JPH0476474B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field to which the invention pertains] The present invention uses light (light in a broad sense here, including ultraviolet rays,
(visible light, infrared rays, X-rays, gamma rays, etc.)
The present invention relates to a photoreceptor member sensitive to magnetic waves. moreover
For details, use coherent light such as laser light.
The present invention relates to a light-receiving member suitable for. [Description of prior art] How to record digital image information as an image and
The laser is modulated according to the digital image information.
– By optically scanning the light-receiving member with light
forming an electrostatic latent image and then developing the latent image;
Furthermore, perform processing such as transfer and fixing as necessary.
There are known methods for recording images, among them
In the electrophotographic image forming method, laser
Therefore, small and inexpensive He-Ne laser or semiconductor
Body laser (usually has an emission wavelength of 650 to 820 nm)
It is common to record images using
Ru. By the way, it is not suitable for using semiconductor lasers.
As a light-receiving member for electrophotography, its photosensitivity
Area integrity is superior compared to other types of photoreceptive materials.
In addition to its high Bitkers hardness,
It is evaluated based on the fact that there are few problems of harm, for example,
In 1982-86341 and Japanese Patent Application 56-83746
Amorphous materials containing silicon atoms, such as those seen in
(hereinafter abbreviated as "a-Si")
The material is attracting attention. However, the light receiving member
If the receptor layer is a single-layer a-Si layer, its high light
Required for electrophotography while maintaining sensitivity
Ten¹²To ensure dark resistance of Ωcm or more, hydrogen atoms
or halogen atoms, or in addition to these, boron atoms
structure in a controlled manner in layers with a specific amount range of
Therefore, it is necessary to contain the
Therefore, it is necessary to strictly control various conditions.
Tolerances for the design of light-receiving members as required
There are considerable limitations. And such design
Even if the dark resistance is low to some extent, the problem of tolerance can be solved.
Improvements have been made by making it possible to effectively utilize the high light sensitivity of
Suggestions for improvement have been made. That is, for example,
Publication No. 54-121743, Japanese Unexamined Patent Publication No. 57-4053, Special
As seen in 1982-4172, the photoreceptive layer
Layered structure with two or more layers with different conductive properties
As a result, a depletion layer is formed inside the photoreceptor layer, or
JP-A No. 57-52178, No. 52179, No. 52180,
Only in the publications No. 58159, No. 58160, and No. 58161.
between the support and the photoreceptive layer, or/and
A multilayer structure with a barrier layer on the upper surface of the photoreceptive layer.
The photoreceptor area has increased apparent dark resistance by
material has been proposed. However, such a photoreceptive layer has a multilayer structure.
Light-receiving members have variations in the thickness of each layer.
When performing laser recording using
is coherent monochromatic light, so the laser in the photoreceptive layer
Free surface on the laser light irradiation side, each layer constituting the light-receiving layer
and the layer interface between the support and the photoreceptive layer (hereinafter, this self-
"Interface" in the sense of combining both surface and layer interface
It is called. ) each of the half-rays reflected from the
This often leads to conflicts. This interference development results in
So-called interference fringes appear and cause image defects.
It causes. Especially for mid-tone images with high gradation.
In the case of forming a
This will give you a clear image. Another important point is the semiconductor laser used.
As the wavelength range of light becomes longer, the photoreceptive layer
The absorption of the laser light will decrease, so the
There is a problem in that the interference phenomenon described above becomes noticeable. i.e., e.g. two or more layers (multilayer)
In the case of composition, each of those layers
Interference effects occur, and each interference is synergistic.
This is where the interference fringes appear.
This directly affects the transfer member, causing
The interference fringes corresponding to the interference fringe pattern are transferred and fixed on the
and appear in the visible image, resulting in a defective image.
There is a problem that I encountered. As a measure to solve these problems, (a) support surface
Diamond cutting the surface to ±500Å to ±10000Å
A method of forming a light scattering surface by providing unevenness (for example,
(Refer to Japanese Patent Application Laid-Open No. 162975/1983), (b) Aluminum
The surface of the support is treated with black alumite, or
disperses carbon, color pigments, and dyes in resin.
A method of providing a light absorption layer by
-Refer to Publication No. 165845), (c) Aluminum support surface
The surface is treated with satin-like alumite, or sandblasted.
Support is created by creating fine grain-like unevenness by
A method of providing a light scattering and anti-reflection layer on the surface of the support (for example,
(see Japanese Unexamined Patent Publication No. 57-16554) have been proposed.
I'm here. Although these proposed methods may produce some results,
Nono completely eliminates interference fringe patterns that appear on images.
It's not good enough. In other words, in method (a), a specific
It has a large number of uneven surfaces, which creates a light scattering effect.
The appearance of interference fringes due to
However, the light scattering is still specular reflection.
Because the light component remains, interference fringes due to the specularly reflected light
In addition to the pattern remaining, the surface of the support
The light scattering effect causes the irradiation spot to spread.
However, this results in a substantial decrease in resolution. For method (b), black alumite treatment is used.
complete absorption is not possible and reaction on the surface of the support
The emitted light remains. In addition, colored pigment dispersion resin
If a layer is provided, when forming the a-Si layer, the resin
The photoreceptive layer is formed when a degassing phenomenon occurs from the layer.
The quality will deteriorate significantly, and the resin layer is a-Si layer type.
The book was damaged by the plasma generated during its creation.
In addition to reducing the absorption function of the
This adversely affects the subsequent formation of the a-Si layer due to
There are problems such as: Regarding method (c), for example, consider the incident light.
If so, a part of it is reflected on the surface of the photoreceptive layer and
The remaining light enters the light-receiving layer and becomes transparent.
There will be too much light. At the surface of the support, the transmitted light
Some of it is scattered and becomes diffused light, and the rest is
It is specularly reflected and becomes reflected light, and a part of it becomes emitted light.
The emitted light is mixed with the reflected light.
It is an interfering component and will remain in any case.
However, the interference fringe pattern does not completely disappear. By the way, regarding preventing interference in this case,
to prevent multiple reflections from occurring inside the photoreceptive layer.
There are also attempts to increase the diffusivity of the surface of the support.
However, in such a case, the light is instead absorbed within the photoreceptive layer.
diffuses and causes halation, which is eventually solved.
Image resolution will decrease. In particular, in light-receiving members with a multilayer structure, support
Even if the body surface is irregularly roughened, the reaction on the first layer surface will not occur.
Emitted light, reflected light on the second layer, specularly reflected light on the support surface
Each of these interferes with each other to reduce the thickness of each layer of the light-receiving member.
A pattern of interference fringes occurs. Therefore, multi-layered light
In the receiving member, the surface of the support is irregularly roughened.
Therefore, it is impossible to completely prevent interference fringes.
It is. In addition, the surface of the support may be coated by methods such as sandblasting.
When roughening a surface irregularly, the roughness will vary between lots.
There is a lot of variation in
However, the surface roughness is uneven, causing problems in manufacturing control.
be. In addition, relatively large protrusions are randomly shaped.
These large protrusions are photoreceptors.
This results in local breakdown of the layer. In addition, the surface of the support is simply roughened regularly.
Usually, light is applied along the uneven shape of the surface of the support.
Because the receptive layer is deposited on the uneven slope of the support,
The slope of the unevenness of the light-receiving layer becomes parallel to that part.
In minutes, the incident light causes bright areas and dark areas.
Also, the thickness of the photoreceptive layer as a whole is
Due to the non-uniformity, light and dark stripes appear. subordinate
Therefore, simply roughening the surface of the support regularly will not
It is not possible to completely prevent the occurrence of striped patterns. In addition, a multilayer structure is formed on a support whose surface is regularly roughened.
Even when a photoreceptive layer is deposited on the support surface,
The difference between the specularly reflected light on the surface and the reflected light on the photoreceptive layer surface.
In addition to interference, interference due to reflected light at the interface between each layer
Because of the addition of
It becomes more complicated than the degree of expression. [Purpose of the invention] The present invention provides a photoreceptor mainly composed of a-Si.
Regarding light-receiving members having layers, the above-mentioned problems can be solved.
The purpose is to eliminate them and make them meet various requirements.
That is. That is, the main purpose of the present invention is to
The chemical and photoconductive properties mostly depend on the usage environment.
Stable virtually all the time without any light fatigue
Excellent, no deterioration even after repeated use
Excellent durability and moisture resistance, with no or almost no residual potential
a-Si, which is not observed and manufacturing control is easy
Provides a light-receiving member having a light-receiving layer composed of
It's about doing. Another object of the present invention is to provide photosensitivity in the entire visible light range.
High degree of accuracy, especially matching with semiconductor lasers
Composed of a-Si, which has excellent properties and fast photoresponse.
To provide a light-receiving member having a light-receiving layer
be. Still another object of the present invention is to provide high photosensitivity and high SN.
Made of a-Si with specific characteristics and high electrical voltage resistance.
Provided is a light-receiving member having a light-receiving layer made of
There is a particular thing. Another object of the invention is the layer provided on the support.
and the support and between each laminated layer.
Excellent adhesion, dense and stable structural arrangement.
A photoreceptive layer composed of a-Si with high layer quality
An object of the present invention is to provide a light-receiving member having the following features. Still another object of the present invention is to use coherent monochromatic light.
Suitable for image formation, suitable for long-term repeated use.
However, interference fringes and spots do not appear during reverse development.
There are no image defects or image blur, and the density is very low.
is high, halftones appear clearly, and resolution is high.
With a-Si, you can obtain high-quality images.
Provided is a light-receiving member having a light-receiving layer configured.
There are many things. [Structure of the invention] The present inventors have previously described the conventional light-receiving member.
The above problems should be overcome to achieve the above objectives.
As a result of extensive research, we have obtained the knowledge described below.
Based on this knowledge, we have completed the present invention. That is, the present invention provides silicon atoms on a support.
and selected from oxygen atoms, carbon atoms and nitrogen atoms.
an amorphous material containing at least one type of
A light-receiving member comprising a light-receiving layer composed of
The photoreceptive layer contains germanium atoms or tin atoms.
a layer containing at least one of the children;
Contains neither rumanium atoms nor tin atoms.
It has a multi-layered structure with two layers in order from the support side.
and the surface of the support has a plurality of spherical traces.
It has an uneven shape due to depressions, and the spherical trace depressions
It may have multiple microscopic irregularities within the groove.
The present invention relates to a light-receiving member having the following features. By the way, as a result of intensive research by the inventors,
The findings obtained are summarized, with multiple layers on the support
In the light-receiving member, a plurality of
Providing unevenness with spherical trace depressions, and the spherical trace
Providing a plurality of even smaller uneven shapes within the trace depression
Due to this, the problem of interference fringes that appear during image formation
The problem will be significantly resolved. This knowledge was confirmed by various experiments conducted by the inventors.
It is based on the facts obtained from. Here is a diagram to make it easier to understand.
This will be explained below using FIG. 1 shows the layers of a light receiving member 100 according to the present invention.
This is a schematic diagram showing the structure, showing multiple minute spherical traces.
It has an uneven shape due to depressions, and the spherical trace depressions
A support that has multiple microscopic irregularities within the groove.
101, along the uneven slope surface.
Contains at least one of a nium atom or a tin atom
layer 102' containing germanium atoms and tin
a layer 102'' that does not contain any atoms.
A light-receiving member including a light-receiving layer 102 is shown.
Ru. Figures 2 and 4 show the light receiving member of the present invention.
Explain how the problem of interference fringes is resolved
This is a diagram for Figure 3 shows a support with a regularly roughened surface.
Conventional photoreceptor with multilayered photoreceptor layers deposited
It is an enlarged view of a part of the material. The smell of the figure
301 is the first layer, 302 is the second layer, 30
3 is the free surface, 304 is the boundary between the first layer and the second layer.
Each side is shown. As shown in Figure 3,
The surface of the support is simply made regular by cutting or other means.
If the surface is only roughened, it is usually due to irregularities on the surface of the support.
Since the photoreceptive layer is formed along the shape of the support,
The uneven surface of the surface and the uneven surface of the photoreceptive layer.
are in a parallel relationship. This causes, for example, the photoreceptor layer to
Consisting of two layers, a layer 301 and a second layer 302.
In a light receiving member having a multilayer structure,
For example, the following problems are regularly encountered. Immediately
The interface 304 between the first layer and the second layer and the free
Since the surface 303 is in a parallel relationship, the interface 304
Reflected light R at₁and the reflected light R on the free surface₂is the direction
coincide, and interference fringes are generated depending on the thickness of the second layer.
Ru. Figure 2 shows the uneven shape due to multiple spherical trace depressions.
A multilayer photoreceptive layer is deposited on a support with
FIG.
Ru. In the figure, 201 is the first layer, 202 is the first layer, and 202 is the first layer.
second layer, 203 is the free surface, 204 is the first layer
and the interface with the second layer, respectively. Second
As shown in the figure, there are multiple microscopic spheres on the surface of the support.
When providing an uneven shape with trace depressions, the support
The light-receiving layer provided on top is formed along the uneven shape.
For depositing a first layer 201 and a second layer 202
The interface 204 with and the free surface 203 are each
Spherical trace depressions are formed along the uneven shape of the support surface.
It is formed into an uneven shape by scratching. shape on the interface 204
The curvature of the formed spherical trace depression is R₁, on the free surface
The curvature of the formed spherical trace depression is R₂Then,
R₁and R₂What is R?₁≠R₂Therefore, at the interface 204
The reflected light and the reflected light at the free surface 203 are each
with different reflection angles, i.e. in FIG.
θ₁,θ₂is θ₁≠θ₂However, the direction is different, and the
l shown in Figure 2₁,l₂,l₃using l₁+l₂−l₃expressed in
None of the wavelengths that are transmitted remain constant, but change.
, so it is compatible with the so-called Newton ring phenomenon.
Shearing interference occurs, and the interference fringes become hollow.
It will be dispersed within. This allows
The image that appears through the light-receiving member
From a secondary perspective, even if interference fringes were to appear,
They are invisible to the naked eye.
Ru. That is, the use of a support having such a surface shape.
is formed by forming a multilayered photoreceptive layer thereon.
In a light-receiving member, light passing through the light-receiving layer
is reflected at the layer interface and the support surface, causing them to dry.
The resulting image may appear striped.
To efficiently prevent
This leads to obtaining a light-receiving member. FIG. 4 shows the light receiving member of the present invention shown in FIG.
FIG. 3 is an enlarged view of a part of the support surface in FIG. No.
As shown in Figure 4, in the light receiving member of the present invention
The support surface is one of the surfaces within the spherical trace depression 401.
Further minute irregularities or a group of irregularities 40 on the part or the whole
2 is formed. Even more minute irregularities like this
When the unevenness group 402 is provided, it is written using FIG.
In addition to the interference prevention effect mentioned above,
The convexity 402 provides a scattering effect, which
The occurrence of interference fringes is more reliably prevented.
Ru. By the way, in the conventional technology, as mentioned above,
Diffuse reflection can be achieved by randomly roughening the surface of the support.
This prevents the occurrence of interference fringes. deer
In such cases, sufficient interference fringes can be prevented from occurring.
Not only will it not be possible to obtain the desired effect, but also the
For example, when cleaning
Problems also arise when cleaning the product. Immediately
In other words, the surface of the light-receiving layer is formed by recesses provided on the support.
Due to the unevenness along the convexity, the blade is difficult to receive light.
Mainly applies to the convex and convex parts of the layer, cleaning
In addition, the convex parts of the photoreceptive layer and the blade surface
As a result, the durability of both will increase.
There are many problems. On the other hand, in the light receiving member of the present invention,
The minute unevenness that causes scattering effects creates spherical traces.
Because it exists in the depression (concave part), it is difficult to clean it when cleaning.
, the blade contacts the recess in the photoreceptive layer.
This eliminates the problem that the blade and photoreceptive layer surface
It also has the advantage of not placing a large load on the
Ru. Now, it is provided on the surface of the support of the light receiving member of the present invention.
The curvature, width, and
and the height of even minute irregularities within the spherical trace depression.
is the interference fringe in the light receiving member of the present invention.
To efficiently obtain the effect of preventing the occurrence of
It is important. The inventors have conducted various experiments
As a result, we investigated the following points. In other words, the curvature of the uneven shape due to the spherical trace depression is
When R and width are D, the following formula: D/R≧0.035 If it satisfies the
0.5 or more Newton rings due to ring interference
It will exist. Furthermore, the following formula: D/R≧0.55 If it satisfies the
There is one or more Newton rings due to ring interference.
There will be. For these reasons, it is possible that
The interference fringes are dispersed within each trace depression, and the light
To prevent interference fringes from occurring on the receiving member
The above D/R is 0.035, preferably 0.055 or more. It is desirable that Further, the upper limit of D/R is preferably 0.5. This is because when D/R is larger than 0.5, the depression Width D becomes relatively large, leading to image unevenness, etc.
This is because the situation becomes easier. In addition, the width D of the unevenness due to the trace depression is large.
It is also about 500 μm, preferably 20 μm or less, more preferably
More preferably, the thickness is 100 μm or less. D is
If it exceeds 500μm, image unevenness is likely to occur.
At the same time, there is a risk that the resolution will be exceeded.
In such cases, effective interference fringe prevention effects can be used.
becomes difficult to obtain. The height of the minute irregularities formed within the spherical trace depression,
That is, the surface roughness γmax within the spherical trace depression is 0.5 to
Preferably, it is in the range of 20 μm. γmam
If the diameter is 0.5 μm or less, sufficient scattering effect cannot be obtained.
Moreover, if the thickness exceeds 20μm, it will become a spherical trace depression.
Compared to the unevenness caused by
becomes too large and the dents no longer have a spherical shape.
It has the effect of preventing interference fringes from occurring.
You won't get enough. Also, on such supports
Increasing the non-uniformity of the photoreceptive layer provided on the
This is preferable because it tends to cause image defects.
It's not right. The present invention is based on the above-identified facts.
The light receiving member provided by the present invention is as follows.
The main structure is as follows. That is, germanium atoms or tin atoms are placed on the support.
Layer containing at least one of the atoms (a)
and contains both germanium atoms and tin atoms.
The layer (B) without the silicone
in oxygen atoms, carbon atoms, and nitrogen atoms.
an amorphous material containing at least one selected from
Light with a multi-layered light-receiving layer made of materials
A receiving member, wherein the surface of the support is in the recess.
When the width D is 500 μm or less, the radius of curvature R and the width d of the depression are
is 0.035≦D/R in multiple spherical trace depressions.
It has an unevenness according to
It is confirmed that minute irregularities of 0.5 to 20 μm are formed.
This is a characteristic light-receiving member. Support in the light receiving section of the present invention having the above structure
The unevenness caused by the plurality of spherical trace depressions on the surface of
Even if they have the same radius of curvature, or almost the same radius of curvature,
Formed by a depression with the same radius of curvature and width
It may be. Light reception in the light receiving member of the present invention having the above configuration
The layer consists of atoms belonging to a group or groups of the periodic table.
May contain. In this case, the light-receiving layer contains
atoms belonging to group or groups of the periodic table
Therefore, the distribution concentration of those atoms is compared on the support side.
The concentration is relatively high on the surface side of the photoreceptive layer.
or virtually at a concentration close to zero.
It is possible to make the distribution non-uniform in the layer thickness direction.
Wear. In the light receiving member of the present invention having the above structure, the front
Germanium atoms or tin atoms contained in the layer (a)
Regarding the atoms, the distribution concentration of those atoms is on the support side.
It is said that the concentration is relatively high, and the layer (b) (i.e., gem mani
layer containing neither umium atoms nor tin atoms)
In the layer thickness direction, the concentration is much lower on the side than on the support side.
It can be distributed non-uniformly. contained in the light-receiving layer of the light-receiving member of the present invention having the above structure.
The oxygen atoms present are among the carbon and nitrogen atoms.
For at least one kind of atom selected from
The distribution concentration of these atoms is relatively high on the support side.
and on the surface side of the photoreceptive layer, compared to the support side.
Very low or virtually zero concentration
so that it is distributed non-uniformly in the layer thickness direction so that
can do. Light reception in the light receiving member of the present invention having the above configuration
The layer contains atoms belonging to a group or groups of the periodic table.
It has a charge injection prevention layer containing it as one of the constituent layers.
can do. Light reception in the light receiving member of the present invention having the above configuration
The layer may have a barrier layer as one of the constituent layers.
can. Regarding the preparation of the light-receiving layer of the light-receiving member of the present invention
In order to efficiently achieve the above-mentioned objects of the present invention,
Therefore, it is necessary to precisely control the layer thickness at the optical level.
Glow discharge method, sputtering
vacuum deposition methods such as ion plating method and ion plating method.
Usually used, but in addition to these, optical CVD method, thermal
CVD method etc. can also be adopted. Hereinafter, the optical receiver of the present invention will be described according to the illustrated embodiment.
Although the specific contents of the container member will be explained, the light receiving member of the present invention
The container members are not limited by these examples.
do not have. FIG. 1 explains the layer structure of the light-receiving member of the present invention.
This is a diagram schematically shown for the purpose of
0 is a light receiving member, 101 is a support, 102 is a light receiving member.
layer, 102' is germanium atom or tin atom
A layer containing at least one of 10
2″ is both a germanium atom and a tin atom
103 indicates the free surface of the layer that does not contain
ing. support The support 101 in the light receiving member of the present invention is
The surface has a resolution higher than that required for the light-receiving member.
It has minute irregularities, and the irregularities are composed of multiple spherical shapes.
It is due to a trace depression, and the spherical trace depression
Multiple microscopic irregularities are formed within the groove.
It is something. Below, the support in the light-receiving member of the present invention will be described.
The shape of the surface and its preferred manufacturing example are shown in the fourth and fifth sections.
As will be explained with reference to the drawings, in the light receiving member of the present invention,
The surface shape of the support and its manufacturing method are
Therefore, it is not limited. FIG. 4 shows a support in the light-receiving member of the present invention.
A typical example of the surface shape of
This is a partially enlarged schematic diagram of the section. In Fig. 4, 401 is a support, and 402 is a support.
Body surface, 403 is an uneven shape due to spherical trace depressions,
404 is an even smaller hole provided within the spherical trace recess.
It has an uneven shape. Furthermore, FIG. 4 shows how to obtain the surface shape of the support.
It also shows one example of a preferred manufacturing method, and 4
03' has minute irregularities 404' on the surface
A rigid sphere is shown, and the rigid sphere 403' is used as a support.
Let it fall naturally from a predetermined height from the surface 402.
by colliding with the support surface 402.
A spherical trace with minute irregularities 404 inside.
It is shown that it is possible to form an uneven shape 403 due to depressions.
are doing. Then, a rigid sphere 40 with approximately the same diameter R'
Using multiple 3', from the same height h,
Support by dropping simultaneously or sequentially
The body surface 402 has approximately the same curvature R and approximately the same
Forming a plurality of spherical trace depressions 403 having a width D of
can do. Figure 5 shows a plurality of spheres on the surface as described above.
The support is formed with an uneven shape due to the concave and convex shape.
Some typical examples are shown below. The smell of the figure
501 is a support, 502 is a surface of the support, and 50
3 has a plurality of even finer uneven shapes in the depression.
A spherical trace depression (in Fig. 5, a spherical trace depression)
Multiple microscopic uneven shapes formed within the trace depression
Although not shown in the figure, inside the spherical trace depression 503
Assume that each has a microscopic uneven shape.
Ru. ), 503 is a rigid material with minute irregularities on its surface.
Body sphere (similarly, minute irregularities on the surface are shown in the figure)
However, there are minute irregularities on the surface of the rigid sphere.
shall have the following conditions. ) respectively.
There is. In the example shown in FIG. 5A, the surface 5 of the support 501
Multiple spheres with almost the same diameter in different parts of 02
503', 503', ... from almost the same height
Almost the same curvature and almost the same width when dropped
The multiple trace depressions 503, 503, ... are overlapped with each other.
Regularly uneven shapes formed densely so as to overlap each other.
It is formed into a shape. In this case, each other
To form overlapping depressions 503, 503,...
is when the sphere 503' collides with the support surface 502.
The spheres 503' and 50 are arranged so that their periods are shifted from each other.
Yes, it is necessary to allow 3',... to fall naturally.
It's no good. In addition, in the example shown in FIG. 5B,
The two types of spheres 503', 503', ... are almost the same.
or from a different height, the support 5
The surface 502 of 01 has two types of curvature and two types of width.
The plurality of depressions 503, 503,... are overlapped with each other.
The height of the unevenness on the surface is
It has irregular irregularities. Furthermore, Figure 5C (front view and cross section of the support surface)
In the example shown in the top view), the surface 502 of the support 501
, a plurality of spheres 503', 50 having approximately the same diameter
3',... are dropped irregularly from almost the same height,
Multiple depressions with almost the same curvature and multiple types of widths
503, 503, ... so that they overlap with each other.
This is caused by the formation of irregular irregularities.
Ru. As described above, the support of the light receiving member of the present invention
Forms an uneven shape with spherical trace depressions on the surface
Moreover, within the spherical trace depression, there are a plurality of microscopic dents.
In order to shape the uneven shape, it is necessary to
A rigid sphere with an uneven shape is dropped onto the surface of a support.
A preferred example is the method of
In the case of , the diameter of the hard sphere, the height to which it falls, and
The hardness of the support surface, the shape of the irregularities on the surface of the rigid sphere, and
and the size of the rigid sphere, or the amount of rigid spheres that are caused to fall.
By selecting appropriate conditions, it is possible to
Spherical trace depression with desired average curvature and average width
or fill the desired size in the spherical trace depression.
It is possible to form irregularities with a predetermined density.
Wear. That is, by selecting the above conditions,
The height and height of the irregularities formed on the surface of the support
It is formed in the pitch of unevenness or in the concave part of uneven shape.
The height of the unevenness and the pitch of the unevenness of the even finer unevenness
It is possible to freely adjust the height etc. according to the purpose.
to obtain a support having a desired uneven shape.
be able to. Then, the support of the light-receiving member has an uneven surface.
To make it into a finished product, use a lathe, milling machine, etc.
Created by cutting with a diamond cutting tool.
Someone who has proposed a method to do this that is reasonably effective.
However, in this method, the use of cutting oil,
Removal of chips unavoidably generated by cutting, cutting surface
It is essential to remove the cutting oil that remains in the
In the end, processing is complicated and inefficient, etc.
However, in the present invention, the support
As mentioned above, the uneven surface shape is shaped into a spherical trace depression.
The above problems can be completely eliminated by forming more
Efficiently and easily create supports with desired uneven surfaces
Can be created. The support 101 used in the present invention is electrically conductive.
Even if it is electrically insulating
It may also be electrically insulating. conductive
Examples of the support include NiCr, stainless steel,
Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pb
Metals such as these or alloys thereof can be mentioned. As the electrically insulating support, polyester, polyester, etc.
polyethylene, polycarbonate, cellulose, aluminum
acetate, polypropylene, polyvinyl chloride, polycarbonate
Polyvinylidene chloride, polystyrene, polyamide, etc.
synthetic resin film or sheet, glass, ceramic
Examples include Mitsuku, paper, etc. Electrical insulation properties of these
The support preferably has at least one surface
Conductive treatment and a photoreceptive layer on the conductive treated surface side.
It is desirable to provide For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In₂O₃, SnO₂, ITO (In₂O₃+SnO₂) etc.
By providing a thin film consisting of
Or synthetic resin film such as polyester film
NiCr, Al, Ag, Pb, Zn, Ni,
Gold such as Au, Cr, Mo, Ir, Nb, Ta, V, Tl, Pt, etc.
Vacuum evaporation, electron beam evaporation, sputtering
Provided on the surface with a ring etc., or attached with the metal mentioned above.
The surface is laminated to make it conductive.
Give. The shape of the support body is cylindrical, belt-shaped,
It can be of any shape such as a plate, but depending on the purpose,
Its shape can be determined as desired.
It is possible. For example, the light receiving member 1 in FIG.
Since 00 is used as an electrophotographic image forming member,
If available, use an endless belt for continuous high-speed copying.
Alternatively, it is desirable to have a cylindrical shape. Support thickness
may be adjusted as appropriate to form the desired light-receiving member.
However, flexibility is required as a light receiving member.
If the support is
It can be made as thin as possible within the range. death
However, in manufacturing and handling the support, mechanical
In terms of optical strength, etc., the thickness is usually 10μ or more. Next, the light receiving member of the present invention was used as a light receiving member for electrophotography.
When used as a container member, the support surface
An example of a surface manufacturing device is shown in FIGS. 6A and 6B.
However, the present invention is not limited thereby.
It's not something you can do. Aluminum is used as a support for electrophotographic light receiving members.
By applying normal extrusion processing to minium alloy etc.
Make it into a hole tube or mandrel tube and then draw it out.
Heat treatment is applied to the drawn pipe obtained through processing as necessary.
Cylindrical shape that has undergone treatment such as heat refining
A substrate is used, and the cylindrical substrate is shown in FIGS. 6A and 6B.
The uneven shape is formed on the surface of the support using manufacturing equipment.
I will make it happen. Form the above-mentioned uneven shape on the surface of the support
For example, the sphere used for this purpose is stainless steel.
metal, aluminum, steel, nickel, brass, etc.
Various rigid spheres such as metal, ceramic, plastic, etc.
Among others, durability and low cost
Rigid spheres made of stainless steel and steel due to
is desirable. The hardness of such a rigid sphere is
The hardness may be higher or lower than that of the holding body.
However, if the sphere is used repeatedly,
It is desirable that the hardness be higher than the hardness. The specific shape as described above is formed on the surface of the support of the present invention.
To form, on the surface of various rigid spheres as described above
It is necessary to use a material with unevenness, and
A rigid sphere with an uneven surface is, for example, embossed.
Methods of applying plastic processing such as
Mechanical treatments such as surface roughening methods (Nashiji method)
Methods of forming unevenness by
A method of forming irregularities using chemical methods such as etching.
It is created by processing a rigid sphere using
can be done. Furthermore, by forming unevenness like this
Finishing such as electrolytic polishing, chemical polishing, etc. is applied to the surface of the rigid sphere.
Polishing, anodic oxidation film formation, chemical conversion film formation,
For attaching, enameling, painting, vapor deposition film formation, and CVD method
Surface treatment such as film formation is performed to create an uneven shape (high
), hardness, etc. can be adjusted as appropriate. Figures 6A and 6B are for explaining an example of manufacturing equipment.
FIG. In the figure, 601 is an aluminum sheet for making a support.
cylinder, and the cylinder 601 is
The surface may be finished to an appropriate degree of smoothness. S
The cylinder 601 is supported by a rotating shaft 602.
and is driven by an appropriate driving means 603 such as a motor.
and is rotatable approximately around its axis.
604 is pivotally supported by a bearing 602, and a cylinder 6
It is a rotating container that rotates in the same direction as 01, and
The inside of the container 604 has an uneven surface.
A large number of rigid spheres 605 are accommodated. rigid sphere 6
05 is provided on the inner wall of the rotating container 604.
Ru. carried by a plurality of protruding ribs 606
and by the rotation of the rotating container 604,
transported to the department. If the rotation speed of the rotating container is
When the speed of
The sent rigid sphere 605 is placed on the cylinder 601.
It fell toward the cylinder, collided with the cylinder surface, and left a mark on the surface.
Forms a trace depression. Note that holes are uniformly punched in the wall of the rotating container 604.
A shower provided on the outside of the container 604 when the container 604 is rotated.
-The cleaning liquid is sprayed from the pipe 607, and the
Under 601, rigid sphere 605, and rotating container 604
It can also be made so that it can be washed. in this way
In this case, the rigid spheres or the rigid sphere and the rotating container
attached due to static electricity caused by contact with
It is not necessary to wash out the garbage etc. to the outside of the rotating container 604.
to form the desired support without adhesion of rubber, etc.
be able to. The cleaning solution includes drying of the cleaning solution.
It is necessary to use a material with no unevenness or dripping.
Therefore, non-volatile substances alone or trichlor
Mixing with cleaning liquids such as ethane and trichlorethylene
It is preferable to use a compound. photoreceptive layer In the light receiving member of the present invention, the above-mentioned support
101, composed of a-Si (O.C.N) (H.X)
The photoreceptive layer 102 has a photoreceptive layer 102.
2 is a germanium atom from the support 101 side.
(Ge) or at least one of tin atoms (Sn)
A layer containing one [i.e., a-Si(Ge, Sn) (O.
layer composed of C.N) (H.X)] 102' and gel
Contains neither manium nor tin atoms
layer [i.e. composed of a-Si (O.C.N) (H.X)
It has a multilayer structure in which layers] 102″ are laminated in order.
Ru. The photoreceptive layer 102 further includes
Containing a substance that controls conductivity accordingly
I can do it. Halogen atom (X) contained in the photoreceptive layer
Specifically, fluorine, chlorine, bromine, and iodine
In particular, fluorine and chlorine are preferred.
can be mentioned. and photoreceptive layer 102
The amount of hydrogen atoms (H) contained in the
amount of hydrogen atoms (X), or hydrogen atoms and halogen
The sum of the amounts of atoms (H+X) is usually 1 to 40 atomic
%, preferably 5 to 30 atomic%
Yes. Further, in the light-receiving member of the present invention, the light-receiving layer
In order to efficiently achieve the purpose of the present invention, the layer thickness of
One of the important factors is the desired
When designing the light-receiving member, so that the characteristics
It is necessary to pay sufficient attention to the
100μ, preferably 1 to 80μ, more preferably
The thickness should be 2 to 50μ. By the way, the light-receiving layer of the light-receiving member of the present invention has a gel.
Contains rumanium atoms and/or tin atoms
The purpose of this is mainly to
The aim is to improve the absorption spectral characteristics of
Ru. That is, germanium atoms or
By containing / and tin atoms, the present
The light-receiving member of the invention exhibits various excellent properties.
However, especially in the visible light range,
of the entire range from relatively short wavelengths to relatively long wavelengths.
It has excellent photosensitivity and fast photoresponsiveness to light of different wavelengths.
becomes. And this means that the semiconductor laser
This is especially true when it comes to lines. In the light-receiving layer of the light-receiving member of the present invention
is a germanium atom or/and a tin atom.
Uniform distribution in the layer 102' in contact with the support 101
or non-uniformly distributed state.
It is made to contain. (here uniform distribution
The state is a germanium atom or/and a tin atom.
The distribution concentration of is parallel to the support surface of layer 102'.
Uniform in the plane direction, and the layer thickness direction of the layer 102'
It refers to uniform distribution in both directions, and also refers to non-uniform distribution.
The state is a germanium atom or/and a tin atom.
The distribution concentration of is parallel to the support surface of layer 102'.
Uniform in the plane direction, but in the thickness direction of the layer 102'
It is said that there is non-uniformity. ) And in the layer 102' of the present invention, in particular:
Germanium atoms and/or tin atoms are present in layer 10
A state in which there is more distribution on the support side than on the 2″ side.
It is desirable to contain it so that
If the end of the support is exposed to germanium,
Extremely large distribution concentration of tin atoms and/or tin atoms
By doing so, long wavelength light sources such as semiconductor lasers can be used.
When using layer 102'', almost no absorption
The long-wavelength light that cannot be contained in the layer 102' is
Support surface that can be virtually completely absorbed
Interference caused by reflected light from
Ru. Further, in the light receiving member of the present invention, the layer 10
2' and layer 102'', respectively,
have a common component: silicon atoms
This ensures sufficient chemical stability at the laminated interface.
has been done. The germanium source contained in the layer 102' will be described below.
of tin atoms and/or tin atoms in the layer thickness direction of the layer 102'.
Some typical examples of distribution states are shown in germanium
This will be explained using Figures 7 to 15, taking the mu atom as an example.
Ru. In Figures 7 to 15, the horizontal axis is germanium.
The vertical axis represents the distribution concentration C of the umium atoms in the layer 102'.
Indicates the layer thickness, t_Bis the end of the layer 102' on the support side.
position, t_Tis the layer 102″ side opposite to the support side
Indicates the position of the end face. That is, germanium atoms
The contained layer 102' is t_Bt than the side_Ttowards the side
Layering is done. In addition, in each figure, the layer thickness and concentration are indicated.
If the values are shown as they are, the differences between each figure will not be clear.
The illustrations are shown in extreme form to
This is an explanatory model to make it easier to understand.
It is formal. FIG. 7 shows the gel contained in layer 102'.
First typical example of the distribution state of Ni atoms in the layer thickness direction
is shown. In the example shown in Figure 7, the germanium atom
the surface of the support on which the layer 102' contained is formed;
Interface position t where layer 102' contacts_BMoret₁position
Then, the distribution concentration C of germanium atoms is the concentration C₁
germanium atoms in layer 1 while taking a constant value
02′, position t₁Rather than concentration C₂More interface
position t_Tis gradually and continuously reduced until
Ru. Interface position t_TIn this case, the fraction of germanium atoms is
The cloth density C is substantially zero. (Here, “substantially zero” means that the amount is below the detection limit.
It is. ) In the example shown in FIG.
The distribution concentration C of rumanium atoms is at position t_BMore position_T
Concentration C up to₃gradually and continuously decreasing from
position t_Tconcentration C at_FourForm a distribution state such that
are doing. In the case of Figure 9, position t_BMore position_TUntil,
The distribution concentration C of germanium atoms is the concentration C_Fiveconstant
position and position t₂and position t_TBetween
Gradually and continuously decreased, position t_TIn, the distribution
The concentration C is substantially zero. In the case of Figure 10, the distribution of germanium atoms
Concentration C is at position t_BMore position_Tup to the concentration C₆Yo
At the beginning, the position is gradually decreased, and the position t₃steeper than
position t is continuously decreased in speed_Tsubstantially in
It is considered to be zero. In the example shown in Figure 11, germanium atoms
The distribution concentration C of is given by the position t_Band position t_FourIn between,
Concentration C₇is a constant value, and the position t_TThe distribution concentration in
C is assumed to be zero. position t_Fourand position t_Tminutes between
The cloth density C is linearly proportional to the position t._FourMore position_Tleading to
has been reduced to. In the example shown in FIG. 12, the distribution concentration C
is position t_BMore position_Fiveuntil the concentration C₈Take a constant value of
position t_Fivefrom position t_Tuntil the concentration C₉More concentration C_Ten
It is said that the distribution state decreases linearly until
Ru. In the example shown in FIG. 13, the position t_BMore position
t_TUntil , the distribution concentration C of germanium atoms is
Concentration C₁₁It is reduced more linearly and reaches zero.
It's on. In Figure 14, position t_BMore position₆leading to
Until the distribution concentration C of germanium atoms is the concentration
C₁₂More concentration C₁₃is linearly decreased until the position
t₆and position t_TBetween, the concentration C₁₃with a constant value of
An example is shown. In the example shown in Figure 15, germanium
The distribution concentration C of atoms is the position t_Bconcentration C at₁₄in
Yes, position t₇This concentration C until it reaches₁₄the beginning
is gradually decreased, and t₇around the position of
is sharply decreased at position t₇Then the concentration C₁₅considered to be
Ru. position t₇and position t₈At first, the relationship between
decreased, and then decreased slowly and gradually.
position t₈At concentration C₁₆and position t₈and position t₉between
The position t is gradually decreased.₉In, the concentration
C₁₇leading to. position t₉and position_TThe concentration between
C₁₇As shown in Figure 15, it becomes more substantially zero.
It is reduced according to a curve of such a shape. As described above, as shown in FIGS. 7 to 15, the layer 102'
germanium atoms and/or tin contained in
We will explain some typical examples of the distribution state of atoms in the layer thickness direction.
As explained above, in the light receiving member of the present invention, the support
On the support side, germanium atoms or/and
The interface t_T~ side
, the distribution concentration C is smaller than that on the support side.
germanium atom with a significantly lowered portion
Or/and the distribution state of tin atoms is the constituent layer 102'
It is desirable that the That is, the layer constituting the light receiving member in the present invention
102' is preferably on the support side as described above.
Germanium atoms and/or tin atoms are present in the
It has a localized area where it is contained at a relatively high concentration.
is desirable. In the light receiving member of the present invention, the localized region is
Please explain using the symbols shown in Figures 7 to 15.
For example, the interface position t_BIt is desirable that it be provided within 5μ.
Yes. Then, the above localized region is at the interface position t_BMore than 5μ thick
In some cases, it is defined as the entire layer area up to
Sometimes it is considered part of the area. The localized region may be part or all of layer 102'.
The characteristics required for the photoreceptive layer to be formed
It is determined appropriately according to gender. The localized region contains germanium atoms contained within it.
distribution state of tin atoms and/or tin atoms in the layer thickness direction.
distribution concentration of germanium atoms and/or tin atoms.
The maximum value Cmax of
or more than 1000 atomic ppm, more preferably
5000 atomic ppm or more, optimally 1×10^Fouratomic
layer to achieve a distribution state of ppm or more.
preferably formed. That is, in the light receiving member of the present invention, germanium
Layer 1 containing nium atoms and/or tin atoms
02' is a layer thickness from the support side of 5μ or less (t_Bfrom
The maximum value Cmax of the distribution concentration exists in the layer area of 5μ layer)
It is preferable that it be formed so as to. In the light-receiving member of the present invention, in the layer 102'
Germanium atoms or/and tin base to be contained
The content of children can efficiently achieve the purpose of the present invention.
It is necessary to decide as appropriate according to your wishes, and usually
is 1~6×10^Fiveatomic ppm, preferably
is 10~3×10^Fiveatomic ppm, more preferably 1
×10²~2×10^FiveSet to atomic ppm. In the photoreceptive layer of the photoreceptor member of the present invention, oxygen atoms,
At least one selected from carbon atoms and nitrogen atoms
The purpose of containing one type of compound is mainly to improve the photoreceptor area.
High light sensitivity and high dark resistance of materials, support and light
This improves the adhesion between the receptor layer and the receptor layer. In the photoreceptive layer of the present invention, oxygen atoms, carbon
At least one selected from atoms and nitrogen atoms
When containing seeds, uniform distribution in the layer thickness direction
It may be contained in a non-uniform manner in the thickness direction or
The purpose of the above-mentioned question is whether to contain the
It varies depending on the location and expected effects.
Therefore, the amount to be included will also differ.
Ru. In other words, high dark resistance for high photosensitivity of the light-receiving member
If the purpose is to
In this case, the photoreceptor
Carbon atoms, oxygen atoms, nitrogen atoms contained in the layer
The amount of at least one selected from among the following is relatively small
That's fine. In addition, we aim to improve the adhesion between the support and the photoreceptive layer.
When the target is the support side edge of the photoreceptive layer
Is it contained uniformly in the constituent layer 102'?
Or, at the end of the photoreceptive layer on the side of the support, the carbon source is
a small group selected from children, oxygen atoms, and nitrogen atoms.
A distribution state in which the concentration of one type of spider is high.
In this case, it is contained in the photoreceptive layer.
selected from oxygen atoms, carbon atoms, and nitrogen atoms.
The amount of at least one type of material exposed is determined by the amount of
Relatively large amounts are used to ensure improvement. In the light-receiving member of the present invention, contained in the light-receiving layer
Among the oxygen atoms, carbon atoms and nitrogen atoms that cause
However, the amount of at least one selected from
Considering the characteristics required for the photoreceptive layer, such as
In addition, characteristics at the contact interface with the support, etc.
The decision shall be made taking into consideration the relevance.
typically 0.001 to 50 atomic%, preferably 0.002
~40atomic%, optimally 0.003~30atomic%
Ru. By the way, it is contained in the entire layer area of the photoreceptive layer.
Or, the layer thickness of some layer regions to be included.
occupies a large proportion of the thickness of the photoreceptive layer.
The above-mentioned upper limit of the content is set at a lower level.
Ru. That is, in that case, for example, containing
The layer thickness of the layer region is 2/5 of the layer thickness of the photoreceptive layer.
In such cases, the amount to be included is usually
30 atomic% or less, preferably 20 atomic% or less,
Optimally, it is set to 10 atomic% or less. Next, the oxygen source contained in the photoreceptive layer of the present invention
a small number selected from carbon atoms, carbon atoms, and nitrogen atoms
Both have a relatively large amount on the support side.
and from the end of the support side to the end of the free surface end
With the end of the free surface of the photoreceptive layer decreasing
In the near future, the amount will be relatively small or
When the distribution is qualitatively close to zero,
Some typical examples are shown in Figures 16 to 24.
This will be explained by. However, the present invention
It is not limited by. [Hereinafter, carbon
A small number selected from atoms, oxygen atoms, and nitrogen atoms.
One type of spider is written as "atom (O, C, N)"
Ru. ] In Figures 16 to 24, the horizontal axis is the atom
The vertical axis represents the distribution concentration C of (O, C, N) in the photoreceptive layer.
indicates the layer thickness of t_Bis the interface position between the support and the photoreceptive layer.
Place, t_Tis the position of the end face on the free surface side of the photoreceptive layer.
show. Figure 16 shows atoms contained in the photoreceptive layer.
The first standard for the distribution state of (O, C, N) in the layer thickness direction
An example of the type is shown. In the example, atoms (O, C,
Interface position t between the photoreceptive layer containing N) and the support_B
More position₁up to the distribution concentration of atoms (O, C, N)
Degree C is C₁The position t₁more free surface
Side end surface position t_Tup to the distribution concentration of atoms (O, C, N)
degree C is concentration C₂Continuously decreases from position t_Tsmell
The distribution concentration of atoms (O, C, N) is C₃becomes. In one of the other typical examples shown in FIG.
Distribution concentration of atoms (O, C, N) contained in the layer
C is position t_Bfrom position t_Tuntil the concentration C_Fourmosquito
continuously decreases from position t_Tconcentration C at_FiveTona
Ru. In the example shown in FIG. 18, the position t_Bfrom position t₂to
is the distribution concentration C of atoms (O, C, N) is the concentration C₆Na
The position t is maintained at a constant value.₂from position t_Tuntil
is the distribution concentration C of atoms (O, C, N) is the concentration C₇
Gradually and continuously decreases from position t_THara in the
The distribution concentration C of children (O, C, N) is essentially zero.
Become. In the example shown in Figure 19, the atoms (O, C, N)
Position t of distribution concentration C_BMore position_TUntil the
Concentration C₈Continuously gradually decreases from position t_Tsmell
Therefore, the distribution concentration C of atoms (O, C, N) is essentially
It becomes zero. In the example shown in Figure 20, the atoms (O, C, N)
The distribution concentration C is at the position t_BMore position₃between
concentration c₉is at a constant value of t, and the position t₃from position t_TBetween
In this case, the concentration C₉From concentration C_Tenuntil the primary
Functionally decreasing. In the example shown in Figure 21, the atoms (O, C, N)
The distribution concentration C is at the position t_BMore position_Fouruntil it reaches
Concentration C₁₁is at a constant value of t, and the position t_FourMore position_Twas in
until the concentration C₁₂From concentration C₁₃linear function until
decrease. In the example shown in FIG. 22, atoms (O, C,
The distribution concentration C of N) is at the position t_Bfrom position t_Tleading to
up to, concentration C₁₄linear until it becomes essentially zero.
In the example shown in Figure 23, which decreases functionally, the atoms
The distribution concentration C of (O, C, N) is at the position t_Bfrom position
t_FiveConcentration C up to₁₅From concentration C₁₆One until
decreases in a sub-functional manner, position t_Fivefrom position t_Tuntil the concentration
C₁₆maintain a constant value. Finally, in the example shown in FIG.
The distribution concentration C of C, N) is at the position t_Bconcentration at
C₁₇and position t_Bfrom position t₆Until the concentration C₁₇mosquito
At the beginning, it slowly decreases and reaches position t.₈Nearby there is a sudden
sharply decreased, position t₈Then the concentration C₁₆becomes. next,
position t₃from position t₇decreases rapidly at first
a little, then slowly gradually decreases, position t₇Nii
Then the concentration C₁₉becomes. further position t₇and position t₈between
decreases very slowly and gradually until position t₈smell
concentration C₂₀becomes. Furthermore, position t₈from position t_Tto
Until then, the concentration C₂₀becomes essentially zero from
gradually decreases to As shown in the examples shown in Figures 16 to 24, the light receiving
Distribution of atoms (O, C, N) at the support side end of the container layer
Having a part with high concentration C, on the free surface side of the photoreceptive layer
At the end, the distribution concentration C is quite low.
or have a concentration substantially close to zero.
In the case where the photoreceptive layer has a part, the support of the photoreceptive layer
The distribution concentration of atoms (O, C, N) at the side edges is relatively
Providing localized areas of high concentration, preferably
The localized region is located at the interface between the support surface and the photoreceptive layer.
t_BBy providing the support within 5μ from the
Achieves even more efficient adhesion with the container layer.
can be done. The localized region does not contain atoms (O, C, N).
The end of the light-receiving layer on the support side is partially covered with the entire layer area.
It may be part or part of the
The amount of misalignment depends on the photoreceptive layer being formed.
It is determined as appropriate according to the characteristics. Atoms (O, C, N) to be contained in the localized region
The amount is the maximum value of the molecular concentration C of atoms (O, C, N)
is more than 500 atomic ppm, preferably 800 atomic ppm
ppm or more, optimally 1000 atomic ppm or more
It is desirable to have such a distribution state. Furthermore, in the light receiving member of the present invention, if necessary,
By applying a substance that controls conductivity to the photoreceptive layer,
Uniform or non-uniform distribution in the area or some layer areas
It can be contained in The substance that controls the conductivity is a semiconductor component.
I can name the so-called impurities in the field.
belongs to group of the periodic table, giving P-type conductivity.
atoms (hereinafter simply referred to as "group atoms"), or
Atoms belonging to group of the periodic table that give n-type conductivity
(hereinafter simply referred to as "group atoms") are used.
Ru. Specifically, the group atoms include B (boron).
element), Al (aluminum), Ga (gallium), In
(Thallium), Tl (Thallium), etc.
However, particularly preferred are B and Ga.
Group atoms include P (phosphorus), As (arsenic), and Sb.
(antimony), Bi (bismane), etc.
However, particularly preferred are P and Sb. A substance that controls conductivity in the photoreceptive layer of the present invention.
or where group atoms are contained.
If so, either contain it in the entire layer area or
Whether it is included in the layer area depends on the purpose as described below.
It varies depending on the purpose and expected effect.
Therefore, the amount contained also differs. That is, the conductivity type and/or conductivity of the photoreceptive layer
If the main purpose is to control the
Contained in the entire layer area of the receptor layer, in this case, the first
Relatively little content of group atoms or group atoms
usually 1×10^-3~1×10³At atomic ppm
Yes, preferably 5×10^-2~5×10²atomic
ppm, optimally 1×10^-1~2×10²At atomic ppm
be. In addition, in the constituent layer 102' in contact with the support,
Contain group atoms or group atoms in a uniform distribution
group atoms in the layer thickness direction
Or the distribution concentration of group atoms is on the side in contact with the support.
When containing at a high concentration in
is such a group atom or any group containing an atom
There is a constituent layer (constituent layer 102' in FIG. 1).
or containing group atoms or a high concentration of group atoms.
This layer region functions as a charge injection blocking layer.
It becomes roto. That is, when containing group atoms
In this case, the free surface of the photoreceptor layer undergoes polar charging treatment.
When received, it is injected from the support side into the photoreceptive layer.
can more efficiently prevent the movement of electrons.
In addition, when group atoms are contained, the light
When the free surface of the receptor layer is subjected to polar charging treatment
In this case, the number of holes injected from the support side into the photoreceptive layer is
Movement can be more effectively prevented. stop
Therefore, the content in such cases is relatively large.
Specifically, 30 to 5×10^Fouratomic ppm, good
Preferably 50 to 1×10^Fouratomic ppm, optimally 1
×10²~5×10³Set as taomic ppm. Furthermore, the applicable
In order to efficiently perform the effect as a charge injection blocking layer,
group atoms or group atom or group atom
A layer provided at the end of the support containing the child or
The layer thickness of the layer region is t, and the layer thickness of the photoreceptive layer is T.
In this case, it is desirable that the relationship t/T<0.4 holds true.
preferably, and more preferably, the value of the relational expression is 0.35 or more.
Ideally, it should be below 0.3.
Yes. In addition, the layer thickness t of the layer or layer region is generally
3×10^-3~10μ, preferably 4×
Ten^-3~8μ, optimally 5×10^-3~5μ is desirable.
Yes. Group atoms or group atoms contained in the photoreceptive layer
The amount of atoms is relatively large on the support side.
from the support side to the side with the free surface.
near the free surface of the photoreceptive layer.
be relatively small or virtually nil.
Group atoms or group atoms are distributed so that
A typical example is when the aforementioned photoreceptor layer is exposed to an oxygen source.
at least one of the following: a carbon atom or a nitrogen atom;
No. 16 exemplified in the case of containing one of the following
This will be explained using an example similar to that shown in FIGS.
However, the present invention is not limited by these examples.
It is not something that will be done. Then, as in the examples shown in Figures 16 to 24,
group atoms or on the side of the photoreceptive layer near the support
has a part with a high distribution concentration C of group atoms, and
On the free surface side of the receptor layer, the distribution concentration C is
Areas of very low concentration or virtually zero concentration
If the part has a high concentration, the support side
Group atoms or distribution concentration of group atoms near the area
providing a localized region with a relatively high concentration of
Preferably, the localized region is placed in a field that contacts the support surface.
By providing it within 5μ from the surface position,
A layer with a high distribution concentration of atoms or group atoms
The above-mentioned operation in which the region forms a charge injection blocking layer
The effects of this work can be achieved even more efficiently. The above describes the distribution state of group atoms or group atoms.
We have described the effects of each individually, but the
A light-receiving member with characteristics that can achieve the desired purpose
For obtaining these group atoms or group
The distribution of atoms and the content of the atoms in the photoreceptive layer
Adjust the amount of group atoms or group atoms as appropriate.
Use in combination as appropriate. For example, charge injection into the support side end of the photoreceptive layer.
When a blocking layer is provided, a charge injection blocking layer (Fig.
02') of the light-receiving layer (Fig. 1 10)
2') conductivity contained in the charge injection blocking layer
Controls the conductivity of a polarity different from the polarity of the substance that controls it.
It may also contain a substance that controls the
The material that controls polar conductivity is used as a charge injection blocking layer.
Contained in a much smaller amount than that contained in
You can force it. Furthermore, in the light receiving member of the present invention, the support
As a constituent layer provided at the end on the body side, it prevents charge injection.
Instead of layers, the so-called
A barrier layer may also be provided or the barrier layer
It is also possible to use both the charge injection blocking layer and the charge injection blocking layer as constituent layers.
can. As a material for forming such a barrier layer,
is Al₂O₃, SiO₂,Si₃N_FourInorganic electrical insulation materials such as
and organic electrical insulating materials such as polycarbonate and polycarbonate.
can be done. The light-receiving member of the present invention has a layer structure as described above.
As a result, the above-mentioned amorphous silicon
A photoreceptor having a multilayer photoreceptor layer configured
It can solve all the problems of materials, especially coherence.
When monochromatic laser light is used as a light source
Also, the interference fringe pattern in the image formed by interference phenomenon
Significantly prevents the appearance of
image can be formed. Further, the light receiving member of the present invention has a light receiving member in the entire visible light range.
It has high photosensitivity, especially on the long wavelength side.
Due to its excellent characteristics, it is especially suitable for use with semiconductor lasers.
Excellent twitching and fast photoresponse.
with excellent electrical, optical, and photoconductive properties;
Indicates pressure resistance and usage environment characteristics. In particular, it has been applied as a light-receiving member for electrophotography.
In some cases, the residual potential has no effect on image formation.
Its electrical characteristics are stable, and it has high sensitivity and high
It has a signal-to-noise ratio and is resistant to light fatigue and repeated use.
Good usage characteristics, high density, and vivid halftones.
Stable, clear, high-resolution, high-quality images
can be obtained repeatedly. Next, the method for forming the photoreceptive layer of the present invention will be explained.
do. There is no amorphous material constituting the photoreceptive layer of the present invention.
The glow discharge method, the sputtering method, or the
Technology that utilizes discharge phenomena such as on-plating method
This is done by the empty deposition method. The manufacturing method for these is
Manufacturing conditions, level of equipment capital investment, manufacturing scale,
Factors such as characteristics desired for the light-receiving member to be produced
be selected and adopted as appropriate, depending on the desired characteristics.
Conditions for manufacturing photoreceptive members with
is relatively easy to control, and together with silicon atoms
Carbon atoms and hydrogen atoms can be easily introduced, etc.
Therefore, glow discharge method or spatter
The method using the method is preferred. Then, glow discharge method and
Formed using the puttering method in combination with the same equipment system.
You may. For example, a-Si(H,
To form a layer consisting of X), basically
Raw materials for supplying silicon that can supply silicon atoms (Si)
Along with the gas, hydrogen atoms (H) or/and halogen for introducing
The internal pressure of the raw material gas for introducing Gen atoms (X) is reduced.
The product can be introduced into a deposition chamber that can be
– A specified device that causes an electric discharge and is placed in a specified position in advance.
A layer consisting of a-Si(H,X) is deposited on the surface of the support.
Form. As the raw material gas for supplying Si, SiH_Four,
Si₂H₆,Si₃H₈,Si_FourH_Tengaseous state or gas such as
Examples include silicon hydride (silanes) that can be
In addition, the ease of layer formation work and good Si supply efficiency, etc.
At the point, SiH_Four,Si₂H₆is preferred. In addition, as a raw material gas for introducing the halogen atoms,
Examples include many halogen compounds, such as
Halogen gas, halides, interhalogen compounds
gases such as halogen-substituted silane derivatives
Preference is given to halogenated compounds in the form of
stomach. Specifically, fluorine, chlorine, bromine, and iodine
Logen gas, BrF, ClF, ClF₃,BrF_Five,BrF₃,
IF₇, interhalogen compounds such as ICl, IBr, and
SiF_Four,Si₂F₆, SiCl_Four, SiBr_FourSilicon halides such as
etc. Silicon halide as mentioned above
When using gaseous or gasifiable substances
without using separate raw material gas for Si supply.
It is composed of a-Si containing halogen atoms.
This method is particularly effective because it allows the formation of a layer of In addition, as a raw material gas for supplying hydrogen atoms,
is hydrogen gas, HF, HCl, HBr, HI, etc.
ionide, SiH_Four,Si₂H₆,Si₃H₈,Si_FourH_TenHydrogen such as
Silicon oxide or SiH₂F₂,SiH₂I₂,SiH₂Cl₂,
SiHCl₃,SiH₂Br₂,SiHBr₃halogen-substituted water such as
Substances that are in a gaseous state or can be gasified, such as silicon oxide
In the field using these raw material gases,
In some cases, it is called control of electrical or photoelectric properties.
The inclusion of hydrogen atoms (H), which is extremely effective in
It is effective because the amount can be easily controlled.
be. and the hydrogen halide or the halogen
When using hydrogen-substituted silicon hydride, halogen source
Since a hydrogen atom (H) is also introduced at the same time as a child,
Particularly effective. Reactive sputtering method or ion platey
Forming a layer consisting of a-Si (H,
For example, in the case of sputtering method,
For introducing halogen atoms, refer to the above
Halogen compounds or silicon containing the above halogen atoms
A gas of an elementary compound is introduced into the deposition chamber and the gas is purified.
All you have to do is create a lasma atmosphere. In addition, when introducing hydrogen atoms, hydrogen atom guide
Required raw material gas, e.g. H₂Or the above scenario
Gases such as orchids are placed in a deposition chamber for sputtering.
Introduce it and create a plasma atmosphere of the gas.
Bye. For example, in the case of the reactive sputtering method, Si
Gas for introducing halogen atoms using a target
and H₂If necessary, use an inert gas such as He or Ar.
A plasma atmosphere is created by introducing the
forming and sputtering the Si target.
In particular, from a-Si(H,X) on the support
form a layer of Structured with a-SiGe(H,X) by glow discharge method.
Silicon atoms (Si)
Raw material gas for Si supply that can supply
Raw material gas for Ge supply that can supply Mu atoms (Ge)
and a hydrogen atom (H) or/and a halogen atom (X)
Hydrogen atoms (H) and/or halogen atoms that can be supplied
(X) Supply raw material gas to a composting machine that can reduce the internal pressure.
Introduce the gas into the deposition chamber at the desired pressure, and
set in a predetermined position by causing a glow discharge in the
a-SiGe on the surface of a predetermined support
A layer composed of (H, X) is formed. Raw material gas for supplying Si, raw material for supplying halogen atoms
It can be used as a raw material gas and a raw material gas for supplying hydrogen atoms.
The substance composed of the above-mentioned a-Si(H,X) is
The same material used to form the layer
used. In addition, substances that can be used as raw material gas for the Ge supply
In terms of quality, GeH_Four, Ge₂H₆, Ge₃H₈, Ge_FourH_Ten,
Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆, Ge₈H₁₈, Ge₉H₂₀etc
germanium hydride in the gaseous state or gasifiable
can be used. Especially when creating layers.
In terms of ease of handling and good Ge supply efficiency,
GeH_Four, Ge₂H₆, and Ge₃H₈is preferred. a-SiGe (H,X) by sputtering method
To form a layer composed of
A target made of germanium and a target made of germanium.
or silicon and germanium.
Using a target consisting of
by sputtering in a gas atmosphere.
Now. a-SiGe using ion plating method
When forming a layer composed of (H, X),
For example, polycrystalline silicon or single crystal silicon and polycrystalline silicon.
Crystal germanium or single crystal germanium
Each is housed in the evaporation port as an evaporation source, and this evaporation
Source: resistance heating method or electron beam method
(E.B. method) etc. to heat and evaporate the flying evaporated matter.
through the desired gas plasma atmosphere.
It can be done with. Sputtering method and ion plating
In either case, halogen is not present in the layer formed.
In order to contain atoms, the above-mentioned halides or
is a deposition chamber containing silicon compound gas containing halogen atoms.
to form a plasma atmosphere of the gas.
Bye. Also, when introducing hydrogen atoms, hydrogen
Raw material gas for atomic supply, e.g. H₂Or the above
Hydrogenated silanes or/and germanium hydrogenated
gases such as aluminum are introduced into the deposition chamber for sputtering.
to form a plasma atmosphere of these gases.
That's fine. Furthermore, raw material gas for supplying halogen atoms
As for the above-mentioned halides or halogens,
Silicon compounds containing are listed as effective.
However, in addition, halogens such as HF, HCl, HBr, HI, etc.
Hydrogenide, SiH₂F₂,SiH₂I₂,SiH₂Cl₂, SiHCl₃,
SiH₂Br₂,SiHBr₃halogen-substituted silicon hydrides such as
and GeHF₃, GeH₂F₂, GeH₃F, GeHCl₃,
GeH₂Cl₂, GeH₃Cl, GeHBr₃, GeH₂Br₂,
GeH₃Br, GeHI₃, GeH₂I₂, GeH₃Hydrogenation of I etc.
Germanium rogenide, etc., GeF_Four, GeCl_Four,
GeBr_Four, GeI_Four, GeF₂, GeCl₂, GeBr₂, GeI₂etc.
Gaseous or gaseous materials such as germanium halides, etc.
Substances that can be converted into carbonaceous substances can also be used as effective starting materials.
Ru. Glow discharge method, sputtering method or ion
Using the metal plating method, tin-containing
Amorphous silicon (hereinafter referred to as “a-SiSn (H,
X)”. ) forms a photoreceptive layer consisting of
To do this, the above-mentioned a-SiGe (H,
During the formation of the layer for which germanium atoms are supplied,
The starting material is used as a starting material for supplying tin atoms (Sn).
Instead, it is used to control its amount in the layer formed.
This is done by containing the Serves as raw material gas for supplying the tin atoms (Sn) mentioned above.
As a substance that absorbs water, tin hydride (SnH_Four)or
SnF₂, SnF_Four, SnCl₂, SnCl_Four, SnBr₂, SnBr_Four,
SnI₂, SnI_FourGaseous tin halides such as
can be gasified, and halogen
When tin oxide is used, it is
Forming a layer composed of a-Si containing rogen atoms
It is particularly effective because it can be achieved. inside
However, ease of handling during layer creation work and Sn supply efficiency
SnCl_Fouris preferred. And SnCl_FourDeparture for tin atom (Sn) supply
When used as a substance, to gasify it,
Solid SnCl_FourIn addition to heating Ar, He,
Blow in an inert gas such as
It is preferable to publish the
The desired gas is placed in a deposition chamber with a reduced pressure inside.
Introduce it at a low pressure. glow discharge method, sputtering method, or
Using the on-plating method, a-Si(H,X)
Or a-Si(Ge, Sn) (H, Y) with further atoms
(O, C, N) or group atom or group atom
Forming a layer composed of amorphous material containing
a-Si(H,X) or a-Si(Ge,
During the formation of a layer of (Sn) (H, Y), atoms (O,
C, N) Starting materials or/and group atoms for introduction
Alternatively, the starting material for introducing the group atom may be
-Si(H,X) or a-Si(Ge,Sn)(H,Y) type
into the layer to be formed.
It is possible to contain them while controlling their amount.
I'll do it anyway. Starting materials for the introduction of such atoms (O, C, N)
In terms of quality, it consists of at least atoms (O, C, N).
Gaseous substances or substances that can be gasified as constituent atoms
If so, you can use most of them. Specifically, the starting material for introducing oxygen atoms (O)
For example, oxygen (O₂), ozone (O₂),monoxide
Nitrogen (NO), nitrogen dioxide (NO₂), nitric oxide,
(N₂O), nitrogen sesquioxide (N₂O₃), nitrogen tetroxide
(N₂O_Four), nitrogen pentoxide (N₂O₃), nitrogen trioxide
(NO₂), silicon atom (Si) and oxygen atom (O)
Hydrogen atoms (H) are constituent atoms, for example, di
Siloxane (H₂SiOSiH₃), trisiloxane
(H₃SiOSiH₂OSiH₃) and other lower siloxanes.
as a starting material for the introduction of carbon atoms (C).
For example, methane (CH_Four), ethane (C₂H₆),
Propane (C₃H₈), n-butane (n-C_FourH_Ten),
Pentane (C_FiveH₁₂) etc. Saturated carbonization with 1 to 5 carbon atoms
Hydrogen, ethylene (C₂H_Four), propylene (C_FiveH₆),
Butene-1 (C_FourH₆), butene-2(C_FourH₈), Isobu
Chyrene (C_FourH₈), pentene (C_FiveH_Ten) etc. carbon number
2 to 5 ethylene hydrocarbons, acetylene
(C₂H₂), methylacetylene (C₃H_Four) Butin
(C_FourH₆) etc. Acetylene hydrocarbons having 2 to 4 carbon atoms
Starting material for introducing nitrogen atom (N)
For example, nitrogen (N₂),ammonia
(NH₈), hydrazine (H₂NNH₂), hydrogen azide
(HN₃), ammonium azide (NH_FourN₃), three
Nitrogen (F₃N), nitrogen tetrafluoride (F_FourN) etc.
It will be done. Specifically, as a starting material for introducing group atoms,
For boron atom introduction, B₂H₆, B_FourH_Ten,
B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Hydrogen such as
Boron oxide, BF₃, BCl₃,BBr₃Boron halides such as
etc. In addition, AlCl₃, GaCl₃,Ga
(CH₃)₂,InCl₃, TlCl₃etc. can also be mentioned. Specifically as a starting material for the introduction of group atoms.
is PH for introducing phosphorus atom.₃,P₂H_FourHydrogen such as
Phosphorus, PH_FourI, P.F.₃, P.F._Five, PCl₃, PCl_Five, PBr₃,
PBr_Five, Pi₃Examples include halogenated phosphorus such as. this
et al., AsH₃,AsF₃,AsCl₃, AsBr₃,AsF_Five,
SbH₃, SbF₃, SbF_Five, SbCl₃, SbCl_Five, BiH₃,
BiCl₃, BiBr_Fiveetc. are also starting materials for the introduction of group atoms.
This can be cited as an effective method. As described above, the light receiving member of the present invention
The receiving layer can be prepared using glow discharge method, sputtering method, etc.
A gel that is formed using
manium atom or/and tin atom, group atom or
is a group atom, or a hydrogen atom or/and a halo
The content of each of the gene atoms is controlled by the flow into the deposition chamber.
The gas flow rate of each starting material for supplying atoms is
or the gas flow rate ratio between each starting material for supplying atoms.
This is done by controlling the Further, the temperature of the support during formation of the photoreceptive layer of the present invention,
Conditions such as gas pressure and discharge power in the deposition chamber are set as desired.
In order to obtain a light-receiving member with the characteristics of
factors, and the function of the layer to be formed must be taken into account.
It is selected as appropriate. Furthermore, these layers
The formation conditions are as follows:
It may also vary depending on the type and amount of offspring.
From, the type of atoms to be included or their amount, etc.
It is also necessary to take this into consideration when making a decision. Specifically, a layer consisting of a-Si (H,
or atoms (O, C, N) or/and group atoms or
Is a-Si(H,X) containing group atoms?
When forming a photoreceptive layer consisting of
is usually 50 to 350°C, particularly preferably 50°C.
~250℃. The gas pressure inside the deposition chamber is usually 0.01
~1Torr, particularly preferably 0.1~0.5Torr
shall be. In addition, the discharge power is 0.005~50W/cm²and
It is normal, but more preferably 0.01~
30W/cm², particularly preferably 0.01 to 20W/cm²and
Ru. When forming a layer consisting of a/SiGe(H,X)
or atoms (O, C, N) or/and
a-SiGe containing group atoms or group atoms
When forming a layer consisting of (H, X),
The support temperature is usually 50 to 350°C, but more preferably
Preferably 50 to 300℃, particularly preferably 100 to 300℃
shall be. And the gas pressure inside the deposition chamber is usually 0.01
~5Torr, preferably 0.001~3Torr
However, it is particularly preferably 0.1 to 1 Torr. Also,
Discharge power is 0.005~50W/cm²It is normal to
Yes, but preferably 0.01 to 30W/cm²and especially good
Preferably 0.01~20W/cm²shall be. However, these supports for layer formation are
Specifics of support temperature, discharge power, and gas pressure in the deposition chamber
These conditions are usually not easily determined individually.
It's a shame. Therefore, the desired property
mutual and organic association to form a layer of crystalline material.
It is desirable to determine the optimal conditions for layer formation based on the
Delicious. By the way, the gel contained in the photoreceptive layer of the present invention
Rumanium atom or/and tin atom, oxygen atom,
carbon atom, nitrogen atom, group atom or group atom
children, or hydrogen atoms and/or halogen atoms.
In order to make the distribution state uniform, it is necessary to form a photosensitive layer.
It is necessary to keep the above conditions constant when
It is essential. In addition, in the present invention, when forming the photoreceptive layer,
The germanium atoms or germanium atoms contained in the layer are
is/and tin atom, or group atom or group atom
The distribution concentration of group atoms is changed in the layer thickness direction to obtain the desired value.
To form a layer having a distribution state in the layer thickness direction,
When using the glow discharge method, germanium
aluminum atom or/and tin atom, oxygen atom, carbon atom
or a nitrogen atom, or a group atom or a group atom
Introducing the starting material gas into the deposition chamber for child introduction
Change the gas flow rate accordingly according to the desired rate of change.
formed while keeping other conditions constant. So
Specifically, to change the gas flow rate,
Normal use, e.g. manually or with an externally driven motor
The route of the gas flow system is
Gradually open the predetermined needle valve provided in the
All you have to do is perform the next change operation. At this time, the flow rate
The rate of change of is not necessarily linear; for example,
A pre-designed rate of change curve using
Control the flow rate according to the desired content curve to obtain the desired content curve.
You can also do that. In addition, the photoreceptive layer is formed using a sputtering method.
germanium atom or tin atom, acid
elementary atom, carbon atom or nitrogen atom, or group
The distribution concentration of atoms or group atoms in the layer thickness direction is defined as the layer thickness.
shape the distribution state in the desired layer thickness direction by changing the
The process is similar to that using the glow discharge method.
In addition, germanium atoms or tin atoms, or
group atoms or the starting material for the introduction of group atoms into a gas
when introducing the gas into the deposition chamber.
Vary the gas flow rate according to the desired rate of change. 〔Example〕 Hereinafter, the present invention will be further explained according to Examples 1 to 11.
Although explained in detail, the present invention is not limited by these.
It is not something that will be done. In each example, the photoreceptive layer was prepared using a glow discharge method.
It was formed using Figure 25 shows the glow discharge method.
This is an apparatus for manufacturing a light-receiving member of the present invention. 2502, 2503, 2504, 250 in the diagram
5,2506 gas cylinders have each of the present invention.
The raw material gas for forming the layer is sealed,
As an example, 2502 is SiF_Fourgas
(99.999% purity) cylinder, 2503 is H₂diluted with
B₂H_FourGas (purity 99.999%, below B₂H_Four/H₂and
Omitted. ) cylinder, 2504 is SH_FourGas (purity
99.999%) cylinder, 2505 is GeF_FourGas (purity
99.999%) cylinder, 2506 is inert gas (He)
It's a cylinder. And 2506′ is SnCl_Fouris in
It is an airtight container. To allow these gases to flow into the reaction chamber 2501
is the valve 252 of the gas cylinders 2502 to 2506
2-2526, leak valve 2535 is closed
Also, check that the inflow valves 2512-2
516, outflow valves 2517-2521, auxiliary valves
Make sure that lubricants 2532 and 2533 are open.
First, open the main valve 2534 to react.
The chamber 2501 and gas piping are evacuated. then vacuum
Forming a photoreceptive layer on the Al cylinder 2537
An example of this case is described below. First, from gas cylinder 2502, SiF_Fourgas, gas
B from cylinder 2503₂H₆/H₂gas, gas cylinder
Ge from 2505_FourGas, from gas cylinder 2505
GeF_FourValves 2522, 2523,
Open 2525 and check the outlet pressure gauges 2527, 252
The pressure of 8,2529,2530 is 1Kg/cm²adjusted to
and inflow valves 2512, 2513, 2514,
Gradually open the 2515 and set the mass flow control.
La, within 2507, 2508, 2509, 2510
to flow into. Subsequently, the outflow valve 2517,
2518, 2519, 2520 Auxiliary valve 253
2 gradually opens to let gas flow into the reaction chamber 2501.
let SiF at this time_FourGas flow rate, GeF_Fourgas flow
Amount, B₂H₆/H₂Gas flow rate and CH_FourThe ratio of gas flow rates is
Outflow valves 2517, 25 to the desired value.
18, 2519, 2520, and the reaction chamber
Check the vacuum gauge so that the pressure inside 2501 reaches the desired value.
While checking the reading of 2536, check the main valve 2534.
Adjust the aperture. and the base cylinder 253
7 temperature is 50~400 by heating heater 2538
Make sure the temperature is set to a range of °C.
After that, set the power supply 2540 to the desired power and react.
When a glow discharge is generated in the chamber 2501,
using a microcomputer (not shown).
to follow the pre-designed flow rate change line.
te, SiF_Fourgas, GeF_Fourgas CH_Fourgas and B₂H₆/H₂
The base cylinder while controlling the gas flow rate of the gas
First, on 2537, silicon atoms, carbon atoms, and
Layer 10 containing rumanium atoms and boron atoms
2' is formed. Layer 102' is formed to a desired layer thickness.
At this stage, the outflow valves 2518, 252
0 completely and change the discharge conditions as necessary.
Continue the glow discharge by following the same procedure except for
Germanium atoms are formed on the layer 102' by
It is possible to form a layer 102″ that does not substantially contain
can. Gas outflow valve required when forming each layer
Needless to say, close all outflow valves except for
Also, when forming each layer, there is no difference in the formation of the previous layer.
The used gas is inside the reaction chamber 2501 and the outflow valve 2
Gases leading from 517 to 2521 into the reaction chamber 2501
To avoid any residue remaining in the piping,
Close valves 2517 to 2521 and auxiliary valve 253
2, open 2533 and fully close main valve 2534.
It is necessary to open the system and evacuate the system to high vacuum once.
Do accordingly. In addition, if tin atoms are included in the photoreceptive layer,
In this case, SnCl is used as the raw material gas._Fourstarting material and
When using a gas that has been
solid SnCl_Fourusing heating means (not shown)
At the same time, the SnCl_FourAr, He, etc.
Inert gas such as Ar, He etc. from inert gas cylinder 2506
Blow sexual gas and pubbling. Occurred
SnCl_FourThe gas is the aforementioned SiF_Fourgas, GeF_Fourgas and
B₂H₆/H₂into the reaction chamber using the same procedure as gas etc.
Let it flow. Test example 1 Chemically treated SUS stainless steel rigid sphere with a diameter of 0.6 mm.
The surface was etched to form irregularities.
The processing agents used include hydrochloric acid, hydrofluoric acid, sulfuric acid,
Examples include acids such as chromic acid and alkalis such as caustic soda.
can be done. In this test example, concentrated hydrochloric acid 1
Hydrochloric acid solution mixed at a volume of pure 1 to 4
The immersion time of the hard sphere, the acid concentration, etc. were changed using
The shape of the unevenness was adjusted as appropriate. Test example 2 Rigid spheres treated by the method of Test Example 1 (Table
Using the height γmax of surface unevenness = 5 μm),
Using the equipment shown in the figure,
Treat the surface of the Linder (diameter 60mm, length 298mm),
Irregularities were formed. The diameter R′ of the true sphere, the falling height h and the curvature R of the trace depression,
When we investigated the relationship with the width r, we found that the curvature R of the trace depression
and the width r are the conditions such as the diameter R′ of the perfect sphere and the falling height h.
It was confirmed that it can be determined by Also, traces
Pitch of depressions (density of trace depressions, and unevenness of pits)
h) is the rotational speed, rotational speed or stiffness of the cylinder.
Adjust to the desired pitch by controlling the amount of fall of the true sphere, etc.
It has been confirmed that it can be done. Furthermore, R
As a result of considering the size of R and D, R is
If it is less than 0.1 mm, the rigid sphere can be made smaller and lighter.
The fall height must be ensured and the shape of the trace depression
undesirable as it makes it difficult to control
However, if R exceeds 2.0 mm, the rigid sphere will be heavily weighted.
To adjust the falling height, for example, compare D.
If you want to make it relatively small, you can lower the drop height to the extreme.
control the formation of vestigial depressions.
This is undesirable because it makes it difficult to
If it is less than 0.02mm, the rigid sphere will be made smaller and lighter.
The lower height must be ensured and the formation of trace depressions
This is undesirable as it makes it difficult to control
Both were confirmed. Furthermore, when we tried the formed trace depressions, we found that
Inside the trace depression, there is a microscopic groove corresponding to the surface unevenness of the rigid sphere.
It was confirmed that small irregularities were formed. Example 1 Aluminum alloy cylinder as in Test Example 2
D shown in the upper column of Table 1A, and
Cylindrical Al support (cylinder) with D/R No. 101 to 106) were obtained. Next, the Al support (cylinder No. 101 to 106)
Above, under the conditions shown in Table 1B below, as shown in Figure 25.
A photoreceptive layer was formed using the manufacturing apparatus shown. These light receiving members are shown in FIG.
Using an image exposure device, wavelength 780nm, spot diameter
Perform image exposure by irradiating 80 μm laser light.
Then, development and transfer were performed to obtain an image. obtained
The occurrence of interference fringes in images is shown in the bottom column of Table 1A.
It was hot in the cage. Note that FIG. 26A schematically shows the entire exposure apparatus.
FIG. 26B is a schematic plan view showing the entire exposure apparatus.
It is a side view schematically showing a body. In the figure, 260
1 is a light receiving member, 2602 is a semiconductor laser, 2
603 is fθ lens, 2604 is polygon mirror
Showing. Next, as a comparison, a conventional diamond cutting tool
Aluminum alloy cylinder surface treated with
Dar No. 107 (diameter 60mm, length 298mm, uneven pitch 100μ
m, depth of unevenness 3 μm) in the same manner as above.
A light-receiving member was prepared. Obtained light-receiving member
When observed with an electron microscope, it was found that the support surface and the light
The layer interface of the receptor layer and the surface of the photoreceptor layer are parallel to each other.
Was. Using this light-receiving member, similar to the above
The image is formed using
The same evaluation as above was performed. The result is
It was as shown in the bottom column of Table 1A.

[Table] ×…Unsuitable for practical use, △…Possible for practical use, ○…Good practicality, ◎…Excellent practicality

[Table] Example 2 The same procedure as in Example 1 was carried out except that the photoreceptive layer was formed according to the layer formation conditions shown in Table 2B.
A photoreceptive layer was formed on the Al support (cylinder Nos. 101 to 107). In addition, when forming the photoreceptive layer,
The gas flow rates of SiF ₄ gas and GeF ₄ gas were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG. When an image was formed on the obtained light-receiving member in the same manner as in Example 1, the occurrence of interference fringes in the obtained image was as shown in the lower column of Table 2A.

[Table] ×…Unsuitable for practical use △…Improved for practical use ○…Good practicality ◎…Particularly good practicality

[Table] Example 3 A spherical trace depression (D=450±50 (μm) ,D/-/R
= 0.05) with Al support (cylinder No. 301 ~
306) was obtained. Next, a light-receiving layer was formed on the Al support (cylinder Nos. 301 to 306) using the manufacturing apparatus shown in FIG. 25 under the conditions shown in Table 3B below. Note that GeH ₄ gas and SiH ₄ gas contained in the photoreceptive layer
The gas flow rates of gas and NH ₃ gas were automatically adjusted by microcomputer control according to the gas flow rate change line shown in FIG. When an image was formed on the obtained light-receiving member in the same manner as in Example 1, the occurrence of interference fringes in the obtained image was as shown in the lower column of Table 3A.

[Table] ×…Unsuitable for practical use △…Possible for practical use ○
…Good practicality ◎…Practical
Particularly good

[Table] Example 4 The same procedure as in Example 3 was carried out except that the photoreceptive layer was formed according to the layer formation conditions shown in Table 4B.
A photoreceptive layer was formed on the Al support (cylinder Nos. 301 to 306). In addition, when forming the photoreceptive layer,
The gas flow rates of SiF ₄ gas and GeF ₄ gas were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG. When an image was formed on the obtained light-receiving member in the same manner as in Example 1, the occurrence of interference fringes in the obtained image was as shown in the lower column of Table 4A.

[Table] ×…Unsuitable for practical use △…Possible for practical use ○
…Good practicality ◎…Practical
Especially good

[Table] Examples 5 to 10 Al support of Example 1 (Cylinder No. 103 to 106)
A light-receiving member was produced in the same manner as in Example 1 except that a light-receiving layer was formed thereon according to the layer forming conditions shown in Tables 5 to 10. In Examples 5 to 10, the flow rate of the gas used during the formation of the photoreceptive layer was automatically adjusted by microcomputer control according to the flow rate change lines shown in FIGS. 30 to 35, respectively. Further, boron atoms contained in the photoreceptive layer were introduced as much as possible so that B ₂ H ₆ /SiF ₄ +GeF ₄ was approximately 100 ppm, and the entire layer was doped at approximately 200 ppm. Image formation was performed on the obtained light-receiving member in the same manner as in Example 1. No interference fringes were observed in any of the images obtained, and they were of extremely good quality.

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[Summary of effects of the invention]

The light-receiving member of the present invention has the above-described layer structure, thereby solving all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when a monochromatic laser beam is used as a light source, it is possible to significantly prevent the appearance of interference fringes in a formed image due to interference phenomena, and to form an extremely high-quality visible image. In addition, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers, and has a high photoresponsiveness. It exhibits excellent electrical, optical, photoconductive properties, electrical voltage resistance, and use environment characteristics. In particular, when applied as a light-receiving member for electrophotography, 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.

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing an example of the light-receiving member of the present invention, and FIGS. 2 and 3 are diagrams for explaining the principle of preventing the generation of interference fringes in the light-receiving member of the present invention. FIG. 2 is a partially enlarged view showing that the generation of interference fringes can be prevented in a light-receiving member in which irregularities formed by spherical trace depressions are formed on the surface of the support, and FIG. 3 is a diagram showing a conventional surface. FIG. 3 is a diagram showing that interference fringes occur in a light-receiving member in which a light-receiving layer is deposited on a regularly roughened support.
FIGS. 4 and 5 are schematic diagrams for explaining the uneven shape of the support surface of the light-receiving member of the present invention and the method for producing the uneven shape. FIG. 6 is a diagram schematically showing a configuration example of a device suitable for forming an uneven shape when provided on a support of a light-receiving member of the present invention, and FIG. 6A is a front view, and FIG. Figure 6B is a longitudinal sectional view. 7 to 15 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the photoreceptive layer of the present invention, and FIGS. These are diagrams showing the distribution state of atoms, nitrogen atoms, group atoms, or group atoms in the layer thickness direction. In each diagram, the vertical axis indicates the layer thickness of the photoreceptive layer, and the horizontal axis indicates the distribution concentration of each atom. It represents. FIG. 25 is an example of an apparatus for manufacturing the light-receiving layer of the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. FIG. 26 is a diagram illustrating an image exposure apparatus using laser light. FIGS. 27 to 35 are diagrams showing changes in the gas flow rate ratio in forming the photoreceptive layer of the present invention, in which the vertical axis represents the layer thickness of the photoreceptive layer, and the horizontal axis represents the gas flow rate of the gas used. Regarding FIGS. 1 to 3, 100...light-receiving member, 101...support, 102...light-receiving layer, 1
02′...layer containing at least one of germanium atoms or tin atoms, 102″...
...layer containing neither germanium atoms nor tin atoms, 201,301...first layer, 20
2,302...second layer, 103,203,30
3... Free surface, 204,304... Interface between the first layer and the second layer, 40 for Figures 4 and 5
1,501...Support, 402,502...Support surface, 403,503...Spherical trace depression, 40
3', 503'...Rigid sphere having an uneven shape on the surface, 404...Minute uneven shape formed in the spherical trace depression, 404'... uneven shape formed on the surface of the rigid sphere, Regarding Fig. 6, 601...Cylinder, 602...Rotating shaft (receiving), 603...Driving means, 604...Rotating container, 605...Rigid sphere having an uneven shape on the surface, 606...Ribs provided on the inner wall of the container, 607...Shower tube, regarding Fig. 25, 2501...Reaction chamber, 2502-25
06... Gas cylinder, 2506'... Sealed container for SnCl ₄ , 2507-2511... Mass flow controller, 2512-2516... Inflow valve, 2
517-2521...Outflow valve, 2522-2
526... Valve, 2527-2531... Pressure regulator, 2532, 2533... Auxiliary valve, 2
534... Main valve, 2535... Leak valve, 2536... Vacuum gauge, 2537... Base cylinder, 2538... Heater, 2539
...Motor, 2540...High frequency power supply, No. 26
Regarding the figure, 2601...light receiving member, 2602
... Semiconductor laser, 2603 ... fθ lens, 2
604...Polygon mirror.

Claims (1)

[Claims] 1. A layer (a) containing at least one of germanium atoms or tin atoms and a layer (b) containing neither germanium atoms nor tin atoms are placed on a support from the support side. and a multilayered photoreceptive layer made of an amorphous material containing silicon atoms and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms. , the surface of the support has a recess width D
is 500 μm or less, and the radius of curvature R and width D of the depression are
It has unevenness due to a plurality of spherical trace depressions with 0.035≦D/R, and further inside the spherical trace depressions.
A light-receiving member characterized in that minute irregularities of 0.5 to 20 μm are formed. 2. The light-receiving member according to claim 1, wherein the light-receiving layer contains atoms belonging to Group 1 or Group 3 of the periodic table. 3. The light-receiving member according to claim 1, wherein the light-receiving layer has, as one of its constituent layers, a charge injection prevention layer containing atoms belonging to Group 1 or Group 3 of the periodic table. 4. The light-receiving member according to claim 1, wherein the light-receiving layer has a barrier layer as one of the constituent layers. 5. The light-receiving member according to claim 1, wherein the irregularities formed by the spherical trace depressions have the same radius of curvature. 6. The light-receiving member according to claim 1, wherein the unevenness caused by the spherical trace depressions is formed by depressions having substantially the same radius of curvature and width. 7. The light-receiving member according to claim 1, wherein the support is a metal body. 8. The distribution concentration of atoms belonging to Group 3 or Group 3 of the periodic table contained in the photoreceptive layer is relatively high on the support side, and is considerably lower on the surface side of the photoreceptor layer than on the support. The light-receiving member according to claim 2, wherein the light-receiving member has a concentration substantially close to zero and is non-uniformly distributed in the layer thickness direction. 9 The distribution concentration of germanium atoms or tin atoms contained in the layer (a) is relatively high on the support side, and the layer (b) side containing neither germanium atoms nor tin atoms is compared to the support side. The light-receiving member according to claim 1, wherein the light-receiving member has a fairly low concentration and is non-uniformly distributed in the layer thickness direction. 10 The distribution concentration of at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms contained in the photoreceptive layer is relatively high on the support side, and The light-receiving member according to claim 1, wherein the light-receiving member has a considerably lower concentration or substantially zero concentration than the body side and is distributed non-uniformly in the layer thickness direction.