven motor. At this time,
For example, a desired content rate curve can be obtained by controlling the flow rate using a microcomputer or the like according to a rate of change curve designed in advance.

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

Second, if a target containing a mixture of silicon atoms and 5t3N4t is used as a sputtering target, for example, the mixing ratio of silicon atoms and Sis% should be adjusted in the direction of the layer thickness of the target. This is done by changing it in advance.

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 second region (S) 106. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, as a starting material for introducing a group Ⅰ atom, B, H, B4 are used for introducing a boron atom. ,ByoH9,B,H,,,B,
H. , B, H, 2, B, H, 4, etc., BCI, , BBrJ, and the like. In addition, A I Cl, , G e Cl, , Ge
(CH,), I nc13, T u CM, etc. can also be mentioned.

In the present invention, the starting materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms are PH,
Hydrogenated phosphorus such as PyuH4, PH resin, P F,, P F
,, PCfL,, PC! L,, PB r,, PBr
, , PI, and other phosphorus halides. In addition,
As H,, As F,, As C13,AsB
r,, AsF,, S bHj, S bF,, 5bF
r, sbc, SbCl, BiH, BiC, BiB, 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 (PN) that constitutes the first layer (I) 102 and is unevenly distributed on the support 101 side and is made of steel containing a substance that controls conduction characteristics is as follows: It is determined as desired according to the characteristics required of the layer region (PN) and other layer regions forming the first layer (I) 102 formed on the layer region (PN). However, the lower limit thereof is preferably 30λ or more, more preferably 40λ or more, and optimally 50λ or more. Further, when the content of the substance controlling the conductive properties contained in the layer region (PN) is 30 atomic ppm or more, the upper limit of the layer thickness of the layer region (PN) is preferably 10% or less, preferably 8p or less, optimally 5IL
In the photoconductive member 100 shown in FIG. 1, the second layer (I) 103 formed on the first layer (I) 102 has a free surface and is preferably In order to achieve the objects of the present invention in terms of moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability.

Furthermore, in the present invention, since each of the amorphous materials constituting the first layer (B i02 and the second layer (x)to3) has a common constituent element of silicon atoms, both layers The laminated interfaces of (1) 102 and (1) 103 are sufficiently acidified to ensure chemical stability.

The second layer (1) to3 in the present invention is an amorphous material (hereinafter referred to as r a -(Si
xo+-x) y(H,X)+-yJ. However, 0
<x, y<1).

The formation of the second layer (I) 103 composed of a - (S ixo + - x) y (H, This is done by the brating method, etc. 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 produced.
The second layer (and) 10 is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having desired characteristics, and in which oxygen atoms and halogen atoms are formed together with silicon atoms.
The glow discharge method or the sputtering method, which has the advantage that it can be easily introduced into the liquid, is preferably employed.

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

In order to form the second layer ([) 103 by the glow discharge method, the raw material gas for forming a-(S 1xorx) y(H, The gas that has already been formed on the support 101 is mixed and introduced into the deposition chamber in which the support 101 is installed, and the introduced gas is turned into gas plasma by generating a glow discharge. What is necessary is to deposit a-(S 1xOj-x) y(H,X) ry on the first layer (I) 102.

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

When using a raw material gas that has a silicon atom as one of silicon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, for example, a raw material gas that has silicon atoms as a constituent atom and an oxygen atom as a constituent atom. If necessary, a raw material gas containing hydrogen atoms and/or a raw material gas containing halogen atoms may be mixed at a desired mixing ratio, or silicon atoms may be used as constituent atoms. The raw material gas and the raw material gas whose constituent atoms are oxygen atoms and hydrogen atoms and/or the raw material gas whose constituent atoms are oxygen atoms and halogen atoms are also mixed at a desired mixing ratio, or A raw material gas whose constituent atoms are silicon atoms, and a raw material gas whose constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms, or raw material gases whose constituent atoms are silicon atoms, oxygen atoms, and halogen atoms. Can be used in combination.

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

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

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

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

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

Secondly, S i as a target for sputtering
It is formed by using a target composed of 02, a target composed of silicon atoms and a target composed of SiO□, or a target composed of silicon atoms and SiO. Oxygen atoms can be introduced into the second layer (I[) 103. At this time, if the aforementioned raw material gas for introducing oxygen atoms is also used, the second layer (T!L) can be formed by controlling the flow rate.
It is easy to arbitrarily control the amount of oxygen atoms introduced into 103.

The content of oxygen atoms introduced into the second layer (1) 103 can be determined by controlling the flow rate when the raw material gas for introducing oxygen atoms is introduced into the deposition chamber, or by controlling the flow rate of the raw material gas for introducing oxygen atoms into the deposition chamber, or by controlling the flow rate of the raw material gas for introducing oxygen atoms into the deposition chamber. The proportion of oxygen atoms contained therein can be arbitrarily controlled as desired by adjusting the proportion of oxygen atoms contained therein, or by adjusting the proportion of oxygen atoms contained therein when preparing the gouget, or by both.

The starting materials used as the raw material gas for supplying silicon atoms used in the present invention include S i H4+ S i,
H&, S+,? Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Hr+Si+H1o1, can be used effectively, especially in terms of ease of handling in layer creation work and good silicon atom supply efficiency. DeS
Preferred examples include i H+, S i, H, and 7.

Using starting materials such as these, the second (7) N (]j
L) Hydrogen atoms may also be introduced into 103 along with silicon atoms.

In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gases for supplying silicon atoms include silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, SiF4. Si,F,,SiC
Preferred examples include silicon halides such as M, SiBr4° and the like. Furthermore, S i, H2F2
．． S i H2I.

, S i H2C1,, S i HCJI,, S
i H, B r,.

Halogen-substituted silicon hydrides such as S i HB r and halides that have a hydrogen atom as one of their constituents in a gaseous state or can be gasified are also effective second layers (, [() 10
This results in a vehicle that can be cited as a starting material for supplying silicon atoms for the formation of 3.

Even when these silicon compounds containing halogen atoms are used, halogen atoms can be introduced together with silicon atoms into the second layer (In) 103 to be formed by appropriately selecting the layer forming conditions as described above. I can do it.

Among the above-mentioned starting materials, silicon halide compounds containing hydrogen atoms are extremely effective for controlling electrical or photoelectric properties at the same time as introducing halogen atoms into the layer when forming the second layer (IF) 103. Since a hydrogen atom can also be introduced, it is used as a suitable starting material for introducing a halogen atom in the present invention.

In addition to the above-mentioned materials, examples of effective starting materials used as raw material gas for introducing halogen atoms when forming the second layer (i) 103 in the present invention include fluorine,
Halogen gas of chlorine, bromine, iodine, BrF, CfLF
, CfLFj.

BrF BrF3. IF,, IF7. IC text, interhalogen compounds such as IBrp, HF, HCIL, HBr
.

Examples include hydrogen halides such as H1.

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms used when forming the second layer (jL) 103 include oxygen atoms as constituent atoms or nitrogen atoms and oxygen atoms. For example, oxygen (0,
), ozone (03), -nitrogen oxide (NO), nitrogen dioxide (Noyo), -nitrogen dioxide (N,0), nitrogen sesquioxide (
Examples include nitrogen tetroxide (N20+), nitrogen sesquioxide (N,Os), and nitrogen trioxide (No,), and the constituent atoms are silicon atoms, oxygen atoms, and hydrogen atoms. , for example, disiloxane (H3S i O
S i H3), trisiloxane (H3S i OS
Examples include lower siloxanes such as H, O3i H3).

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

The second layer (1) 103 in the present invention is carefully formed so that its required properties are imparted as desired.

In other words, substances whose constituent atoms are silicon atoms, oxygen atoms, and optionally hydrogen atoms and/or halogen atoms have structural forms ranging from crystalline to amorphous depending on the conditions for their creation, and in terms of electrical properties, From conductive to semiconducting,
Furthermore, it exhibits properties ranging from insulating to photoconductive to non-photoconductive. Therefore, in the present invention, a −(S ix
The preparation conditions are strictly selected as desired so that O+ -x) V (H,X)+-y is formed. For example, in order to provide the second layer (I) 103 with the main purpose of improving electrical voltage resistance, a-(SixOl-x)
y (H,X)ry is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the second layer (X) 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and irradiation,
a - (S 1xo1- x ) y (H, X) as an amorphous material that has a certain degree of sensitivity to light
ry is created.

On the surface of the first layer (I) 102, a-(Six.

+-x)y Second layer (1) consisting of (H,X)+-y
Support 101 during layer formation when forming 103
The temperature is an important factor that influences the structure and properties of the layer formed. In the present invention, the temperature of the support during layer formation is strictly controlled so that a-(SixOl-x)y (H,X)1-y having the desired properties can be created as desired. is desirable. The second objective of the present invention is to effectively achieve the desired objective! (II)103
Formation of the second layer (I) 103 is carried out by appropriately selecting the temperature of the support in the optimum range in accordance with the formation method, but the temperature of the support during layer formation is preferably 20 to 400°C. , more preferably 50-350°C, optimally 100-300°C
It is desirable that this is the case.

In forming the second layer (JL) 10゛3, delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. Adoption of glow discharge method or sputtering method is advantageous. When forming the second layer (II) 103 using these layer forming methods, the discharge power during layer formation is set in the same manner as the support temperature described above.
-(S 1x01- x ) It is one of the important factors that influences the characteristics of yXry.

a having the characteristics for achieving the object of the present invention;
-(S ixo+-x )y It is desirable that the

The gas pressure in the deposition chamber is preferably o, oi to I Torr.
, more preferably about 0 Torr, 1-0 Torr, and 5 Torr.

In the present invention, the values of the support temperature and discharge power for forming the second layer (I) 103 are preferably within the ranges described above, but these layer forming factors are independently and separately determined. The desired characteristic a −(S ixO+ −x) y (H,X)+
It is desirable that the optimum value of each layer creation factor be determined based on mutual organic relationship so that the second layer (II) 103 consisting of -y is formed.

The amount of oxygen atoms contained in the second layer (1) 103 in the photoconductive member of the present invention is determined based on the desired characteristics to achieve the object of the present invention, similar to the conditions for forming the second layer (1) 103. This is an important factor for forming the resulting second layer (I) 103.

The amount of oxygen atoms contained in the second layer (1) 103 in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the second layer (1.) lo3. It can be determined by

That is, the general formula a −(SixO+−x) y(H,
The amorphous material denoted by
It is written as r a -S 1aO1-aJ.

However, 0<a<1), an amorphous material composed of silicon atoms, oxygen atoms, and hydrogen atoms (hereinafter referred to as r a -(S
ibo 1-b)c Hl-c", provided that 0<b
, c<1), and an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter ra-(Sidol-d) e (H,X)+
-e”. However, if 0<d, e, it is classified as 1).

In the present invention, the second layer (I[) 103 is a-Sia
When composed of Ol-a, the amount of oxygen atoms contained in the second layer (and) 103 is expressed as a in a-5iaCh-a, where a is preferably 0.33 to 0. 99999
, more preferably 0.5-0.99, optimally 0.6-0
．． It is 9.

In the present invention, the second layer (It) 103 is a-(S
ibo+-b)c Hrcte, the amount of oxygen atoms contained in the second layer (I) 103 is a-(
Sibo+-b)c Hl-c When expressed as b and c, b is preferably 0.33 to 0.99999, more preferably 0.5 to 0.99. Optimally 0.6 to 0.9,
C is preferably 0.6 to 0°99, more preferably 0.6
5-0.98. The optimum value is 0.7 to 0.95.

The second layer (x) 103 is a − (SidO+−d)
e(H,X)1-e, the second layer (
I) The content of oxygen atoms contained in 103 is:
a - (S jdot-d) e (H, X) + - d of e
and e, d is preferably 0.33 to 0
．． 99999, more preferably 0.5 to 0.99, optimally 0.6 to 0.9, and e is preferably 0.8 to 0.
The range of 99 and above is one of the important factors for effectively achieving the object of the present invention. The layer thickness is appropriately determined according to the desired purpose so as to effectively achieve the object of the present invention. Furthermore, this layer thickness is the same as the layer (1)
The amount of oxygen atoms contained in 103 and the first layer (I) 1
The relationship with the layer thickness of 02 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 that this layer thickness is also taken into consideration from the economical point of view, taking into account productivity and mass production.

The layer thickness of the second layer (z) to 3 in the present invention is as follows:
Preferably 0.003 to 307t, more preferably 0.0
It is desirable that the OIL is between 0.04 and 20, most preferably between 0.005 and 1.

Further, in the present invention, in order to further promote the effect obtained with oxygen atoms, carbon atoms may be included in the second layer (z) 103 together with oxygen atoms. The raw material gas for introducing carbon atoms into the layer (Jl) 103 includes, for example, saturated hydrocarbons having 1 to 5 carbon atoms, carbon atoms and hydrogen atoms, and saturated hydrocarbons having 2 to 5 carbon atoms.
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Specifically, saturated hydrocarbons include methane (CB, ), ethane (CyuH6), propy(C3H,) +' n-butane (n-C4H1l
) l pentane (C,H,,), ethylene hydrocarbons include ethylene (CJH,), propylene (C,H,)
), butene-1 (C, He), butene-2 (C4H
ρ, inbutylene (C+Hr), pentene (C,H
, As the acetylene hydrocarbon, acetylene (C
, H, ), methylacetylene (c3H4) + butyne (C4HD, etc.).In addition to these, raw material gases containing silicon atoms, carbon atoms, and hydrogen atoms include 5i (C Alkyl silicides such as (C2Hr)4 can be mentioned.

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

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

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. Ru.

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, NiCr2.
AIL, Cr, Mo, Au, Ir, Nb, T
a, V, T i, P t, P d, I
n-03, SnO,, I, T O (I n, O, +
Conductivity is imparted by providing a thin film consisting of S n O, ), etc., or if it is a synthetic resin film such as a polyester film, NiCr, AiL, Ag, Pb
, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta
, V, Ti, Pt, or the like on the surface by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminating the surface with the metal described above to impart conductivity to the surface.

The support 101 may have any shape such as a cylinder, a belt, or a plate, and the shape may be determined as desired. For example, the photoconductive member 100 shown in FIG. If used as a member for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.The thickness of the support 101 is determined as appropriate so that a desired photoconductive member is formed. However, when flexibility is required as a photoconductive member, the thickness is made as thin as possible within a range that allows it to fully perform its function as a support. In such a case, the thickness of the support 101 is preferably 1.5 mm from the viewpoint of manufacturing and handling of the support, mechanical strength, etc.
It is considered to be OIL or higher.

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

FIG. 17 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. As an example, 1102 is 5iH4 gas diluted with He (purity 99. 999%, hereinafter S i
Abbreviated as H4/He. ) cylinder, 1103 is G e H gas diluted with He (purity 99.999%, hereinafter abbreviated as G e H4/He) cylinder, 1104 is N
H, gas (99.99% purity) cylinder, 1105 is H
e gas (99.999% purity) Pon 11.1106 is H
2 gas (purity 99.999%) cylinder.

In order to flow these gases into the reaction chamber 1tot, valves 1122 to 1126 of gas pumps 1102 to 1106,
Make sure the leak valve 1135 is closed,
In addition, inflow valves 1112 to 1116 and outflow valve 111
After confirming that 7 to 1121 and auxiliary buff 1 valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.

Next, when the vacuum gauge 1136 reads approximately 5X10 Torr, the auxiliary valves 1132, 1133. Outflow valve 1
171-1121 are closed.

Next, to give an example of forming a light-receiving layer on a cylindrical substrate 1137 as a support, gas pumps 1102 to c7) S i H4/He
Gas, G e H4/He gas from the gas pump 1103, and NH3 gas from the gas pump 1104 are supplied to the valve 1.
122, 1123, 1124 and outlet pressure gauge 11
27,1128°1129 (7) Pressure 1kg/crr
I', inlet valves 1112, 1113, 111
By gradually opening 4, the water flows into the mass flow controllers 1107, 1108, and 1110, respectively. Subsequently, the outflow valves 1117, 1118, and 1119, and the auxiliary valve 1132 are gradually opened to supply each gas to the reaction chamber 1.
101.

S f Ha/He gas flow rate and G e H at this time
4/Outflow valves 1117, 1118° 1119 so that the ratio of He gas flow rate to N H gas flow rate becomes the desired value.
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. After confirming that the temperature of the base 1137 is set in the heater 1138 to a temperature in the range of l:5o~4oooC, the power supply 1138
40 to a desired power to generate a glow discharge in the reaction chamber 1101, and at the same time apply methods such as G e H4/He gas and manual or external drive motor according to a pre-designed rate of change curve to the valve 1118. The flow rate of NH3 gas is adjusted by appropriately changing the openings of 1120 to 1120, thereby controlling the distribution concentration C(N) of germanium atoms and nitrogen atoms contained in the formed layer.

In the manner described above, the first layer region (G) 105 is formed on the base 1137 to a desired layer thickness by maintaining glow discharge for a desired period of time. At the stage where the first layer region (G) 105 has been formed to the desired layer thickness, the outflow valve 111& is completely closed, and the desired layer is formed according to the same conditions and procedures, except for changing the discharge conditions as necessary. By maintaining the glow discharge for a period of time, a second layer region (S) 106 substantially free of germanium atoms can be formed on the first layer region (G) 105.

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

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

First layer (I) 1 formed to a desired layer thickness as described above
To form the second layer (and) 103 on the 02, for example, S I H4 gas and NO gas are added as necessary by the same valve operation as in the formation of the first layer 102 (I). The diluent may be diluted with a diluent gas such as He and supplied into the reaction chamber 1101 to cause glow discharge according to desired conditions.

In order to contain a halogen atom in the second layer (][) 103, for example, by adding S i F gas and NO gas, or adding S i H gas thereto and forming the second layer ( ) 103 may be formed.

Needless to say, all the 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 inside the reaction chamber. In order to avoid gas remaining in the gas piping leading from the outflow valves 1117 to 1121 into the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valves 1132 and 1133 are opened, and the main valve 1134 is closed.
If necessary, fully open the system and evacuate the system to high vacuum.

The amount of oxygen atoms contained in the second layer (1) 103 can be determined, for example, by changing the flow rate ratio of S i H4 gas and NOO20 introduced into the reaction chamber 1101 as desired in the case of glow discharge, or by sputtering. In the case of forming a layer with
Alternatively, it can be controlled as desired by changing the mixing ratio of silicon powder and S i 02 powder and molding the target. The amount of halogen atoms contained in the second layer 103 can be determined by adjusting the flow rate when a raw material gas for introducing halogen atoms, such as SiF or gas, is introduced into the reaction chamber 1101. will be accomplished.

Further, while one layer is being formed, it is desirable that the base 1137 be rotated at a constant speed by a motor 139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylindrical A! as a support was produced using the manufacturing apparatus shown in Figure 817. Samples (sample Mail-1-17-traditional) were prepared as electrophotographic image forming members on the L substrate under the conditions shown in Table 1.
table).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 8 shows the concentration distribution of nitrogen atoms, and FIG. 19 shows the nitrogen atom content distribution concentration.

Each sample thus obtained was placed in a charging exposure experimental device (15), corona charged for 0.3 seconds (sec) using OKV, and immediately exposed to a light image.

The light image uses a tungsten lamp light source, 2J1uxs
A light amount of sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the sample (imaging member) surface by cascading the sample (imaging member) surface with an e-chargeable developer (including toner and carrier). 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 subjected to the same toner image forming conditions except that an 810 nm GaAs semiconductor laser (10 mW) was used instead of a tungsten lamp as a light source to form an electrostatic image. When the image quality of the toner transfer images was evaluated, it was found that in all samples, clear, high-quality images with excellent resolution and good gradation reproducibility were obtained.

Example 2 Samples (sample Nos. 21-1 to 27-6) as electrophotographic image forming members were prepared on a cylindrical An substrate under the conditions shown in Table 3 using the manufacturing apparatus shown in FIG. 17. (Table 4).

The content distribution concentration of germanium atoms in each sample is the first
FIG. 8 shows the distribution concentration of nitrogen atoms, and FIG. 19 shows the nitrogen atom content distribution concentration.

When each of these samples was subjected to image evaluation tests similar to those in Example 1, all samples provided high quality toner transfer images. In addition, each sample was heated at 38°C and 8°C.
When a repeated use test was conducted 200,000 times in an environment of 0% RH, no deterioration in image quality was observed in any of the samples.

Example 3 Sample tooth 11-1.12-1.13- of Example 1 except that the conditions for creating layer (x) 103 were as shown in Table 5.
Each of the electrophotographic imaging members (sample teeth, 11-1-1-11-18.12-
1-1 to 12-1-8 and 24 samples (13-1-1 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 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 each sample and the evaluation of durability through repeated and continuous use.

Example 4 When forming layer (fl) 103, silicon wafer and Si
n, by changing the target area ratio to the wafer.

Sample No. 11- of Example 1 except that the content ratio of silicon atoms and oxygen atoms in the layer (and) 103 was changed.
Each of the imaging members was made in exactly the same manner as in Example 1. After repeating the image forming, developing, and cleaning steps approximately 50,000 times as described in Example 1 for each of the image forming members thus obtained, image evaluation was performed, and the results shown in Table 7 were obtained. Obtained.

Example 5 The sample of Example 1 except that when forming layer (1) 103, the flow rate ratio of SiH4 gas and No gas was changed to change the content ratio of silicon atoms and oxygen atoms in layer (I) 103. Each of the imaging members was made in exactly the same manner as flo, 12-1.

After repeating the steps up to transfer approximately 50,000 times using the method described in Example 1 for each image forming member thus obtained,
When the image was evaluated, the results shown in Table 8 were obtained.

Example 8 When forming the layer (IIL) 103, SiH4 gas, S
i By changing the flow rate ratio of F4 gas and No gas, layer (and) 1
Each of the image forming members was created in exactly the same manner as Samples +1&) and 13-1 of Example 1, except that the content ratio of silicon atoms and oxygen atoms in Sample No. 03 was changed. After repeating the image forming, developing and cleaning steps as described in Example 1 approximately 50,000 times for each of the image forming members thus obtained, image evaluation was performed and the results shown in Table 9 were obtained.

Example 7 Each of the image forming members was created in exactly the same manner as in Example 1, except that the layer thickness of layer (X) 103 was changed. The image forming, developing and cleaning steps as described in Example 1 were repeated to obtain the results shown in Table 10.

The layer forming conditions in the embodiments of the present invention shown in Table 1O are shown below.

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

[Brief explanation of the drawing]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the light guide member of the present invention, and FIGS. 2 to 10 each show the distribution state of germanium atoms in the first layer (I). An explanatory diagram for explaining, FIG. 11 is a configuration diagram of a layer region containing nitrogen atoms, and FIGS. 12 to 16 respectively explain the distribution state of nitrogen atoms in the first layer (I). Explanatory diagram for doing so, No. 17
Figure 18 is a schematic explanatory diagram of the device used in the present invention.
19A and 19B are distribution state diagrams showing the content distribution concentration state of each atom in the example of the present invention. DESCRIPTION OF SYMBOLS 100... Photoconductive member, 101... Support, 102... First layer (I), 103... Second layer (■), 104... Photoreceptive layer. Figure 1 C C C Figure 11 C (N)

Claims (1)

[Scope of Claims] (1) A support for a photoconductive member, a first layer region (G) made of an amorphous material containing germanium atoms, and provided on the support, and a silicon atom. a first layer comprising an amorphous material comprising a photoconductive second layer region (S) provided on the first layer region (G), and the second layer; A photoreceptive layer is provided thereon and is composed of a second layer made of an amorphous material containing silicon atoms and oxygen atoms, and the first layer contains nitrogen atoms and The distribution concentration of nitrogen atoms in the thickness direction is
A photoconductive member characterized by a back side having a first region, a third region, and a second region designated as C(1), C(3), and C(2) in this order from the support side (however,
The distribution concentration C(3) alone does not reach the maximum, and if any one of the distribution concentrations C(1), C(2), and (3) becomes O, the other two become 0. (not and not equal). (2) The photoconductive member according to claim 1, wherein at least one of the first layer region CG) and the second layer region (S) contains hydrogen atoms. (3) The photoconductor according to claims 1 and 2, wherein at least one of the first layer region (G) and the second layer region (S) contains a halogen atom. Element. (4) The photoconductive member according to claim 1, wherein the distribution state of germanium atoms in the first layer region (G) is non-uniform. (5) The photoconductive member according to claim 1, wherein the germanium atoms are uniformly distributed in the first layer region (G). (6) The photoconductive member according to claim 1, wherein the first layer region (G) 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.