JPS62102249A - Light receiving material - Google Patents

Abstract

PURPOSE:To prevent the generation of interference fringes in formed image by further providing plural smaller rugged shapes within plural spherical recesses of traces on the surface of a base and successively forming a layer contg. at least either of germanium atoms or tin atoms and layer contg. neither thereof an said base. CONSTITUTION:A light receiving layer is provided with the light receiving layers consisting of the 1st layer 102 and 2nd layer 103 along the slopes of the ruggedness on the base 101 having the plural very small rugged shapes consisting of the spherical recesses of traces and further having the plural rugged shapes within the spherical recesses of traces as the light receiving material 100. The layers 102 is constituted by providing the layer 102' constituted of the amorphous material contg. at least either of the germanium atoms or tin atoms and the layer 102'' constituted of the amorphous material contg. at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms and contg. neither of the germanium atoms or tin atoms from the base 101 side. The formation of the interference fringe patterns in the formed image by interference is thus prevented.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention relates to the use of light (here, light in a broad sense, such as ultraviolet rays, visible light,
It relates to a light-receiving member that is sensitive to electromagnetic waves such as infrared rays, X-rays, gamma rays, etc.

More specifically, the present invention relates to a light receiving member suitable for using coherent light such as laser light.

[Description of prior art]

As a method for recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is developed. Further, there are known methods of recording images that perform processes such as transfer and fixing as necessary. Among them, in the image forming method using electrophotography, a small and inexpensive He-Ne laser or a semiconductor laser ( Generally, image recording is performed using a light emitting wavelength (usually having an emission wavelength of 650 to 820 wavelengths).

By the way, as a light-receiving member for electrophotography suitable when using a semiconductor laser, in addition to being superior in consistency of its photosensitivity region compared to other types of light-receiving members,
Amorphous materials containing silicon atoms (hereinafter referred to as A light-receiving member made of ra-8iJ (abbreviated as ra-8iJ) has been attracting attention.

However, in the light-receiving member, if the light-receiving layer is a single-layer a-8i layer, it is difficult to maintain its high photosensitivity and ensure a dark resistance of 1012Ω or more, which is required for electrophotography. , it is necessary to structurally contain hydrogen atoms, halogen atoms, or boron atoms in addition to these in a specific amount range in a controlled manner in the layer, so various conditions must be adjusted during layer formation. There are considerable limitations on the latitude in the design of the light-receiving member, such as the need for tight control. Proposals have been made to improve such design tolerance problems by making it possible to effectively utilize the high light sensitivity even if the dark resistance is low to some extent. That is, for example, JP-A-54-121743, JP-A-57-4053, and JP-A-57-417.
As seen in Japanese Patent Laid-Open No. 57-52178, the photoreceptor layer may have a two or more layer structure in which layers with different conductivity properties are laminated to form a depletion layer inside the photoreceptor layer. No. 52179, No. 52180, No. 58159,
As seen in Patent Publications No. 58160 and No. 58161, a barrier layer is provided between the support and the photoreceptive layer or/and on the upper surface of the photoreceptor layer to form a multilayer structure, and the apparent appearance is A light-receiving member with increased dark resistance has been proposed.

However, in such a light-receiving member in which the light-receiving layer has a multilayer structure, the thickness of each layer varies, and when performing laser recording using this material, since the laser light is coherent monochromatic light, the light-receiving layer The free surface on the laser beam irradiation side, each layer constituting the photoreceptive layer, and the layer interface between the support and the photoreceptor layer
From now on, the term "free surface" and "layer interface" will be used together.
It is called "interface". ) The reflected light beams that are reflected from each other often cause interference.

This interference phenomenon causes the so-called,
This appears as an interference fringe pattern and causes image defects. Particularly in the case of forming a half-tone image with high gradation, a blurred image with extremely poor distinguishability is produced.

Another important point is that as the wavelength range of the semiconductor laser light used becomes longer, the absorption of the laser light in the photoreceptive layer decreases, so there is a problem that the above-mentioned interference phenomenon becomes more noticeable. .

That is, for example, in a device with a structure of two or more layers (multilayer), interference effects occur in each of those layers, and each interference acts synergistically to create an interference fringe pattern. This directly affects the transfer member, and there is a problem that interference fringes corresponding to the interference fringe pattern are transferred and fixed onto the member and appear in a visible image, resulting in a defective image.

As a measure to solve these problems, (a) the surface of the support is diamond-cut to provide unevenness of ±500A to ±100OOA to form a light scattering surface (for example,
8-162975), (b) a method of providing a light absorption layer by treating the surface of the aluminum support with black alumite, or dispersing carbon, coloring pigments, and dyes in a resin (for example, Japanese Patent Application Laid-Open No. 8-162975); (Refer to Publication No. 57-165845), (c) Provide a light scattering and anti-reflection layer on the surface of the support by subjecting the surface of the aluminum support to satin-like alumite treatment or by sandblasting to provide fine roughness in the form of grains. Methods (for example, see Japanese Patent Laid-Open No. 16554/1983) have been proposed.

Although these proposed methods provide some results, they are not sufficient to completely eliminate the interference fringe pattern that appears on images.

That is, in method (a), a large number of specific irregularities are provided on the surface of the support, and although the appearance of interference fringes due to the light scattering effect is somewhat prevented, the light scattering still remains. Because the specularly reflected light component remains,
In addition to the interference fringe pattern caused by the specularly reflected light remaining, the irradiation spot spreads due to the light scattering effect on the surface of the support, resulting in a substantial decrease in resolution.

Regarding method (b), complete absorption is not possible with black alumite treatment, and the reflected light on the support surface remains. In addition, when providing a colored pigment dispersed resin layer,
When forming a-3i'd, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed photoreceptive layer is significantly reduced;
Problems such as the resin layer being damaged by plasma during the formation of the A-3T layer, reducing its original absorption function, and adversely affecting the subsequent formation of the A-8T layer due to deterioration of the surface condition. have

Regarding method (C), for example, if we look at the incident light, a part of it is reflected on the surface of the photoreceptive layer and becomes reflected light,
The remainder enters the inside of the light-receiving layer and becomes transmitted light. At the surface of the support, part of the transmitted light is scattered and becomes diffused light, the rest is specularly reflected and becomes reflected light, and part of it becomes emitted light and goes outside. However, since the emitted light is a component that interferes with the reflected light and remains in any case, the interference fringe pattern still does not completely disappear.

By the way, in order to prevent interference in this case, some attempts have been made to increase the diffusivity of the surface of the support so that multiple reflections do not occur within the photoreceptive layer, but such attempts instead cause light to be absorbed within the photoreceptive layer. is diffused and causes halation, which ultimately results in a decrease in resolution.

In particular, in a multilayered light-receiving member, even if the surface of the support is irregularly roughened, the light reflected from the first layer surface, the light reflected from the second layer, and the specularly reflected light from the support surface are all affected. The interference results in an interference fringe pattern depending on the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it is impossible to completely prevent interference fringes by irregularly roughening the surface of the support.

In addition, when the surface of the support is irregularly roughened by methods such as sandblasting, the roughness varies greatly between lots, and even within the same lot, the roughness is uneven, making it difficult to manufacture. There are management issues. In addition, relatively large protrusions are often formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer.

Furthermore, if the surface of the support is simply roughened regularly,
Since the light-receiving layer is deposited along the uneven shape of the surface of the support, the inclined surface of the unevenness of the support and the inclined surface of the unevenness of the light-receiving layer become parallel, and in that part, the incident light is directed to the bright area. , which results in dark areas, and because of the non-uniformity of the layer thickness of the photoreceptive layer, a striped pattern of light and darkness appears in the entire photoreceptive layer. Therefore, simply by regularly roughening the surface of the support, it is not possible to completely prevent the occurrence of interference fringes.

Also, when a multilayered light-receiving layer is deposited on a support whose surface is regularly roughened, specular reflection light on the support surface and
In addition to the interference with the reflected light on the surface of the light-receiving layer, there is also interference due to the reflected light at the interface between each layer, so the degree of interference fringe pattern development in the single-layered light-receiving member becomes even more complicated.

[Purpose of the invention]

The object of the present invention is to eliminate the above-mentioned problems and to provide a light-receiving member having a light-receiving layer mainly composed of a-8i, which satisfies various demands.

That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent light fatigue resistance, and exhibit no deterioration phenomenon even after repeated use. To provide a light-receiving member having a light-receiving layer made of a-8T, which has excellent durability and moisture resistance, has no or almost no residual potential, and is easy to manage in production. be.

Another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8t, which has high photosensitivity in the entire visible light range, has excellent matching properties with semiconductor lasers, and has a fast photoresponse. It is about providing.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8t, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
A-
An object of the present invention is to provide a light-receiving member having a light-receiving layer made of 3t.

Still another object of the present invention is to be suitable for image formation using coherent monochromatic light, to be free of interference fringes and spots during reversal development even after repeated use over a long period of time, and to be free from image defects and image formation. To provide a light-receiving member having a light-receiving layer made of A-8T, capable of obtaining a high-quality image with no blur, high density, clear halftones, and high resolution. It is in.

[Structure of the invention]

The present inventors have conducted intensive research to overcome the above-mentioned problems with conventional light-receiving members and achieve the above-mentioned objectives, and as a result, have obtained the following knowledge, and have developed the present invention based on this knowledge. It was completed.

That is, the present invention provides a first layer made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms, on a support, silicon atoms, oxygen atoms, carbon atoms, and and a second layer made of an amorphous material containing at least one selected from nitrogen atoms, the first layer comprising at least one of germanium atoms and tin atoms. and a layer containing neither germanium atoms nor tin atoms, in order from the support side,
The present invention relates to a light-receiving member in which the surface of the support has a concavo-convex shape formed by a plurality of spherical trace depressions, and a plurality of fine concavo-convex shapes are further provided within the spherical trace depressions.

By the way, the findings obtained by the present inventors as a result of extensive research are summarized as follows: In a light-receiving member having a plurality of layers on a support, the surface of the support is provided with irregularities formed by a plurality of spherical trace depressions, Furthermore, by providing a plurality of finer uneven shapes within the spherical trace recess, the problem of interference fringes that appear during image formation can be significantly resolved.

This knowledge is based on the facts obtained by the present inventors through nine different experiments.

This will be explained below using drawings to facilitate understanding.

FIG. 1 is a schematic diagram showing the layer structure of a light-receiving member 100 according to the present invention, which has an uneven shape formed by a plurality of minute spherical trace depressions, and further includes a plurality of microscopic trace depressions within the spherical trace depressions. A light-receiving member is shown in which a light-receiving layer consisting of a first layer 102 and a second layer 103 is provided on a support 101 having an uneven shape and along the slope of the unevenness.

This is a diagram for

FIG. 3 is an enlarged view of a part of a conventional light-receiving member in which a multi-layered light-receiving layer is deposited on a support whose surface is regularly roughened. In the figure, 301 indicates the first layer, 302 the second layer, 303 the free surface, and 304 the interface between the first layer and the second layer. As shown in FIG. 3, when the surface of the support is simply roughened regularly by means such as cutting, the light-receiving layer is usually formed along the uneven shape of the surface of the support. The inclined surface of the unevenness on the surface of the support and the inclined surface of the unevenness of the light-receiving layer are in a parallel relationship.

Due to this, for example, the photoreceptive layer is the first layer 301.
In a light-receiving member having a multilayer structure consisting of two layers, ie, a first layer and a second layer 302, the following problems regularly arise, for example.

That is, since the interface 304 between the first layer and the second layer and the free surface 303 are in a parallel relationship, the directions of the reflected light R1 at the interface 304 and the reflected light R1 at the free surface match, and the second Interference fringes occur depending on the layer thickness.

FIG. 2 is an enlarged view of a part of a light-receiving member in which a multi-layered light-receiving layer is deposited on a support having an uneven shape formed by a plurality of spherical trace depressions. In the figure, 2
01 is the first layer, 202 is the second layer, 203 is the free surface, and 204 is the interface between the first layer and the second layer. As shown in FIG. 2, when the surface of the support is provided with an uneven shape formed by a plurality of minute spherical trace depressions, the light-receiving layer provided on the support is deposited along the uneven shape, so that the first The interface 20 between the layer 201 and the second layer 202
4 and the free surface 203 are each formed into an uneven shape with spherical trace depressions along the uneven shape of the support surface. The curvature of the spherical trace depression formed at the interface 204 is R
+, If the curvature of the spherical trace depression formed on the free surface is R2, then R1 and R2 are R1 + R2, so the interface 2
The reflected light at 04 and the reflected light at the free surface 203 have different reflection angles, that is, θ1 in FIG.
θ2 is θ1-kFθ2, and the direction is different, and the wavelength shift, which is expressed as 21-2-right using the stone 22.23 shown in Figure 2, is not constant but changes. Therefore, shearing interference corresponding to the so-called Newton's ring phenomenon occurs, and the interference fringes become dispersed within the depression. As a result, even if interference fringes appear microscopically in the image appearing through such a light-receiving member, they are not visible to the naked eye.

In other words, the use of a support having such a surface shape is for a light-receiving member having a multi-layered light-receiving layer formed thereon, and the light that has passed through the light-receiving layer is transmitted to the layer interface and the support. Reflection on the surface and their interference effectively prevent the formed image from having a striped pattern, leading to a light-receiving member capable of forming an excellent image.

FIG. 4 is an enlarged view of a part of the support surface in the light-receiving member of the present invention shown in FIG.

As shown in FIG. 4, the surface of the support in the light-receiving member of the present invention has further minute irregularities or a group of irregularities 402 formed on a part or the entire surface within the spherical trace recess 401. When such finer asperities or a group of asperities 402 are provided, in addition to the interference prevention effect described using FIG. The occurrence of interference fringes can be more reliably prevented.

By the way, in the prior art, as described above, the surface of the support is randomly roughened to cause diffused reflection and to prevent the occurrence of interference fringes.

However, in such a case, not only is it not possible to obtain a sufficient effect of preventing the occurrence of interference fringes, but also problems arise when cleaning is performed using, for example, a blade after image transfer. That is, the surface of the photoreceptive layer is
Because unevenness occurs along the unevenness provided on the support,
The blade mainly hits the convex and convex portions of the light-receiving layer, resulting in poor cleaning performance and increased abrasion between the convex portions of the photo-receiving layer and the surface of the blade, resulting in poor durability of both, which poses a problem.

On the other hand, in the light-receiving member of the present invention, the minute unevenness that causes the scattering effect is present in the spherical trace depression (recess), so that the blade comes into contact with the recess of the light-receiving layer during cleaning. This also has the advantage that no large load is applied to the blade or the surface of the photoreceptive layer.

Now, the curvature and width of the irregularities formed by the spherical trace depressions provided on the support surface of the light-receiving member of the present invention, and the height of the finer irregularities within the spherical trace depressions are determined in the light-receiving member of the present invention. This is important for efficiently obtaining the effect of preventing the occurrence of interference fringes. The present inventors have investigated the following points as a result of various experiments.

That is, the curvature of the uneven shape due to the spherical trace depression is expressed as R1 width is D
In this case, if the following formula is satisfied, 0.5 or more Newton rings due to shearing interference will exist in each trace depression. Furthermore, if the following formula is satisfied, one or more Newton rings due to shearing interference will exist in each trace depression.

For this reason, in order to disperse the interference fringes generated throughout the light receiving member into each trace depression and to prevent the occurrence of interference fringes in the light receiving member, the above-mentioned frequency should be set to 0.03.
5, preferably 0.055 or more.

This is because, when 100 is larger than 0.5, the width of the depression becomes relatively large, resulting in a situation where image unevenness and the like are likely to occur.

In addition, the width of the unevenness due to the trace depression is at most 500
It is desirable that the thickness be 1 tm 8 degrees, preferably 200 μm or less, more preferably 100 μm or less. D is 500μ
If it exceeds m, image unevenness is likely to occur, and
There is a possibility that the resolution may be exceeded, and in such a case, it becomes difficult to obtain an efficient effect of preventing interference fringes.

The height of the minute irregularities formed in the spherical trace depression, that is, the surface roughness rrrl of the spherical trace depression is 0.5 to 20μ.
The range is preferably m. If rmax is less than 0.5 degrees, a sufficient scattering effect cannot be obtained;
If it exceeds 0 μm, the minute irregularities within the spherical trace depressions become too large compared to the irregularities caused by the spherical trace depressions, and the trace depressions no longer have a spherical shape, so that the effect of preventing the occurrence of interference fringes is insufficient. You won't be able to get it. Furthermore, this is not preferable because it increases the non-uniformity of the light-receiving layer provided on such a support, making image defects more likely to occur.

The photoreceptive layer formed on a support having a specific surface shape as described above consists of a first layer and a second layer, and the second layer is made up of silicon atoms in order from the support side. , at least one of a germanium atom or a tin atom, and preferably at least one of a hydrogen atom or a halogen atom.
Ge, Sn) (H,X)J. ] and an amorphous material [hereinafter referred to as [a -8t (H,X
)j. ], and the second layer may further contain a substance that controls conductivity. Particularly preferably, it has a charge injection blocking layer containing a substance that controls conductivity as one of its constituent layers, or it has l″t/ and a barrier layer as one of its constituent layers.

Further, the second layer is an amorphous material [hereinafter referred to as “a-
It is written as 8i(0*C9N)(H,X). ] Consists of.

Regarding the preparation of the first layer and the second layer of the light-receiving member of the present invention, in order to efficiently achieve the above-mentioned objects of the present invention, it is necessary to accurately control the layer thickness at an optical level. Therefore, vacuum deposition methods such as glow discharge method, sputtering method, and ion blating method are usually used, but in addition to these methods, photo-CVD method, thermal CVD method, etc. can also be adopted.

Hereinafter, the specific contents of the light-receiving member of the present invention will be explained according to the illustrated examples, but the light-receiving member of the present invention is not limited to these examples.

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention, in which 100 is the light-receiving member, 101 is the support, 102 is the first layer, 102 ' is a layer containing at least one of germanium atoms or tin atoms, 102'' is a layer containing neither germanium atoms nor tin atoms, 103 is a second layer, and 104 is a free-cloth C
11i is shown.

Support The support 101 in the light-receiving member of the present invention has a surface having irregularities smaller than the resolving power required for the light-receiving member, and the irregularities are due to a plurality of spherical trace depressions, and , a plurality of even smaller irregularities are formed within the spherical trace depression.

Below, the surface shape of the support in the light-receiving member of the present invention and a preferred manufacturing example thereof will be explained with reference to FIGS. 4 and 5. , but is not limited to these.

FIG. 4 schematically shows a typical example of the surface shape of the support in the light-receiving member of the present invention by partially enlarging a portion of its uneven shape.

In FIG. 4, 401 is a support, 402 is a support surface,
Reference numeral 403 indicates an uneven shape formed by a spherical trace depression, and 404 indicates an even finer uneven shape provided within the spherical trace depression.

Furthermore, FIG. 4 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support, and 403' indicates a rigid sphere having minute irregularities 404' on the surface. By letting the sphere 403' fall naturally from a predetermined height position from the support surface 402 and colliding with the support surface 402, an uneven shape 403 is formed by a spherical trace depression having minute unevenness 404 in the depression. It shows. Then, by using a plurality of rigid spheres 403' having approximately the same diameter R' and dropping them simultaneously or sequentially from the same height h, approximately the same curvature R and y are applied to the support surface 402. A plurality of spherical trace depressions 403 having the same width D can be formed.

FIG. 5 shows some typical examples of supports having irregularities formed by a plurality of spherical trace depressions on the surface as described above. In the figure, 501 is a support;
Reference numeral 502 denotes the surface of the support, and 503 indicates a spherical trace depression having a plurality of finer uneven shapes within the hollow (in addition, in FIG. 5, a plurality of finer uneven shapes formed within the spherical trace depression are not shown) (However, it is assumed that each of the spherical trace depressions 503 has a finer uneven shape.)
503' is a rigid sphere having a minute unevenness on its surface (similarly, the minute unevenness on the surface is not shown, but it is assumed that the surface of the rigid sphere has a minute unevenness) .) are shown respectively.

In the example shown in FIG. 5(4), the surface 502 of the support 501
A plurality of spheres 503' having approximately the same diameter are located at different parts of the body.

503', . . . are regularly dropped from approximately the same height to form a plurality of trace depressions 5 having approximately the same curvature and approximately the same width.
03.503, . . . are formed densely so as to overlap each other to form a regularly uneven shape. In this case, the depressions 503, 503, . . .
In order to form the spheres 503' and 5, the timings of the collisions of the spheres 503' with the support surface 502 are shifted from each other.
Needless to say, it is necessary to allow the objects 03', . . . to fall naturally.

Further, in the example shown in FIG. 5(B), two types of spheres 503', 503', etc. having different diameters are dropped from approximately the same height or different heights, and the surface of the support body 501 is 5
02, a plurality of depressions 503 with two types of curvature and two types of width.
503. ... are formed densely so as to overlap each other to form irregularities with irregular heights on the surface.

Furthermore, in the example shown in FIG. 5(C) (front view and cross-sectional view of the surface of the support), a plurality of spheres 503', 503', . A plurality of depressions 503, 503, which are irregularly dropped from approximately the same height and have approximately the same curvature and multiple types of widths.
They are made to overlap each other to form irregular irregularities.

As described above, in order to form an uneven shape by spherical trace depressions on the surface of the support of the light-receiving member of the present invention, and to form a plurality of finer uneven shapes within the spherical trace depressions, A preferred example is a method in which a rigid sphere with minute irregularities is dropped onto the surface of a support. By appropriately selecting various conditions such as the shape and size of the surface irregularities or the amount of rigid spheres to be dropped, a spherical trace depression having a desired average curvature and average width can be formed on the support surface, or within the spherical trace depression. It is possible to form irregularities of a desired size and shape at a predetermined density. That is, by selecting the above conditions, it is possible to control the height and pitch of the unevenness formed on the surface of the support, or the height and pitch of the unevenness of even minute unevenness formed in the concave part of the unevenness. It is possible to freely adjust the pitch etc. according to the purpose, and it is possible to obtain a support having a desired uneven shape.

In order to make the support of the light-receiving member have an uneven surface, a method has been proposed in which cutting is performed using a diamond cutting tool using a lathe, milling machine, etc., and although this is a reasonably effective method, This method requires the use of cutting oil, the removal of chips that inevitably occur during cutting, and the removal of cutting oil that remains on the cutting surface.In the end, processing is complicated and efficiency is reduced. However, in the present invention, since the uneven surface shape of the support is formed by the spherical trace depressions as described above, the above-mentioned problems can be completely eliminated and the support can have the desired uneven surface. can be created efficiently and easily.

The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A6.
Cr, Mo, Au, Nb, Ta.

Examples include metals such as V%'ri, pt, pb, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, paper, and the like. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is glass, NiCr, A,
g, Cr, Mo, Au, Ir, Nb, Ta, V,
Ti, Pt1Pd, InzOs, 5n02.
Conductivity can be imparted by providing a thin film made of ITO (In*Os+SnO*), or if it is a synthetic resin film such as polyester film, NiCr
%k13 %Ag %Pb, Zn %Ni.

Au, Cr, Mo, Ir, Nb, Ta, V, TA, Pt
A thin film of a metal such as the above is provided on the surface by vacuum evaporation, electron beam evaporation, slatting, etc., or the surface is laminated with the above metal to impart conductivity to the surface. The shape of the support can be any shape such as a cylinder, a belt, a plate, etc., and the shape can be determined as appropriate depending on the purpose and desire. For example, if the light-receiving member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferable to use an endless belt or a cylindrical shape for continuous high-speed copying. The thickness of the support is appropriately determined so as to form a desired light-receiving member, but if flexibility is required as a light-receiving member, the thickness should be determined within a range that allows the support to fully perform its function. can be made as thin as possible. However, from the viewpoint of the structure and handling of the support, mechanical strength, etc., it is usually 10 μm.
This is considered to be the above.

Next, when the light-receiving member of the present invention is used as a light-receiving member for electrophotography, an example of an apparatus for manufacturing the support surface will be described with reference to FIG. 6(A) and FIG. 6a3). However, the present invention is not limited thereto.

As a support for a light-receiving member for electrophotography, an aluminum alloy or the like is subjected to ordinary extrusion processing to form a boathole tube or a mandrel tube, and the drawn tube obtained by further drawing and coloring is heat-treated and conditioned as necessary. A cylindrical (cylinder-shaped) substrate that has been subjected to a quality treatment, etc. is used, and a sixth
(A), (B) i! ! ! ] Using the manufacturing equipment shown in
An uneven shape is formed on the surface of the support.

Examples of the spheres used to form the above-mentioned uneven shape on the surface of the support include various rigid spheres made of metals such as stainless steel, aluminum, steel, nickel, and shinko, ceramics, and plastics. Rigid spheres made of stainless steel and steel are desirable for reasons such as flexibility and cost reduction. The hardness of such a rigid sphere may be higher or lower than the hardness of the support, but if the sphere is to be used repeatedly, it is preferably higher than the hardness of the support.

In order to form the above-mentioned specific shape on the surface of the support of the present invention, it is necessary to use each of the above-mentioned hard spheres having an uneven surface. For example, methods that apply plastic processing such as embossing and corrugation, methods that form unevenness by mechanical processing such as roughening methods such as surface roughening method (Nashiji method), and chemical processing such as etching with acid or alkali. It can be produced by processing a rigid sphere using a method of forming irregularities using a method of forming irregularities. Furthermore, the surface of the rigid sphere with the unevenness formed in this way is subjected to depolishing, chemical polishing, finish polishing, etc., or anodized film formation, chemical conversion film formation, plating, waxing, painting, vapor deposition film formation, CVD method. The uneven shape (height), hardness, etc. can be adjusted as appropriate by surface treatment such as film formation.

Figure 6, 03) is a schematic cross-sectional view for explaining an example of a manufacturing apparatus.

In the figure, 601 is an aluminum cylinder for making a support.
The surface of the cylinder 601 may be finished in advance to an appropriate degree of smoothness.

The cylinder 601 is pivotally supported by a rotating shaft 602.
It is driven by a suitable driving means 603 such as a motor, and is rotatable approximately around an axis.

Reference numeral 604 denotes a rotating container that is supported by a bearing 602 and rotates in the same direction as the cylinder 601. Inside the container 604, there are many rigid spheres 605 having an uneven surface.
is accommodated. The rigid sphere 605 is supported by a plurality of protruding ribs 606 provided on the inner wall of the rotating container 604, and is transported to the upper part of the container by the rotation of the rotating container 604. When the rotational speed of the rotating container is at a certain appropriate speed, the rigid sphere 605 that has been transported along the container wall to the top of the container falls onto the cylinder 601 and collides with the cylinder surface, forming a trace depression on the surface. .

Incidentally, holes are uniformly bored in the wall of the rotating container 604, and cleaning liquid is sprayed from a shower pipe 607 provided outside the container 604 when the container 604 is rotated, so that the cylinder 601, the rigid sphere 605, and the rotating container 604 can be cleaned. You can also make it look like this. In this case, dust and the like that have adhered to each other due to static electricity caused by contact between the rigid spheres or between the rigid sphere and the rotary container are washed out of the rotary container 604, and a desired support body free of dust and the like is washed out. can be formed. It is necessary to use a cleaning liquid that does not cause uneven drying or dripping, and for this reason, it is preferable to use a nonvolatile substance alone or a mixture with a cleaning liquid such as hatrichloroethane or trichlorethylene.

First layer In the light-receiving member of the present invention, the first layer 102 is provided on the support 101 described above, and the second layer is provided on the support 101.
From the 01 side, germanium atoms (Ge) or tin atoms (
a-8T [hereinafter referred to as r a-8L (Ge, S
n) (H,X) j. ] and a-8i [hereinafter referred to as
It is written as r a −St (H,X)J. ] It has a multilayer structure in which layers 102'' are laminated in order.

The light-receiving layer 102 can further contain a substance for controlling conductivity, if necessary.

Specific examples of the halogen atom (X) contained in the first layer include fluorine, chlorine, bromine, and iodine,
Particularly preferred are fluorine and chlorine. Then, the hydrogen atoms contained in the first layer 102 (
The amount of H) or the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 4.
0 atomic%, preferably 5-30 atoms
It is desirable to set it as ic%.

Furthermore, in the uninvented light-receiving member, the first j- layer thickness is one of the important factors for efficiently achieving the object of the present invention, and is one of the important factors in ensuring that the light-receiving member has desired characteristics. As given above, it is necessary to pay sufficient attention when designing the light-receiving member, and the thickness is usually 1 to 100μ, preferably 1 to 100μ.
80tt, more preferably 2 to 50μ.

Incidentally, the purpose of containing germanium atoms and/or tin atoms in the first layer of the light-receiving member of the present invention is mainly to improve the absorption spectrum characteristics of the light-receiving member on the emission wavelength side.

That is, by containing germanium atoms and/or tin atoms in the first layer, the light-receiving member of the present invention exhibits various excellent properties, especially in the visible light region. It has excellent photosensitivity and fast photoresponsiveness to light in the entire range of wavelengths from relatively short wavelengths to relatively short wavelengths. This is particularly noticeable when a semiconductor laser is used as a light beam.

In the first layer of the light-receiving member of the present invention, germanium atoms and/or tin atoms are contained in a uniformly distributed state in the layer 102' in contact with the support 101, or
Or it can be contained in a non-uniform distribution state (
Here, the uniform distribution state means that the distribution concentration of germanium atoms and/or tin atoms is uniform in the plane direction parallel to the support surface of the layer 102', and is also uniform in the layer thickness direction from J to 102'. Also, the non-uniform distribution state means that the distribution concentration of germanium atoms and/or tin atoms is uniform in the plane direction parallel to the support surface of the layer 102'; This means that the layer is non-uniform in the thickness direction. ).

In the 1 m 102' of the present invention, it is particularly desirable that germanium atoms and/or tin atoms be contained in a state where they are more distributed on the support side than on the layer 102# side. Distribution of germanium atoms and/or tin atoms at the body side end 1
11i! By making the wavelength extremely large, when a long wavelength light source such as a semiconductor laser is used, the layer 102'
It is possible to substantially completely absorb the light at the surface of the support, thereby preventing interference caused by light reflected from the surface of the support.

In addition, in the light-receiving member of the present invention, since the amorphous materials constituting the layer 102' and the layer 102# each have a common constituent element of silicon atoms, chemical stability is achieved at the laminated interface. Sufficient gender is ensured.

Hereinafter, germanium atoms contained in the layer 102' and/or
Or some typical examples of the distribution state of tin atoms in the layer thickness direction of the layer 102', taking germanium atoms as an example,
This will be explained with reference to Figures 15 to 15.

7 to 15, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the layer thickness of the layer 102', t
11 indicates the position of the end of the layer 102' on the side of the support, and 11 indicates the position of the end surface of the layer 102'' on the side opposite to the support.

That is, the layer 102' containing germanium atoms has tB
The layer is formed more toward the tT side than the tT side.

In addition, in each figure, the layer thickness and concentration are shown in an extreme form because if the values are shown as they are, the differences between each figure will not be clear, and these figures are only for easy understanding. This is a schematic diagram for explanation.

FIG. 7 shows the first r-type side of the distribution state of germanium atoms contained in the layer 102' in the layer thickness direction.

In the example shown in FIG. 7, the distribution concentration C of germanium atoms is equal to the concentration CI up to a position 11 from the interface position tm where the support surface 4102' contacts the support surface where the layer 102' containing germanium atoms aM is formed. Germanium atoms are contained in the layer 102' while maintaining a constant value, and from the position t1, the concentration is gradually and continuously reduced from the concentration C2 to the interface position tr. At the interface position tT, the distribution degree C of germanium atoms is substantially zero.

(Here, "substantially zero" means that the amount is less than the detection limit.) In the example shown in FIG. A distribution state is formed in which the concentration gradually and continuously decreases from 1 to 2 to reach the concentration C4 at the position tT.

In the case of FIG. 9, from position tB to position tT, the distribution concentration C of germanium atoms is constant at the concentration Cs, and gradually and continuously decreases between position t2 and position tT. At t↑, the distribution #HealthC is substantially zero.

In the case of Fig. 10, the distribution concentration C of germanium atoms is gradually and continuously decreased from the position tB to the position t↑, starting from the concentration WCm, and rapidly and continuously decreasing from the position bjtt1. It is substantially zero at fit↑.

In the example shown in FIG. 11, the distribution concentration C of germanium atoms is the concentration C1 between the position t11 and the position t4.
is a constant value, and the distribution density C is zero at the position t↑. Between position t4 and position tT, the distribution density C is linearly decreased from position t4 to position 11.

In the example shown in FIG. 12, the distribution density C takes a constant value of density C8 up to position #ts, and
, up to position t, the distribution state is such that the concentration decreases linearly from e degrees C0 to concentration Cゎ.

In the example shown in FIG. 13, the distribution concentration fc of germanium atoms is linearly decreased from the concentration Co until reaching position 11, and reaches zero.

In FIG. 14, from position tn to position t6, the distribution concentration C of germanium atoms is linearly decreased from concentration C12 to concentration Cr5i, and from position t6 to position t
An example is shown in which the concentration Cts is set to a constant value between T and T.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a concentration C14 at the position tu, and at first it decreases slowly from this concentration C14 until reaching the position ty, and then rapidly decreases near the position t7. The density is reduced to C15 at the position C15.

Between the position tγ and the position t8, the position fit is rapidly decreased at first, and then slowly and gradually decreased.
At ts, the concentration becomes Cta, and between the positions t and ts, it gradually decreases, and at the position t9, the concentration C1□
leading to. Between position t9 and position tT, the concentration C1
γ is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 7 to 15, some typical examples of the distribution state of germanium atoms and/or tin atoms contained in the layer 102' in the layer thickness direction, the photoreceptor of the present invention In the member, on the support side, there is a part where the distribution concentration C of germanium atoms and/or tin atoms is high, and on the interface tT side, there is a part where the distribution concentration C is considerably lower than on the support side. It is desirable that the constituent layer 102' has a distribution of atoms and/or tin atoms.

That is, the layer 102' constituting the light receiving member in the present invention
Preferably, as described above, the support has a localized region containing germanium atoms and/or tin atoms at a relatively high concentration on the side of the support.

In the light-receiving member of the present invention, the localized region can be explained using the symbols shown in FIGS.
It is more desirable that the distance be within 5μ.

The localized region may be a full-layer region up to 5 μm thick from the interface position ta.

It may also be part of the layer area.

Whether the localized region is a part or all of the layer 102' is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region contains germanium atoms or/
As for the distribution state of tin atoms in the layer thickness direction, the maximum value CmaK of the distribution concentration of germanium atoms and/or tin atoms is preferably 1000 atoms with respect to silicon atoms.
ic ppm or more, more preferably 5000 atoms
c ppm or more, optimally I x 10' atoms
It is desirable that the layers be formed so that a distribution state of cppm or more can be achieved.

That is, in the light-receiving member of the present invention, the layer 102' containing germanium atoms and/or tin atoms has a layer thickness of within 5 μm from the support side (layer region of 5 μ layers from tn).
It is preferable that the maximum value Cma of the distribution concentration exists at .

In the light receiving member of the present invention, the content of germanium atoms and/or tin atoms contained in the layer 102' is as follows:
It is necessary to appropriately decide according to the desire to efficiently achieve the object of the present invention, and usually 1 to 6 x 10' at
omic ppm, preferably 10-3
10' atomic ppm, more preferably I
X 10" ~ 2 X 10' atomic ppm
shall be.

Further, in the light-receiving member of the present invention, the first layer can contain a substance for controlling conductivity in the entire layer region or in a part of the layer region in a uniformly or non-uniformly distributed state.

Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, which are atoms belonging to group Ⅰ of the periodic table (hereinafter simply referred to as ``group Ⅰ'') that give P-type conductivity.
"group atoms". ), or atoms belonging to Group Ⅰ of the periodic table (hereinafter simply referred to as "Group V atoms") that provide n-type conductivity are used. Specifically, the Group Ⅰ atoms include B (boron), M (aluminum), and Ga (gallium).
, In (indium), T, 6 (thallium), etc., but preferable ones are B, Ga, etc.
It is. Further, examples of the Group Ⅰ atoms include P (phosphorus), As (arsenic), sb <antimony), Bi (bismane), etc., but particularly preferred are p and sb.

When the first layer of the present invention contains Group 1 atoms or Group V atoms, which are substances that control conductivity, it is determined whether they are contained in the entire layer region or in a part of the layer region. As will be described later, the amount to be included will vary depending on the intended purpose or expected effect.

That is, when the main purpose is to control the conductivity type and/or conductivity of the first layer, it is contained in the entire layer region of the first layer. The content of group atoms may be relatively small, usually 1×10 to I
x 10 atomic ppm, preferably 5 x 10 to 5 x 10'' atomic ppm, optimally 1 x 10°' to 2 x 10'' atomic ppm
It is m.

In addition, the group 1 atoms or group Ⅰ atoms may be contained in a uniform distribution state in a part of the layer region in contact with the support, or the distribution concentration of group Ⅰ atoms or group Ⅰ atoms in the layer thickness direction may be When it is contained in a high concentration on the side in contact with the support, a constituent layer containing a group 9 atom or a group Ⅰ atom or a layer containing a group 1 atom or a group This layer region functions as a charge injection blocking layer. That is, when the group Ⅰ atoms are contained, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the movement of electrons injected from the support structure into the photoreceptor layer is more effectively controlled. In addition, when the group Ⅰ atoms are contained, when the free surface of the photoreceptive layer is charged to e polarity, it is injected from the support side into the photoreceptor layer. The movement of holes can be more efficiently blocked. In such a case, the content is relatively large, specifically, 30 to 5 x 10' atomic
ppm, preferably 50 to I x 10' atoms
ic ppm, optimally lXl0" to 5 X 10"
Ato and e side ppm. Furthermore, in order to efficiently exhibit the effect of the charge injection blocking layer, it is necessary to set the layer thickness of the layer or layer region provided at the end of the group (III) atoms or the support body containing the group (III) atoms to t and 1. When the layer thickness of the photoreceptive layer is T, it is desirable that the relationship t/T≦0.4 holds true, and more preferably the value of this relational expression is 0.35 or less, optimally 0.3 or less. It is desirable to make it so that

Further, the layer thickness t of the layer or layer region is generally 3
10-” to 10μ, preferably 4×10
-'' to 8μ, optimally 5×10−” to 5μ.

Next, the amount of Group A atoms or Group I atoms contained in the first layer is relatively large on the support side, and decreases from the support side toward the second layer side, and Some typical examples of distribution of Xia group atoms or V group atoms in a relatively small amount or substantially close to zero near the interface with the layer are shown in FIGS. No. U
Although explained by the figures, the present invention is not limited to these examples. In each figure, the horizontal axis represents the distribution concentration C of Group V atoms or Group V atoms, the vertical axis represents the layer thickness of the first layer, and tB represents the interface position between the support and the first layer. t
T indicates the position of the interface between the first layer and the second layer.

FIG. 16 shows a first typical example of the distribution state of Group 1 atoms or Group Ⅰ atoms contained in the first layer in the layer thickness direction. In this layer, the interface position t! where the first layer containing Group 1 atoms or Group V atoms and the support surface are in contact with each other. From ttB to position ti1, the distribution ratio fc of group 1 atoms or group Ⅰ atoms takes a constant value of 01, and from position t1 to the interface position tT with the second layer, group Ⅰ atoms or group Ⅰ atoms The distribution concentration VC of atoms decreases continuously from the concentration C2, and the interface position 11
, the distribution concentration C of group 1 atoms or group Ⅰ atoms is 0.
It becomes 3.

FIG. 17 shows one other typical example.

In this layer, the first layer contains the first group atoms or the second group atoms.
The distribution of group atoms 1a degree C decreases continuously from the concentration c4 from position &ttB to position 11, and the position flttt
The density becomes C3.

In the example shown in FIG. 18, from position 0jtb to position t2, the distribution concentration C of group ■ atoms or group ■ atoms maintains a constant value of concentration C6, and from position t2 to the position meter, the distribution concentration C of group ■ atoms maintains a constant value of concentration C6. The distribution concentration C of the atoms or Group Ⅰ atoms gradually and continuously decreases from the concentration Cγ, and at the position tT, the distribution concentration C of the Group 1 atoms or Group Ⅰ atoms becomes substantially zero. However, here, "substantially zero" refers to a case where the amount is less than the detection limit amount.

In the example shown in FIG. 19, the distribution concentration C of group II atoms or group V atoms is from position tB to position fit tt.
The concentration gradually decreases continuously from C8, and at position tT, the distribution concentration C of Group II atoms or Group V atoms becomes substantially zero.

In the example shown in FIG.
9, and between the position t3 and the position t↑, the density decreases in a negative scale from the density G to the density C+o.

In the example shown in FIG. 21, the distribution concentration C of Old Group atoms or Group V atoms is at a constant value of concentration C11 from position tn to position t4, and from position t4 to position tT, the concentration Ctz is constant. It decreases linearly until the concentration reaches C+3.

In the example shown in FIG. .

In the example shown in FIG.
It decreases in a linear function from s to the concentration Cps, and maintains a constant value of concentration C+g from position to position tr.

Finally, in the example shown in the feed diagram, the distribution concentration C of Group 1 atoms or Group V atoms is the concentration CI? From the position tB to the position t6, the concentration initially decreases slowly from C17, then rapidly decreases near the 5th position t6, and becomes the concentration C+a at the position t6. Next, from position t6 to position t7, the concentration decreases rapidly at first, and then gradually decreases, and reaches the concentration C1e at position t7. Further, the concentration gradually decreases extremely slowly between the positions t7 and t8, and reaches the concentration C20 at the position tI. Furthermore, from position t to position t↑, the concentration C2
It gradually decreases from o to substantially zero.

As in the examples shown in FIGS. 16 to U, the distribution concentration C of Arashi group atoms or V group atoms is on the side closer to the support side of the first layer.
If the concentration distribution C has a portion with a high concentration on the interface side with the second layer, and has a portion with a considerably low concentration or a portion with a concentration substantially close to zero, the distribution concentration C has a portion with a high concentration close to the support side. By providing a localized region in which the distribution concentration of group (III) atoms or group (III) atoms is relatively high in the part, preferably by providing the localized region within 5μ from the interface position in contact with the support surface. The above-mentioned effect that the layer region having a high distribution concentration of Group Ⅰ atoms or Group Ⅰ atoms forms a charge injection blocking layer can be achieved even more efficiently.

As mentioned above, regarding the distribution state of Group ■ atoms or Group ■ atoms,
Although the effects of each have been described individually, in order to obtain a light-receiving member having characteristics that can achieve the desired purpose, the distribution state of these Group 1 atoms or Group II atoms and the content in the first layer are important. The amount of Group 1 atoms or Group V atoms used in appropriate combinations as necessary means that
Needless to say. For example, when a charge injection blocker/m is provided at the end of the first layer on the support side, a conductivity controlling substance contained in the charge injection blocker layer is added to the first layer other than the charge injection blocker layer. The layer may contain a substance that controls conductivity of a polarity different from the polarity of the charge injection blocking layer, or the substance that controls conductivity of the same polarity may be contained in an amount much smaller than that contained in the charge injection blocking layer. It may also be included.

Furthermore, in the light-receiving member of the present invention, as a constituent layer provided at the end on the support side, instead of the charge injection blocking layer,
A so-called barrier layer made of an electrically insulating material can also be provided, or both the barrier layer and the charge injection blocking layer can be constituent layers. Materials constituting the barrier 1- include Aβ203, SiO2, 5ixN4
Inorganic electrical insulating materials such as inorganic electrical insulating materials such as polycarbonate, and self-organic electrical insulating materials such as polycarbonate can be mentioned.

Second layer The second layer 103 of the light-receiving member of the present invention is a layer provided on the above-described first layer 102 and has a free surface 104, that is, a surface layer, and is composed of oxygen atoms, carbon atoms or nitrogen atoms. Amorphous silicon containing at least one of the atoms in a uniform distribution state [hereinafter referred to as ra-8i (0
,C,N) (H.

It is written as XN. ].

The purpose of providing the second layer 103 in the light receiving member of the present invention is to
The purpose is to improve moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, durability, etc. Alternatively, this can be achieved by containing at least one of nitrogen atoms.

Furthermore, in the light receiving member of the present invention, each of the amorphous materials constituting the first layer 102 and the second layer 103 is
Since they have a common constituent atom, silicon atoms, chemical stability can be ensured at the interface between the first layer 102 and the second layer 103.

Oxygen atoms, carbon atoms, and nitrogen atoms are contained in the second layer 103 in a uniformly distributed state, and as the amount of these atoms contained increases, the above-mentioned characteristics improve. However, too much will reduce the layer quality and the electrical and mechanical properties. For this reason, the content of these atoms is usually 0.001 to 90 ato
mic%, preferably 1-90 atomic f
b. Optimally 10 to 80 atomic %.

It is desirable that the second layer also contain at least one of hydrogen atoms or halogen atoms, and the amount of hydrogen atoms (H) contained in the second layer or the ts ratio of halogen atoms (X) The sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 40 atomic '4,
Preferably 5 to 30 atomic units, optimally 5
~25 atomic.

The second layer 103 Vi needs to be formed carefully to obtain desired characteristics. That is, silicon atoms,
The form of a substance containing at least one selected from oxygen, carbon, and nitrogen atoms, or furthermore, hydrogen and/or halogen atoms depends on the content of each constituent atom and other production conditions. ranges from the Shao-crystalline state to the amorphous state, electrical properties range from conductivity to semiconductivity to insulating properties, and photoelectric properties range from photoconductive to non-photoconductive properties. Therefore, it is important to select the content of each constituent atom, production conditions, etc. so that the second layer 103 can be formed with desired characteristics M according to the purpose.

For example, when the second layer 103 is provided with the main purpose of improving electrical voltage resistance, the amorphous material constituting the second layer 103 has a remarkable electrically insulating behavior under the usage conditions. Form. In addition, when the second layer 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the amorphous material constituting the second layer 103 has the above-mentioned degree of electrical insulation. Although it alleviates it to some extent,
It is formed to have a certain degree of sensitivity to the irradiating light.

Furthermore, in the present invention, the layer thickness of the second layer is also one of the important factors for efficiently achieving the purpose of the present invention, and is determined as appropriate depending on the intended purpose. , the oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, hydrogen atoms αL to be contained in the layer, or the characteristics required for the second layer, it is necessary to determine them based on mutual and organic relationships. Furthermore, it is also necessary to consider economic efficiency, which also takes into account productivity and mass production. For this reason, the thickness of the second layer is usually 3 x 10-' to 30 microns, more preferably 4 x 10-' to 20 microns, particularly preferably 5 x 10-' to 10 microns.

By having the above-described layer structure, the light-receiving member of the present invention can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when laser light, which is light, is used as a light source, it is possible to significantly prevent the appearance of interference fringe patterns in formed images due to interference phenomena, and to form extremely high-quality visible images.

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 pressure resistance, and use environment properties.

In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. Therefore, it 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.

Next, a method for forming the photoreceptive layer of the present invention will be explained.

The amorphous material constituting the photoreceptive layer of the present invention is deposited by a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blasting method. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be created. The glow discharge method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the member, and carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. .

Further, the glow discharge method and the sputtering method may be used together in the same apparatus system.

For example, a 5i(H+
In order to form a layer composed of
X) A raw material gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and a-31 (H
,X).

As the raw material gas for supplying Sl, 5IH4, Si2
Examples include silicon hydride (silanes) in a gaseous state or that can be gasified, such as H4, Si, H,, 5i4H+a, etc. In particular, 5IH4 , S i 2H, are preferred.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, and side-lighting halogen gas,
Gaseous or gasifiable compounds such as halides, interhalogen compounds, and halogen-articulated silane derivatives are preferred. Specifically, fluorine, chlorine, bromine, E') halogen gas; x, BrFXCIF, C
lIF5, BrF5, BrF5, IF7,
I(4, interhalogen compounds such as IBr, and SiF
Examples include silicon halides such as 4, Si2F6.5iCfia, and 5iBra. When using silicon halide in a gaseous state or one that can be gasified as described above, a layer thinly acidified with a-31 containing halogen atoms can be formed without using a separate raw material gas for supplying Sl. It is particularly effective because it can be formed.

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, HF, HCj! , HBr, II etc. /”t C
llnonthing, 5iHn, SimHa, 5isH, 5
Silicon hydride such as i4H+o, or 5iH2Fz, 5
IH2I! , 5IHz ('b, S*HCl5SSiH*
Gaseous or gasifiable materials such as halogen-substituted silicon hydride such as Brt and 5iHBri can be used,
When these raw material gases are used, it is effective because the content of hydrogen atoms (H), which is extremely effective in controlling electrical or photoelectric properties, can be easily controlled. . And the hydrogen halide or the halogen fM! ! l! When L-water-accumulated silicon is used, hydrogen atoms (H) are also introduced simultaneously with the introduction of halogen atoms, which is particularly effective.

To form a layer consisting of a-51(H,X) by reactive sputtering method or ion blating method,
For example, in the case of a sputtering method, in order to introduce halogen atoms, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as F2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. good.

For example, in the case of the reactive sputtering method, a Si target is used, and a plasma atmosphere is created by introducing a gas for introducing halogen atoms and an at gas, including inert gases such as He and Ar as necessary, into the deposition chamber. A layer of a-3t(H,X) is formed on the support by sputtering the Si target.

To form a layer composed of a-3iGe (H,
) and hydrogen atoms (H
) or/and supplying halogen atoms (X) A raw material gas for supplying water Xi particles (H) and/or halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be depressurized. , a glow discharge is generated in the deposition chamber, and the a-8i
A layer composed of Ge(H,X) is formed.

When forming a layer composed of the above-mentioned a-3i (H, The one used in the above can be used as is.

In addition, substances that can be used as the raw material gas for supplying Ge include GeH4, Ge2H4, GeHll, Ge1H+o
, Ge1H+t, GeaHw 1GeyH14N Ge
Germanium hydride in a gaseous state or in a gasified state such as 5H+s, GetHw, etc. can be used. especially,
GeHa, Ge, H, and Ge aH are preferred from the viewpoint of ease of handling during layer formation work, good Gc supply efficiency, and the like.

To form a layer composed of a-8iGe (H, etc., by sputtering in a desired gas atmosphere.

@-5iGe(H,X
), for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in an evaporation boat as evaporation sources, and the evaporation sources are heated by resistance. This can be carried out by heating and evaporating by a method such as a method or an electron beam method (E, B method), and causing the flying evaporated material to pass through a desired gas plasma atmosphere.

In both the sputtering method and the ion brate ink method, in order to contain halogen atoms in the layer to be formed, gas of the aforementioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber. Then, a plasma atmosphere of the gas may be formed. Also 1. When introducing hydrogen atoms, a raw material gas for supplying hydrogen atoms, such as F2 or the above-mentioned hydrogenated silanes and/or hydrogenated germanium, is introduced into the deposition chamber for sputtering, and these gases are It is sufficient to form a similar plasma atmosphere. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are effective, but in addition, HF1HC1,
Halogen compounds such as HBr, II, SiH2F2.
5iH212, 5iHICQ2.5iHCjli,
Halogen-substituted silicon hydride such as 5iH2Br2.5iHBri, and GeHFa, GeHBr5, GeHI
F,, GeHCfia, GeHa(JtsGeH@
C1, GeHBr5. GeHBr5, GeHgB
r, GeHIg, GeF212, GeHll % hydrogenated germanium halide, etc., GeFa, GeC1
a, GeBr4, Ge14, GeF2, GeCfh, G
Gaseous or gasifiable materials such as germanium halides such as eBr2, Ge12, etc. can also be used as effective starting materials.

To form a photoreceptive layer composed of amorphous silicon containing tin atoms (hereinafter referred to as ra-8iSn(H,X)J) using a glow discharge method, a sputtering method, or an ion blating method. When forming the layer composed of a-8iGe(H,X) mentioned above,
The starting material for supplying germanium atoms is a tin atom (Sn
) Hydrogen is used in place of the starting material for supply, and is incorporated into the layer to be formed while controlling its amount. Tin oxide (SnH4) and SnF2.5nF
4.5nCj2z, 5nCJI4, SnBr2.5nB
It is possible to use gaseous or gasifiable tin halides such as ra, SnI2, SnI4, etc.
When using tin 0-genide, 7.
This is particularly effective because a layer composed of a-Sl containing rogen atoms can be formed. Among these, 5nCft4 is preferable from the viewpoint of ease of handling during layer creation work and good Sn supply efficiency.

When 5nCQ4 is used as a starting material for supplying tin atoms (Sn), in order to gasify it, solid SnC1m is heated and ArXHe is used.

It is preferable to blow in an inert gas such as the like and perform bubbling using the inert gas, and the gas thus generated is introduced at a desired gas pressure into a deposition chamber whose interior is kept at a reduced pressure.

a-5t(H.

X) or a-St (Ge, Sn) (H,X)
In order to form a layer composed of an amorphous material further containing a military group atom or a group I atom, a-3t(H,
X) or a-8i (Ge, Sn) (H, or a-Si
(Ge, Sn) (H.

X) by their use in conjunction with the starting materials for the formation and their controlled inclusion in the layer to be formed.

Specifically, the starting materials for introducing boron atoms are H2H,, BaH+o, ! 31. H
? , BI H, , B6 island, BIntt, B, tH14, and other boron hydrides, BF-containing Cl1=s, BBr3, and other boron hydrides.

In addition, AItCls, QaCl, s, Qa (C
Hs)t, InCJ! 1, 'rxc et al.

As a starting material for introducing a group V atom, specifically for introducing a phosphorus atom, hydrogen ratios such as PHs XPt&, PH
4I XPFm, PFs, PCl3, PCjls, P
Examples include non-rogen ratios such as Brs, PBr, pH, etc. In addition, As) Is, AsF, , ASCfi
,,ASBrs,ASFII,SbL.

SbF, 5bFl, 5bCn, 5bC1,s XB
Examples include boron chlorides such as CIs and BBrs. In addition, hXcIts, CaCchi, Ga(CL)
t, InCjQHlTnCfls, etc. can also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, PHs, P! Hydrogen ratio such as Ha, PH
aI, PFs, PFs% PCjls, PCits
, PBr3, PBrs.

Examples include halogen ratios such as PI3. In addition, ASH
s, AgF2, ASCQ3, ASBrs, ASFs
1SbI(s % 5bFs, 5bCA, 5b(J
! s, B;) I3, B; Cx, , B1Br5, etc.
These can be mentioned as effective starting materials for introducing group atoms.

At least one kind selected from the group consisting of oxygen atoms, carbon atoms, and nitrogen atoms is contained in the second layer 103 using a glow discharge method, a solar irradiation method, or an ion blating method to form a-8i (0° Formation of the layer composed of C, N) (H, X) is performed in the same manner as in the case of forming the first layer described above.

For example, in order to form a layer or a layer region containing oxygen atoms by a glow discharge method, a source gas containing silicon atoms (Si), a source gas containing oxygen atoms (0), If necessary, a raw material gas containing hydrogen atoms (H) or... rogen atoms (X) may be mixed at a desired mixing ratio, or silicon atoms (Si
) is mixed with a raw material gas containing oxygen atoms (0) and hydrogen atoms (H) at a desired mixing ratio, or silicon atoms (S
i) as a constituent atom and a silicon atom (si
), an oxygen atom (0), and a hydrogen atom (H) as constituent atoms can be mixed and used.

Alternatively, a raw material gas containing oxygen source-7(0) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms.

The starting material for introducing oxygen atoms may be any gaseous material containing oxygen atoms as a constituent atom or a gasified material that can be gasified.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (-), ozone (OS), -nitrogen oxide (No), nitrogen dioxide (NOl), -nitrogen dioxide (NtO), and nitrogen sesquioxide (Ntos). ), nitrogen dioxide (Ntoa), nitrogen sesquioxide (NtOs ), nitrogen trioxide (NO Hssto
stas),) resiloxane (Hs S 10 S I
Examples include lower siloxanes such as HlOSIHs).

K, which forms a layer containing oxygen atoms by a sputtering method, is a single-crystal or polycrystalline Si wafer or a Si
This can be carried out by sputtering a wafer or a wafer containing a mixture of Si and Si in various gas atmospheres.

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

Alternatively, Si and Sin may be used as separate targets, or by using a single target mixed with Si and 5 lots, in an atmosphere of dilution gas as a sputtering gas or at least hydrogen atoms (H )
or/and by sputtering in a gas atmosphere containing halogen atoms (X) as constituent atoms.

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

The second layer containing, for example, carbon atoms is formed by a glow discharge method using a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are carbon atoms (C). , and a raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms at a desired mixing ratio, or silicon atoms (Si
) and a raw material gas containing carbon atoms (C) and hydrogen atoms (H) at a desired mixing ratio, or silicon atoms (S
i) as a constituent atom and a silicon atom (Si
), a raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms, or furthermore, silicon atoms (S
i), a raw material gas containing hydrogen atoms (H) as constituent atoms, and a raw material gas containing carbon atoms (C) as constituent atoms are mixed and used.

Si is effectively used as such raw material gas.
and H as constituent atoms SiH4,5itH,,5Is
Silicon hydride gas such as 3ijlanes such as Ha, Sj*Hm, etc., saturated hydrocarbons having 1 to 4 carbon atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, and ethylene carbonization having 2 to 4 carbon atoms. Examples include hydrogen, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (CtHa), propane (CSH,), n-butane (n-C4HIO), pentane (CsLt),
Examples of ethylene hydrocarbons include ethylene (C1H4),
Propylene (C3H6), butene-1 (C4 mountain), butene-2 (C4Hs), imbutylene (C4Hs), pentene (Cq H+o), acetylene hydrocarbons include acetylene (CtZ), methylacetylene (CSH)
4), butyne (C4 mountain), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CHs)4, sI(CtHa)4, and other alkyl silicides can be used. In addition to these raw material gases, I can of course also be used as the raw material gas for introduction.

K, which forms the second layer composed of a-8iC (H, Sputtering is performed using a wafer as a target in a desired gas atmosphere.

For example, when using a Si wafer as a target, the source gas for introducing carbon atoms, hydrogen atoms, and/or halogen atoms may be Ar, He, or
Si
All you have to do is sputter the wafer.

In addition, if Si and C are used as separate targets, or if Si and C are mixed and used as a single target, hydrogen atoms or /
The raw material gas for introducing halogen atoms may be diluted with a diluent gas if necessary, and introduced into a deposition chamber for sputtering to form gas plasma and perform sputtering. As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method described above can be used as is.

Further, a second layer made of amorphous silicon containing nitrogen atoms, for example, is formed by a glow discharge method.
is a raw material gas containing silicon atoms (si) as constituent atoms, a raw material gas containing nitrogen atoms (N) as constituent atoms, and hydrogen atoms (H) or halogen atoms (X) as constituent atoms as necessary. or a raw material gas whose constituent atoms are silicon atoms (Si) and a raw material gas whose constituent atoms are nitrogen atoms (N) and hydrogen atoms (H). Gases can also be used in mixtures, also in desired mixing ratios.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms ffN)- as constituent atoms.

The starting material for introducing nitrogen atoms may be any gaseous substance containing at least nitrogen atoms or a gasified substance that can be gasified.

Specifically, starting materials for introducing nitrogen atoms include nitrogen (N), ammonia (NHs), which has a nitrogen atom as a constituent atom, or a nitrogen atom and a hydrogen atom as constituent atoms.
, hydrazine (LNN&), hydrogen azide (aNS), ammonium azide (CNH4N5), and nitrogen compounds such as nitrides and azides. In addition, nitrogen trifluoride (F3N), nitrogen tetrafluoride (F4
Examples include halogenated nitrogen compounds such as Nt ), and when these halogenated nitrogen compounds are used, halogen atoms (X) can be introduced in addition to nitrogen atoms (N).

To form a layer region containing nitrogen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or Si3N4 wafer, or a wafer containing a mixture of i9i and Si3N4 is used as a target, and various types of these are used. Sputtering can be performed in a gas atmosphere using a button.

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

Alternatively, by using Si, Si, and N4 as separate targets, or by using a single mixed target of Si and 5jsN4, at least hydrogen atoms can be sputtered in a dilution gas atmosphere as a sputtering gas. (
H) or/and... is achieved by sputtering in a gas atmosphere containing rogen atoms (X) as constituent atoms.

As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms in the raw material gas shown in the example of glow discharge described above can also be used as an effective gas in the case of sputtering. (1) The light-receiving layer of the light-receiving member of the present invention is formed using a glow discharge method, a sputtering method, or the like. Control of each content of atoms, hydrogen atoms and/or halogen atoms is as follows:
This is done by controlling the gas flow rate of each atom supply starting device or the gas flow rate ratio of each atom supply starting material flowing into the deposition chamber.

In addition, conditions such as the support temperature, gas pressure in the deposition chamber, and discharge power during the formation of the first layer and the second layer are important cost factors for KFi in order to obtain a light-receiving member with desired characteristics. ,
It is selected as appropriate after careful consideration of the width of the layer to be formed. Furthermore, the conditions for forming these layers may differ depending on the type and composition of each of the atoms mentioned above to be contained in the first layer and the second layer. It is also necessary to make a decision after consideration.

Specifically, a layer consisting of a-8i(H,)0, or Group 1 atoms or Group II atoms, or oxygen atoms, carbon atoms,
When forming a photoreceptive layer made of a-8i (HIX) containing nitrogen atoms, the support temperature is usually 50°C.
The temperature is preferably 50 to 250°C, particularly preferably 50 to 250°C. The gas pressure inside the deposition chamber is normally 0. O1~l'l'o
rr, particularly preferably 0.1 to 0.5 Torr
shall be. Further, the discharge power is usually 0.005 to 50 W/-, but more preferably 0.01 to 30 W/-.
W/cI11 is particularly preferably 0.01 to 20V-.

a When forming a layer consisting of 5sGe (H*X), or containing Group 1 atoms or Group II atoms, 9a 5
When forming a layer made of iGe(H*X), the support temperature is usually 50 to 350°C, more preferably 50 to 300°C, particularly preferably 100 to 30°C.
The temperature shall be 0°C. The gas pressure inside the deposition chamber is usually 0.0
1 to 5 Torr, preferably 0ff01 to 3
Torr, particularly preferably 0.1 to 1'porr. In addition, the discharge power is usually 0.005 to 50 W/-, but preferably 1 to 30 W/-
It is particularly preferably 0.01 to 2 degrees.

However, the specific conditions for layer formation, such as support temperature, discharge power, and gas pressure in the deposition chamber, are usually difficult to determine individually. Therefore, in order to form an amorphous material layer with desired characteristics, it is desirable to determine optimal conditions for layer formation based on mutual and organic relationships.

By the way, the distribution of germanium atoms and/or tin atoms, oxygen atoms, carbon atoms or nitrogen atoms, Group 1 atoms or Group II atoms, or hydrogen atoms and/or nitrogen atoms contained in the photoreceptive layer of the present invention In order to make the state uniform, it is necessary to keep the above-mentioned conditions constant for K when forming the photosensitive layer.

Further, in the present invention, when forming the photoreceptive layer, 1 germanium atoms and/or tin atoms contained in the layer,
Alternatively, if a glow discharge method is used, K, which changes the distribution concentration of group II atoms or group V atoms in the layer thickness direction to form a layer having a desired distribution state in the layer thickness direction, is germanium atoms. or/and appropriately changing the gas flow rate when introducing into the deposition chamber the gas of the starting material for introducing tin atoms, Group 1 atoms, or Group V atoms, while keeping other conditions constant. form. Specifically, K for changing the gas flow rate is determined by the opening of a predetermined needle valve provided in the middle of the gas flow path system by some commonly used method such as manually or by an externally driven motor. All you have to do is repeat the process to gradually change the value. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

In addition, when forming the photoreceptive layer using a sputtering method, the distribution concentration of germanium atoms, tin atoms, group 1 atoms, or group In order to form the directional distribution state, as in the case of using the glow discharge method, germanium atoms or tin atoms, or the starting material for introducing group I atoms or group V atoms, are used in a gaseous state, and the The gas flow rate when introducing the gas into the deposition chamber is varied according to a desired rate of change.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 11, but the present invention is not limited thereto.

In each example, the photoreceptive layer was formed using a glow discharge method. FIG. 25 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

2502.2503.2504.2505.25 in the diagram
Gas cylinder 06 is sealed with raw material gas for forming each layer of the present invention. As an example, 2502 is SiF4 gas (purity 99.999%)
Cylinder 2503 is a specific gravity gas diluted with H8 (purity 9
9.999%, hereinafter abbreviated as BtHa/Hs. ) cylinder,
2504 is a mountain gas (purity 99.999%) cylinder, 25
05 is a QeF4 gas (purity 99.999%) cylinder, and 2506 is an inert gas (He 2 ) cylinder. 2506' is a sealed container containing 5n (J4).

K, who flows these gases into the reaction chamber 2501, confirms that the leak valves 2535 to the pulps 2522 to 252 of the gas cylinders 2502 to 2506 are closed, and
Inflow pulp 2512-2516, outflow valve 2517-
After confirming that the auxiliary valves 2521 and 2532 and 2533 are open, first open the main valve 2534 to exhaust the reaction chamber 2501 and gas piping. Next, vacuum A2
An example of forming the first layer and the second layer on the cylinder 2537 will be described below.

First, from gas cylinder 2502, 5IF4 gas, from gas cylinder 2503, BtHa/Jin gas, gas cylinder - < 250
Pulpe 2522.2523 of GeF4 gas from 5
．． 2525 and outlet pressure gauge 2527.2528.
Adjust the pressure of 2530 to 1/- and open the inlet valve 25.
12.2513.2515 Gradually open it and let it flow into the mass flow controller, 2507.2508.2510. Subsequently the outflow valve 2517.2518.2
520 The auxiliary valve 2532 is gradually opened to allow gas to flow into the reaction chamber 2501.

At this time, SiF4 gas flow rate, GeF4 gas flow rate, B2
Adjust the outflow valves 2517, 2518, 2520 so that the ratio of H1l/H2 gas flow rate becomes the desired value, and adjust the vacuum gauge 2 so that the pressure inside the reaction chamber 2501 becomes the desired value.
Adjust the opening of the main valve 2534 while checking the reading of 536. After confirming that the temperature of the base cylinder 2537 is set within the range of 50 to 400°C by the heating heater 2538, the power source 2540 is set to the desired power to generate glow discharge in the reaction chamber 2501. At the same time, using a microcomputer (not shown), SiF4 gas, GeFa gas and B2 Ha /
While controlling the gas flow rate of H2 gas, the base cylinder 2
First, a layer 102' containing silicon atoms, germanium atoms, and boron atoms is formed on the layer 537. The layer 102' is vertically formed to the desired layer thickness.
place f-store f ・→>18 i kapu +n
By completely closing the 1Q hole at iZ H+ 73 and continuing glow discharge according to the same procedure except for changing the discharge conditions as necessary, the layer 102' contains substantially no germanium atoms. layer 102
' can be formed.

After forming the first layer 102 having the layers 102' and 102'' in this order from the support side, the second layer 103 is formed on the first layer 102 by the same operation as described above. For example, each of SiF4 gas and CH4 gas is diluted with a diluent gas such as He, Ar, H2, etc. as necessary, and flows into the reaction chamber 1601 at a desired gas flow rate, and the second gas is Deposit layers.

Needless to say, all the outflow valves other than the pulp valves, which are necessary for the outflow of gas when forming each layer, are closed.Also, when forming each layer, the gas used to form the previous layer is allowed to flow out of the reaction chamber 2501. In order to avoid gas remaining in the gas piping leading from the valves 2517 to 2521 into the reaction chamber 2501, the outflow valves 2517 to 2521 are closed, the auxiliary valves 2532 and 2533 are opened, and the main valve 2534 is fully opened to remove the metal in the system. Perform operations to evacuate to high vacuum as necessary.

In addition, in the case of containing tin atoms in the first layer, if a gas containing 5nC134 as a starting material is used as the raw material gas, the solid S
The nc-e4 is heated using a heating means (not shown), and an inert gas such as Ar, He, etc. (D) is blown into the nc-e4 from an inert gas cylinder 2506 to cause bubbling. Generated S nC134
The gas is caused to flow into the reaction chamber by the same procedure as the above-mentioned SiF4 gas, GeFa gas, BzHs/Hz gas, etc.

Test Example 1 A SUS stainless steel rigid sphere with a diameter of 0.6 mm was chemically treated to form unevenness by etching the surface. Examples of the processing agent used include acids such as hydrochloric acid, fluorine, sulfuric acid, and chromium, and alkalis such as caustic soda. In this test example, a hydrochloric acid solution mixed at a volume ratio of 1 to 4 parts pure water to 1 part concentrated hydrochloric acid was used, and the immersion time of the hard sphere, acid concentration, etc. were varied to adjust the shape of the unevenness as appropriate.

Test Example 2゜Using a rigid sphere (height of surface irregularities r□8=5 μm) treated by the method of Test Example 1, using the apparatus shown in Fig. 6(A), 03), a ball made of aluminum alloy was used. cylinder(
A surface with a diameter of 60 days and a length of 298 mm was treated to form irregularities.

When we investigated the relationship between the diameter R' of a true sphere, the falling height h, and the curvature R1 width r of the trace depression, we found that the curvature R and width r of the trace depression are as follows.
It was confirmed that it is determined by conditions such as the diameter R' of the true sphere and the falling height h. In addition, the pitch of the dents (the density of the dents and the pitch of the unevenness) is determined by the rotational speed of the cylinder,
It has been confirmed that it is possible to adjust the pitch to a desired pitch by controlling the number of rotations, the amount of fall of the rigid true sphere, etc.

Furthermore, as a result of considering the sizes of R and D, R is
If it is less than 0.1 wm, the rigid sphere must be made small and light to ensure the falling height, making it difficult to control the formation of vestigial depressions, which is undesirable.
If it exceeds 0 m, the rigid sphere will be made heavier and the falling height will be adjusted. For example, if you want to make D relatively small, you will need to make the falling height extremely low, which can control the formation of dents. Furthermore, if D is less than 0.02 m, the rigid sphere must be made smaller and lighter to ensure the falling height, which is undesirable because it becomes difficult to control the formation of dents. This was confirmed respectively.

When we examined the vestigial depressions that had been formed, it was confirmed that minute irregularities were formed within the vestigial depressions, corresponding to the shape of the surface irregularities of the rigid sphere.

Example 1 The surface of an aluminum alloy cylinder was treated as in Example 2 and ( ), and a cylinder "-shaped M support (cylinder type 101
~106) were obtained.

Next, a light-receiving layer was formed on the M support (cylinder, % 101-106) using the manufacturing apparatus shown in FIG. 5 under the conditions shown in Table 1B below.

These light-receiving members were subjected to image exposure by irradiating laser light with a wavelength of 780 Xll and a spot diameter of 80 μm using the image exposure apparatus shown in FIG. A, and then development and transfer were performed to obtain images. The occurrence of interference fringes in the obtained image was as shown in the lower column of Table 1A.

Note that Figure 26 is a plan view schematically showing the entire exposure apparatus, and Figure 26G is a schematic side view schematically showing the entire exposure apparatus. In the figure, 2601 is a light receiving member, 26
02 is a semiconductor laser, 2603 is an fθ lens, 260
4 indicates a polygon mirror.

Next, as a comparison, we will show an aluminum alloy / cylinder surface treated with a conventional diamond tool, + (41
07) (diameter 60 rNR, length 298 fl, uneven pitch 100 μm, uneven depth 3 μm) was used to explode the light receiving member in the same manner as described above. When the obtained light-receiving member was observed under an electron microscope, it was found that the support surface, the layer interface of the light-receiving layer, and the surface of the light-receiving layer were parallel to each other. Using this light-receiving member, images were formed in the same manner as described above, and the resulting good images were evaluated in the same manner as described above. The results were as shown in the lower column of Table 1A.

Example 2 A photoreceptive layer was formed on the AJ support (cylinders Nu 101 to 107) in the same manner as in Example 1, except that the photoreceptive layer was formed according to the layer forming conditions shown in Table 2B. Note that siF at the time of forming the first layer.

The gas flow rates of the gas and GeFa gas are controlled by the micro combinator according to the flow rate change line shown in FIG.
Adjusted automatically.

An image was formed on the obtained light-receiving member in the same manner as in Example 1, and the occurrence of interference fringes in the obtained image was as shown in the lower column of Table 2A.

Example 3 An A1 support (cylinders N11301 to 306) having a cylindrical shape was obtained in the same manner as in Example 1 except that a rigid sphere having the height of surface irregularities (rmax) shown in the upper column of Table 3A was used.

Next, the A2 support (cylinders 11a1301 to 306
), a light-receiving layer was formed thereon using the manufacturing apparatus shown in FIG. 25 under the conditions shown in Table 3B below. The gas flow rates of GeF, gas, and SiF4 gas during the formation of the first layer 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.

Example 4 A photoreceptive layer was formed on the A2 support (cylinder order 301 to 306) in the same manner as in Example 3, except that the photoreceptive layer was formed according to the layer forming conditions shown in Table 4B.

In addition, 5IF4 gas and Ge at the time of first jz formation
The gas flow rate of gas F was 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.

Examples 5-11 A2 support of Example 1 (cylinder N[l 103-1
06) 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 formation conditions shown in Table @5-If. In addition, in Examples 5 to 11,
The flow rate of the gas used during the formation of the first layer is the same as that of the third layer.
It was automatically adjusted by microcomputer control according to the flow rate change line shown in Figures 0 to 36. Further, the boron atoms contained in the first layer are Btz/S i l;'
4+GeF4 #100 ppm was introduced as much as possible so that the entire layer was doped at about 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 it was of extremely high quality.

[Summary of effects of the invention]

The light-receiving member of the present invention has the above-described layer structure, so that it can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon, and in particular, it can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when laser light, which is monochromatic light, is used as a light source, the appearance of interference fringes in the formed image due to interference phenomena can be significantly prevented, and a visible image of extremely high quality can be formed.

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 optical response. 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 characteristics are stable, and it has high sensitivity and a high signal-to-noise ratio. Therefore, it 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 drawings]

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 interference fringes are prevented from occurring in a light-receiving member in which unevenness is formed by spherical trace depressions 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 an apparatus suitable for forming the uneven shape provided on the support of the light-receiving member of the present invention, and FIG. 6(A) is a front view. , 6th
The figure (mountain) is a longitudinal cross-sectional view. 7 to 15 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the first layer of the present invention, and Figures 16 to 24 are diagrams showing the distribution state of germanium atoms or tin atoms in the first layer of the present invention. FIG. 2 is a diagram showing the distribution state of group atoms or group (Ⅰ) atoms in the layer thickness direction; in each diagram, the vertical axis represents the layer thickness of the photoreceptive layer, and the horizontal axis represents the distribution concentration of each atom. FIG. 25 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method, which is an example of the Jk< position for manufacturing the light-receiving layer of the light-receiving member of the present invention. FIG. 26 is a diagram illustrating an art stage exposure device using laser light. 27th
Figures 36 to 36 are diagrams showing changes in gas flow rate in the first layer formation 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 body 102
．． 201.301...First layer 102'...Layer containing at least one of germanium atoms or tin atoms 102''...Layer containing neither germanium atoms nor tin atoms 103.202.302 ...Second layer 104.203
, 303... Free surface 204, 304... Interfacial cylinder between the first layer and the second layer, 401.501... Support, 402, 502...
...Support surface, 403.503... Spherical trace depression, 403', 503'... Rigid sphere having an uneven shape on the surface, 404... Minute uneven shape formed in the spherical trace depression 404' ...Regarding the uneven shape formed on the surface of the rigid sphere in Fig. 6, 601... Cylinder, 602... Rotating shaft (receiving) 6
03...Driving means, 604...Rotating container 605...
・Rigid sphere 606 with an uneven shape on the surface...Lip 607 provided on the inner wall of the container...Regarding the shower pipe in FIG. 25, 2501...Reverse E chamber, 2502-2506...Gas cylinder 2506'= 5nCjl, airtight container 25
07~2511...Mass flow controller 2512~
2516... Inflow pulp 2517-2521... Outflow pulp 2522-2526... Pulp 2527-2531... Pressure regulator 2532.2533... Auxiliary pulp 2534... Main pulp, 2535... Leak Pulp 2536...Vacuum gauge, 2537...Base cylinder 2538...Heating heater, 2539...Motor 2540...High frequency power source Regarding Fig. 26, 2601...Light receiving member, 2602...Semiconductor Laser 2603...Fθ lens, 2604...Polygon mirror drawing cleaning! (No changes to the contents) Figure 1 Figure 5 Figure 6 (A3 Figure 607, .1d607 Figure 80 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 16 2602 SCCM SCC in Figure 17 and Figure 19 □C □C Figure 22 □C □C Figure 26
MG e F4 gas SiF4 gas SCC
MSCC
MGeH4 gas Si H4 gas procedural amendment (method) January 20, 1985 Director General of the Patent Office Michibe Uga 1, Indication of the case Spring 1985 Patent Application No. 241575 2, Title of the invention Light Reception Department Material 3. Relationship with the case of the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name
(100) Canon Co., Ltd. 4, Agent Address: 6 Kojimachi Green Building, 3-12-6 Kojimachi, Chiyoda-ku, Tokyo, Specification and drawings subject to amendment 7, Contents of amendment The specification and drawings originally attached to the application. As shown in the engraving and attached sheet (no changes to the content)

Claims (1)

[Scope of Claims] (1) A first layer composed of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms, silicon atoms and oxygen atoms, on a support. ,
A light receiving member comprising a light receiving layer comprising a second layer made of an amorphous material containing at least one selected from carbon atoms and nitrogen atoms, wherein the first layer is , a multilayer structure having a layer containing at least one of germanium atoms or tin atoms and a layer containing neither germanium atoms nor tin atoms in order from the support side, and the surface of the support is formed by a plurality of spherical trace depressions. A light-receiving member characterized by having an uneven shape and further having a plurality of minute uneven shapes within the spherical trace depression. (2) The second layer is made of an amorphous material containing silicon atoms and at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform distribution state ( The light-receiving member described in item 1). (3) The light-receiving member according to claim (1), wherein the light-receiving layer contains a substance that controls conductivity. (4) The photoreceptive member according to claim (1), wherein the photoreceptor layer has as one of its constituent layers a charge injection blocking layer containing a substance that controls conductivity. (5) the photoreceptive layer has a barrier layer as one of the constituent layers;
A light receiving member according to claim (1). (6) The light-receiving member according to claim (1), wherein the plurality of uneven shapes provided on the surface of the support are uneven shapes formed by spherical trace depressions having the same curvature. (7) The light-receiving member according to claim (1), wherein the plurality of uneven shapes provided on the surface of the support are uneven shapes formed by spherical trace depressions having the same curvature and the same width. (8) The uneven shape on the surface of the support is an uneven shape due to the vestigial depressions of the rigid spheres obtained by naturally falling a plurality of rigid spheres having uneven surfaces onto the surface of the support. The light-receiving member according to item (1). (9) The uneven shape of the surface of the support body is an uneven shape caused by the trace depressions of the rigid spheres obtained by dropping a plurality of rigid spheres having approximately the same diameter from approximately the same height. A light receiving member according to claim (8). (10) The curvature R and width D of the spherical trace depression are expressed by the following formula: 0.
035≦D/R≦0.5. The light receiving member according to claim (1). (11) The light-receiving member according to claim (10), wherein the width D of the spherical trace depression satisfies the following formula: D≦0.5 mm. (12) The light-receiving member according to claim (1), wherein the height r of the minute irregularities within the spherical trace depression is a value that satisfies the following formula: 0.5 μm≦r≦20 μm. (13) Claim No. 1, wherein the support is a metal body.
) The light-receiving member according to item 1.