JPS62103655A - Light recepting material - Google Patents

Abstract

PURPOSE:To stabilize electrical, optical, and photoconductive characteristics at all times by matching optical band gaps at the boundary face between a photosensitive layer and surface layer, having plural rugged shapes consisting of spherical recesses of traces on the surface of a base and having the plural smaller rugged shapes in said spherical recesses of traces. CONSTITUTION:A light recepting material 100 has the light recepting layers consisting of the photosensitive layer 102 and surface 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 smaller rugged shapes in the spherical recesses of traces. These layers are so constituted that the optical band gap possessed by the surface layer and the optical band gap possessed by the photosensitive layer directly provided with said surface layer are matched at the boundary face between the surface layer and the photosensitive layer. The reflection of incident light at the boundary face between the surface layer and the photosensitive layer is thereby prevented and the problem of interference fringe patterns and uneven sensitivity arising from the uneven layer thickness in the stage of forming the surface layer or/and the uneven layer thickness by the wear of the surface layer is solved.

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. Furthermore, methods for recording images that perform processes such as transfer and fixing as necessary are known. Among them, in image forming methods using electrophotography, the laser is a small and inexpensive He-Ne laser or a semiconductor laser ( It is common practice to perform image recording using a light emitting wavelength (usually having an emission wavelength of 650 to 820 nm).

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 "a-8iJ" is attracting attention.

However, in the light-receiving member, if the light-receiving layer is a single-layer A-8I layer, it will maintain its high photosensitivity while ensuring a dark resistance of 1 (112Ω or more) required for electrophotography. For this reason, it is necessary to structurally contain hydrogen atoms, halogen atoms, or boron atoms in addition to these atoms in a controlled manner in a specific amount range. There are considerable limitations on the design tolerances of light-receiving components, such as the need to strictly control conditions. Proposals have been made to improve the high light sensitivity by making it possible to utilize it effectively.For example, JP-A-54-121743, JP-A-57-4053, and JP-A-57-41.
As seen in Japanese Patent Publication No. 72, the photoreceptive layer has a layer structure of two or more layers having different conductivity characteristics, and a depletion layer is formed inside the photoreceptive layer, or as disclosed in JP-A No. 57-52178.
No. 52179, No. 52180, No. 58159, 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 photoreceptive layer. A light-receiving member has been proposed that has a multilayer structure with an increased apparent dark resistance.

However, in such a light-receiving member whose light-receiving layer has a multilayer structure, the thickness of each layer varies, and when laser recording is performed using this material, part of the laser beam is coherent monochromatic light, so the light reception is difficult. The free surface of the layer on the laser beam irradiation side, each layer constituting the light-receiving layer, and the layer interface between the support and the light-receiving 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 having a structure of two or more layers (multilayer), interference effects occur in each layer, and each interference acts synergistically to produce 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) a method of diamond cutting the surface of the support to provide unevenness of ±500A to ±10,000X to form a light scattering surface (for example,
8-162975), (1)) A method of providing a light absorption layer by subjecting the surface of an aluminum support to black alumite treatment, or dispersing carbon, coloring pigments, or dyes in a resin (for example, as described in Japanese Patent Application Laid-Open No. 8-162975). (Refer to Publication No. 57-165845), (C) A light scattering and anti-reflection layer is formed 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 grain-like irregularities. A method of providing such a structure (for example, see Japanese Unexamined Patent Publication No. 57-16554) has 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 (1)), in black alumite treatment,
Complete absorption is impossible, and the light reflected on the support surface remains. In addition, when a colored pigment-dispersed resin layer is provided, when forming the a-8i layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed light-receiving layer is significantly deteriorated.
The resin layer is damaged by the plasma during the formation of the A-8I layer, reducing its original absorption function and affecting the subsequent formation of the A-8I layer due to deterioration of the surface condition.
Regarding method (C), for example, if we look at the incident light, a part of it will be reflected on the surface of the photoreceptive layer and become reflected light, and the rest will be: The light 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, the emitted light is a component that interferes with the reflected light, and in any case, the interference fringe pattern will not completely disappear because it will remain.

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, causing no-rations and ultimately resulting 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 degree of roughness varies greatly between lofts, and even in the same lot, the degree of 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 are parallel to each other, and the incident light is not bright in that part. Furthermore, since the thickness of the photoreceptive layer is non-uniform throughout the photoreceptive layer, a striped pattern of light and dark appears. Therefore, simply roughening the surface of the support in a regular manner cannot 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 response light at the interface between each layer, so the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member with a single layer structure.

Furthermore, the problem of interference caused by reflected light in such a multilayered light-receiving member is largely related to its surface layer. That is, as is clear from the above, if the thickness of the surface layer is not uniform, an interference phenomenon will occur due to reflected light at the interface between the surface layer and the photosensitive layer in contact with it, causing damage to the light receiving member. It impairs function.

By the way, the state in which the layer thickness of the surface layer is non-uniform is not only suppressed during the formation of the surface layer, but also caused by abrasion, particularly partial abrasion, during use of the light-receiving member. Particularly in the latter case, as described above, not only interference fringes appear, but also changes in sensitivity, unevenness, etc. of the entire light-receiving member.

Attempts have been made to make the surface layer as thick as possible in order to eliminate these problems related to the surface layer, but in this case, a factor that increases the residual potential is formed, and the surface layer On the contrary, the layer thickness unevenness increases, and a light-receiving member having such a surface layer has factors that cause problems such as changes in sensitivity and unevenness in reading when it is formed. In other words, the initial image may not be worth adopting.

[Purpose of the invention]

The object of the present invention is to eliminate the above-mentioned problems and to make a light-receiving member having a light-receiving layer mainly composed of a-8i, satisfying various requirements.

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-8i, 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 photoreceptive member having a photoreceptive layer composed of a-Si, which has high photosensitivity in the entire usable light range, has excellent matching properties with a semiconductor laser, and has a fast photoresponse. Our goal is to provide the following.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Oi and having 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 8i.

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-8i, which can obtain high-quality images with no blur, high density, clear no-ft tones, and high resolution. It's about doing.

[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 photosensitive layer made of an amorphous material having silicon atoms as a matrix on a support, silicon atoms, and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms. A light-receiving member comprising a light-receiving layer having a surface layer made of an amorphous material containing an amorphous material, wherein the optical band gap is matched at an interface between the photosensitive layer and the surface layer, 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 intensive research are summarized below.

That is, in a light-receiving member equipped with a light-receiving layer having a surface layer and a photosensitive layer on a support, the optical band gap of the surface layer and the surface When the layer is configured to match the optical band gap of the photosensitive layer on which it is directly provided, reflection of incident light at the interface between the surface layer and the photosensitive layer is prevented, and layer thickness unevenness or unevenness during the formation of the surface layer is prevented. /And the problems of interference patterns and sensitivity unevenness caused by layer thickness unevenness due to wear of the surface layer can be solved.

Further, in the 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, and a plurality of finer irregularities are provided within the spherical trace depressions. Additionally, the problem of interference fringes that appear during image formation is significantly eliminated.

By the way, the latter finding is based on facts obtained from various experiments conducted by the present inventors.

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 has 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 photosensitive layer 102 and a surface layer 103 is provided on a support 1 (11) having an uneven shape along the slope of the unevenness.

FIGS. 2 and 4 are diagrams for explaining how the problem of interference fringes is solved in the light-receiving member of the present invention.

FIG. 3 is an enlarged view of a part of a conventional light-receiving member in which a multilayer light-receiving layer is deposited on a support whose surface is regularly roughened. At the contact point, 3 (11 is the photosensitive layer, 302 is the surface layer, 303 is the free surface, and 304 is the interface between the photosensitive layer and the surface layer. If the surface of the support is simply roughened regularly, the light-receiving layer is usually formed along the uneven shape of the surface of the support. This is where the surfaces form a parallel relationship.

Due to this, for example, the photosensitive layer 3 (1
In a light-receiving member having a multilayer structure consisting of two layers, ie, a surface layer 302 and a surface layer 302, the following problems regularly arise, for example.

That is, the interface 304 between the photosensitive layer and the surface layer and the free surface 30
3 is in a parallel relationship, the reflected light R1 at the interface 304
and the reflected light R2 on the free surface coincide in direction, and interference fringes are generated depending on the layer thickness of the surface layer.

FIG. 2 is an enlarged view of a part of a light-receiving member in which a light-receiving layer having a multilayer structure is deposited on a support having an uneven shape formed by a plurality of spherical trace depressions. In map reading, 2
(11 is a photosensitive layer, 202 is a surface layer, 203 is a free surface,
Reference numeral 204 indicates the interface between the photosensitive layer and the surface 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 photoreceptive layer provided on the support is deposited along the uneven shape, and the photosensitive layer The interface 204 between 2(11 and the surface layer 202 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 spherical trace formed on the interface 204 If the curvature of the depression is R1, and the curvature of the spherical trace depression formed on the free surface is R2,
Since R1 and R2 are R1% R2, the reflected light at the interface 204 and the reflected light at the free surface 203 have different reflection angles, that is, θ1 and θ2 in FIG. , +θ2, and the directions are different, and the wavelength shift, expressed as Lx + A2 A3 using Ll, Lz, and t3 shown in Fig. 2, is not constant but changes, so it is a so-called Newton ring. A shearing interference corresponding to this 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 of the spherical trace depression 4 (11). Furthermore, when a minute unevenness or a group of unevenness 402 is provided, in addition to the interference prevention effect described using FIG. The occurrence of patterns is 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 uneven convex portions of the light-receiving layer, resulting in poor rinsing properties, and the abrasion of the convex portions of the light-receiving layer and the surface of the blade is severe, resulting in good durability of both. There is 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: % formula % is satisfied, 0.5 or more Newton rings due to shearing interference will exist in each trace depression. Furthermore, if the following formula: -> 0.055 R-1 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 -0.03
5, preferably 0.055 or more.

Further, the upper limit of - is preferably 0.5.

This is because, when - becomes greater than 0.5, the width of the depression becomes relatively large, which tends to cause image unevenness.

In addition, the width of the unevenness due to the trace depression is 500 mm
It is desirable that the thickness be about μm, preferably 200 μm or less, and even more preferably 1004 m or less. When D exceeds 500 μm, image unevenness is likely to occur and 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 within the spherical trace depressions, that is, the surface roughness γmax within the spherical trace depressions is 0.5 to 20 μm.
It is preferable that it is in the range of . If γmax is less than 0.5 μm, a sufficient scattering effect cannot be obtained, and
If it exceeds m, the minute irregularities within the spherical trace depressions become too sharp 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 light-receiving layer of the light-receiving member of the present invention provided on a support having a specific surface shape as described above includes a photosensitive layer and a surface layer, and the photosensitive layer is made of an amorphous material containing silicon atoms as a matrix; Particularly preferably, an amorphous material containing a silicon atom (Si) and at least one of a hydrogen atom (Sakata) and a rogen atom (X) [hereinafter referred to as t-a-8i
(H,X) Written as j. ], or oxygen atom,
The photosensitive layer is composed of a-8i (H, The photosensitive layer may have a multilayer structure, and it is particularly preferable to include a charge injection blocking layer containing the conductivity controlling substance and/or a so-called barrier layer made of an electrically insulating material. It is one of the things that we have.

Further, the surface layer is made of an amorphous material containing silicon atoms and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, particularly preferably silicon atoms (S
i), at least one selected from oxygen atom (0), carbon atom (C) and nitrogen atom (N), and at least one of hydrogen atom (H) and nitrogen atom (X). Containing amorphous material [hereinafter referred to as [a-El
It is written as i(0,C,N)(H,X)j. ].

Regarding the preparation of the light-receiving layer of the light-receiving member of the present invention, in order to efficiently achieve the above-mentioned object of the present invention, it is necessary to accurately control the layer thickness at an optical level. Vacuum deposition methods such as a method, a sputtering method, an ion blating method, etc. are usually used, but in addition to these methods, a photo CVD method, a thermal CVD method, etc. can also be employed.

Hereinafter, specific details 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, 1 (11 is the support, 102 is the photosensitive layer, 103 indicates a surface layer, and 104 indicates a free surface.

Support The support 1 (11) in the light-receiving member of the present invention has a surface having microscopic 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 shape of the surface 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. The shape of the surface of the support in the light-receiving member of the present invention and its manufacturing method 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, 4 (11 is a support, 402 is a support surface, 403 is an uneven shape due to a spherical trace depression, and 404 is a finer uneven shape provided within the spherical trace depression.

Furthermore, FIG. 4 also shows an example of a preferable manufacturing method for obtaining the surface shape of the support, and 403' indicates a rigid sphere having a minute unevenness shape 404' on the surface. By letting the rigid 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 with a spherical trace depression having minute unevenness 404 inside the depression is formed. It shows Shiroko. Then, a rigid sphere 403 with approximately the same diameter R'
By using a plurality of `` and dropping them simultaneously or sequentially from the same height h, a plurality of spherical traces having the same curvature R and the same width are formed on the support surface 402. A depression 403 can be formed.

FIG. 5 shows some typical examples of supports having an uneven shape formed by a plurality of spherical trace depressions on the surface as described above. In the figure reading, 5 (11 is the support, 502 is the support surface, 503 is a spherical trace depression having a plurality of microscopic uneven shapes in the depression (in addition, in FIG. 5, it is formed within the spherical trace depression) Although a plurality of even smaller uneven shapes are not shown, it is assumed that each of the spherical trace depressions 503 has an even smaller uneven shape.)
, 503' is a rigid sphere having minute irregularities on its surface (similarly, the minute irregularities on the surface are not shown in the figure, but
It is assumed that the surface of the rigid sphere has minute irregularities. ) are shown respectively.

In the example shown in FIG. 5(A), the surface 50 of the support 5 (11)
A plurality of spheres 503' having approximately the same diameter are placed at two different locations.
, 503', . . . are regularly dropped to approximately the same height to form a plurality of trace depressions 503, 503, . This is a structure in which a regular uneven shape is formed. In this case, the depressions 503, 503, which overlap with each other,
To form..., the support surface 50 of the sphere 503'
The spheres 503',
Needless to say, it is necessary to allow the parts 503', . . . to fall naturally.

In the example shown in FIG. 5(B), two types of spheres 503', 503', . . . having different diameters are dropped from approximately the same height or different heights, and A plurality of depressions 50 having two types of curvature and two types of width are formed on the surface 502 of
3.503, .

Furthermore, in the example shown in FIG. 5(C) (a front view and a sectional view of the surface of the support), a plurality of spheres 503', 503', . are dropped irregularly from approximately the same height to produce a plurality of depressions 503, 503,... having substantially the same curvature and multiple types of widths so as to overlap with each other, thereby forming irregular unevenness. This is what I did.

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, the height of the irregularities formed on the surface of the support, the edges of the irregularities, or the heights of the even finer irregularities formed in the concave portions of the irregularities can be adjusted. It is possible to freely adjust the pitch etc. of the sheath unevenness 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 are inevitably generated during cutting, and the removal of cutting oil that remains on the cut surface, resulting in complicated processing. However, in the present invention, since the uneven surface shape of the support is formed by spherical trace depressions as described above, the above-mentioned problems can be completely eliminated and it is possible to form the desired uneven surface shape. Supports can be created efficiently and easily.

The support 1 (11) used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, At
%Cr, Mo, Au, Nb, Ta, V.

Examples include metals such as Ti, Pt, and Pb, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polyprogylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, and paper. . 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, AA
, Cr, MOlAu, Engr1Nb, Ta%V, Ti
, Pt.

Pa, Engineering n203.5n02, Engineering To (Engineering n203 +
Conductivity can be imparted by providing a thin film consisting of 5n02), etc., or if it is a synthetic resin film such as d IJ ester film, NiCr, AL, Ag
1Pb, Zn, Ni, Au, Cr, Mo, Cr, N
b. Vacuum deposition of thin films of metals such as Ta, V, TL, Pt, etc.
Electroconductivity is imparted to the surface by providing it on the surface by electron beam evaporation, starching, etc., or by laminating the surface with the metal. 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. It can be made as thin as possible. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

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 surface of the support will be explained with reference to FIGS. 6(A) and 6(B). 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 mandrel tube, and the drawn tube obtained by further drawing processing is subjected to heat treatment and conditioning as necessary. A cylindrical (cylinder-shaped) substrate that has been subjected to a treatment such as quality is used, and a sixth (cylindrical) substrate is applied to the cylindrical substrate.
A) and (B) Using the manufacturing apparatus shown in the figures, 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 brass, 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 various types of rigid spheres having an uneven surface as described above. Methods that apply plastic processing such as embossing and corrugation, surface roughening methods such as surface roughening method (Nashiji method), methods of forming unevenness by mechanical processing, etching treatment with acid or alkali, etc. It can be produced by processing a rigid sphere using a method of forming unevenness using a chemical method. Furthermore, on the surface of the rigid sphere with the unevenness formed in this way, electrolytic polishing, chemical polishing, finish polishing, etc., or anodic oxidation film formation, chemical conversion film formation, plating, waxing, painting, vapor deposition film formation, or film formation by CVD method. Surface treatment such as formation can be performed to adjust the uneven shape (height), hardness, etc. as appropriate.

FIGS. 6A and 6B are schematic cross-sectional views for explaining an example of the manufacturing apparatus.

In the figure, 6 (11) is an aluminum/cylinder for making a support, and the surface of the cylinder 6 may be previously finished to an appropriate degree of smoothness.

The cylinder 6 (11) is rotatably supported by a rotating shaft 602 and driven by an appropriate driving means 603 such as a cylinder or a motor, so that it can rotate approximately around the axis.

604 is rotatably supported by the bearing 602 and is connected to the cylinder 6 (11
It is a rotating container that rotates in the same direction as the container 604.
Inside, there are a large number of rigid spheres 60 with uneven surfaces.
5 is accommodated. The rigid sphere 605 is a rotating container 604
The container is carried by a plurality of protruding ribs 606 provided on the inner wall of the container, 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 6 (11),
It collides with the cylinder surface and forms a trace depression on the surface.

Note that holes are uniformly bored in the wall of the rotating container 604 so that cleaning liquid is sprayed through a shower pipe 607 provided outside the container 604 when the container 604 is rotated. It is also possible to make it washable. In this case, dirt and the like that have adhered due to static electricity generated due to contact between the rigid spheres or between the rigid sphere and the rotating container 604 will be washed out of the rotating container 604, and the garbage will be removed. It is possible to form a desired support without adhesion of substances such as. It is necessary to use a cleaning liquid that does not dry unevenly or drip, and for this reason, non-volatile substances alone, hatrichloroethane, Preferably, a mixture with a cleaning liquid such as trichlorethylene is used.

Photosensitive layer In the light-receiving member of the present invention, the photosensitive layer 102 is provided on the above-mentioned support 1 (11), and is a-8i (
H, X) or a-8i (H,
), and preferably contains a substance that controls conductivity.

The halogen atom (X) contained in the photosensitive layer is as follows:
Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. Hydrogen atoms (H) contained in the photosensitive layer 102
The amount of halogen atoms (X') or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 40a.
tomic%, preferably 5 to 3QatOmiC%.

Furthermore, in the light-receiving member of the present invention, the layer thickness of the photosensitive layer is
One of the important factors for effectively achieving the object of the present invention is to pay sufficient attention when designing the light receiving member so that the desired characteristics are imparted to the light receiving member. usually 1 to 100μ, preferably 1 to 80μ
μ, preferably 2 to 50 μ.

By the way, the photosensitive layer of the light receiving member of the present invention contains oxygen atoms,
The purpose of containing at least one selected from carbon atoms and nitrogen atoms is mainly to increase the photosensitivity and dark resistance of the light-receiving member, and to improve the adhesion between the support and the photosensitive layer. .

In the photosensitive layer of the present invention, when at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms is contained, it is contained in a uniformly distributed state in the layer thickness direction, or in a non-uniformly distributed state in the layer thickness direction. Whether to contain it in a distributed state is
It varies depending on the above-mentioned objectives and expected effects, and accordingly, the amount to be included also varies.

That is, when the purpose is to increase the photosensitivity and dark resistance of a light-receiving member, carbon atoms and oxygen atoms contained in the photosensitive layer are contained in a uniform distribution over the entire layer area of the photosensitive layer. The amount of at least one selected from nitrogen atoms and nitrogen atoms may be relatively small.

In addition, when the purpose is to improve the adhesion between the support and the photosensitive layer, it may be contained uniformly in a part of the layer area at the support side end of the photosensitive layer, or it may be added to the support side end of the photosensitive layer. In this case, at least one selected from carbon atoms, oxygen atoms, and nitrogen atoms is contained in a distribution state such that the distribution concentration thereof is high; in this case, the oxygen atoms, carbon atoms, and nitrogen atoms to be contained in the photosensitive layer are The amount of at least one selected from among these is set to a relatively large amount in order to ensure improved adhesion to the support.

In the light-receiving member of the present invention, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms to be contained in the photosensitive layer may be determined by considering the characteristics required for the photosensitive layer as described above. It is determined by taking into account organic relationships such as the characteristics at the contact interface with the support, and usually Q, QQI ~ 50 atomic%,
Preferably it is 0.002-40 atomic%, optimally 0.003-30 atomic%.

By the way, if it is contained in the entire layer area of the photosensitive layer, or if the ratio of the layer thickness of a part of the layer area to which it is contained is large in the layer thickness of the photosensitive layer, the above-mentioned upper limit of the amount to be included may be reduced. be made into That is, in that case, for example, when the layer thickness of the layer region to be contained is equal to τ of the layer thickness of the photosensitive layer, the amount to be contained is usually 30 atoms.
ic% or less, preferably 20 atomic 1 or less,
Optimally, it is set to 10 at, 0 m1c% or less.

Next, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms to be contained in the photosensitive layer of the present invention is relatively large on the support side, and from the end on the support side to the surface layer side. Some typical examples are cases where the distribution decreases toward the edge and becomes a relatively small amount or substantially close to zero near the edge on the surface layer side of the photosensitive layer. , will be explained with reference to FIGS. 7 to 15. However, the present invention is not limited to these examples. Hereinafter, at least one kind selected from carbon atoms, oxygen atoms and nitrogen atoms [atoms (0, C, N
) Written as J.

In Figures 7 to 15, the horizontal axis represents the distribution concentration C of atoms (0, C, N), the vertical axis represents the layer thickness of the photosensitive layer, and tB represents the interface position between the support and the photosensitive layer. tT indicates the position of the interface between the photosensitive layer and the surface layer.

Figure 7 shows atoms (0, C, N) contained in the photosensitive layer.
The first typical sequence of the distribution state in the layer thickness direction is shown. In this example, from the interface position tB between the photosensitive layer containing atoms (0, C, N) and the support to the position t1, atoms (0, C,
, N) takes a constant value of (11), and from position t1 to interface position tT with the surface layer, atoms (0, C,
The distribution concentration C of atoms (N) decreases continuously from the concentration C2, and the distribution concentration of atoms (0,C,N) becomes 0 at position tT.
It becomes 3.

In another typical example shown in FIG. 8, the distributed concentration C of atoms (0, C, N) contained in the photosensitive layer decreases continuously from the concentration C4 from position tB to position 1. However, the density becomes C5 at position tT.

In the example shown in FIG. 9, the distribution concentration C of atoms (0, C, N) maintains a constant value of concentration C6 from position tB to position t2, and from position t2 to position tT, the distribution concentration C of atoms (0, C, N) maintains a constant value of concentration C6.
, C, N) gradually and continuously decreases from the concentration C, and at the position tT, the distributed concentration C of atoms (0, C, N) becomes substantially zero.

In the example shown in FIG.
, C, N ) is substantially zero.

In the example shown in FIG. 11, the distribution concentration C of atoms (0, C, N) is C9 between position tB and position t3.
It is at a constant value between the position t3 and the position 1T, and decreases in a -order function from the concentration C9 to the concentration CIO.

In the example shown in FIG. 12, the distribution concentration C of the atom (0, C9N) is the concentration C1l from the position tB to the multi-position t4.
The density is at a constant value from the position t4 to the multi-position 1T, and decreases in a -order function from the density C12 to the density C13.

In the example shown in FIG. 13, the distribution concentration C of atoms (◯, C, N) decreases linearly from the concentration C14 to substantially zero from the position tB to the position tT.

In the example shown in FIG. 14, the distribution concentration C of atoms (0, C, N) is C15 from position tB to position t5.
to the concentration C16, which decreases in a quadratic manner, and the position t
5 to position tT, the concentration C16 is kept constant.

Finally, in the example shown in FIG. 15, the distribution concentration C of atoms (0, C, N) is the concentration C at position tB, and from position tB to position t6, the concentration decreases slowly at first from C17. Then, it decreases rapidly near position t6, and at position t
6, the density becomes C18. Next, from position t6 to position 1.
At first, the concentration decreases rapidly, and then gradually decreases until the concentration reaches C1G at position t7.

Further, between the positions t7 and t8, it gradually decreases very slowly, and reaches the density C20 at the position t8. Furthermore, from the position 1T to the position 1T, the concentration C20
gradually decreases from to essentially zero.

As shown in the examples shown in FIGS. 7 to 15, the end of the photosensitive layer on the support side has a portion with a high distribution concentration C of atoms (0+C+N), and the end of the photosensitive layer on the surface layer side has a portion with a high distribution concentration C of atoms (0+C+N). If the distribution concentration C has a considerably low portion or a portion with a concentration substantially close to zero, the distribution concentration of atoms (0, C, N 2 ) at the end of the photosensitive layer on the support side Preferably, the localized region is located at a distance of 500 m from the interface position tB between the support surface and the photosensitive layer.
By providing the thickness within μ, it is possible to more efficiently improve the adhesion between the support and the photosensitive layer.

The localized region may be all or a part of the layer region at the support side end of the photosensitive layer containing atoms (0, C, N 2 ); is determined as appropriate according to the characteristics required of the photosensitive layer to be formed.

The amount of atoms (o, c, N) contained in the localized region is
The maximum value of the molecular concentration C of atoms (0, C2N) is 500 a
tomic ppm or more, preferably Boo atom
ic ppm or more, optimally 1000 atomic
It is desirable to have a distribution state in which the amount is ppm or more.

Furthermore, in the light-receiving member of the present invention, a substance for controlling conductivity can be contained in the photosensitive layer in a uniform or non-uniform distribution in the entire layer region or a part of the layer region.

Examples of the substance that controls the conductivity include so-called impurities in the semiconductor field, and atoms belonging to group Ⅰ of the periodic table (hereinafter simply referred to as ``group Ⅰ'') that give P conductivity.
"group atoms". ), or an atom belonging to Group I of the periodic table (hereinafter simply referred to as "Group V atom") that provides n-type conductivity. Specifically, as group Ⅰ atoms,
B (boron), At (aluminum), Ga (gallium)
, In (indium), and TL (thallium), among which B and Ga are particularly preferred.

Also, as group V atoms, P (phosphorus), A8 (arsenic)
, sb (antimony), and B1 (bismane), among which p and sb are particularly preferred.

When a group II atom or a group V atom, which is a substance that controls conductivity, is contained in the photosensitive layer of the present invention, whether it is contained in the entire layer region or in a part of the layer region will be described later. Thus, the amount to be included will vary depending on the purpose or expected effect.

That is, when the main purpose is to control the conductivity type and/or conductivity of the photosensitive layer, it is contained in the entire layer area of the photosensitive layer. The amount may be relatively small, usually I x 10-3
~1 x IQ" atomic ppm, preferably 5 x 10-2 to 5 x 102102ato
ppm, optimally I x 10" ~ 2 x IQ2
atomic ppm.

In addition, the group (I) atoms or the group (V) 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 the group (I) or group (IV) atoms in the layer thickness direction may be In the case where they are contained in a high concentration on the side in contact with the support, a part of the layer region containing such Group I atoms or Group V atoms or a region containing them in high concentration is used as a charge injection blocking layer. It becomes a functioning place. In other words, 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 side into the photoreceptor layer is made more efficient. In addition, when the group V atoms are contained, when the free surface of the photoreceptive layer is charged to O polarity, it is injected from the support side into the photoreceptor layer. The movement of holes can be more efficiently blocked.

The content in this case is relatively large. Specifically, generally 30 to 5 X 10' atomic
ppm, preferably 50 to I
tomic ppm, optimally I x 102-5 x
IQ3atomic ppm. In order to efficiently exhibit this effect, if the layer thickness of a part of the layer region or the layer region containing a high concentration is t, and the layer thickness of the other photosensitive layer is 1o, then 1/1+10 It is desirable that the relational expression ≦0.4 holds true, more preferably the value of the relational expression is 0.35 or less, most preferably 0.3 or less. Further, the layer thickness of the layer region is generally 3X10-'' to 10μ, but preferably 4X10
−3 to 8 μ, optimally 5×10 −3 to 5 μ.

Next, the amount of group (IV) atoms or group V atoms contained in the photosensitive layer is relatively large on the support side, decreases from the support side toward the side in contact with the surface layer, and in the vicinity of the contact with the surface layer. In this case, a typical example of distributing group (I) atoms or group V atoms so that the amount is relatively small or substantially close to zero is to distribute oxygen atoms,
This can be explained using examples similar to the examples shown in FIGS. 7 to 15, which illustrate the case where at least one selected from carbon atoms and nitrogen atoms is contained. However, the invention is not limited to these examples.

As in the examples shown in FIGS. 7 to 15, the photosensitive layer has a portion with a high distribution concentration C of group (I) atoms or group V atoms on the side closer to the support, and the surface layer side of the photosensitive layer In,
If the distribution concentration C has a portion with a considerably low concentration or a portion with a concentration substantially close to zero, the distribution concentration of group (I) atoms or group V atoms is relatively high in the portion close to the support side. By providing a localized region with a high concentration, preferably by providing the localized region within 5 μm from the interface position in contact with the support surface, the distribution concentration of Group II atoms or Group V atoms is high. The above-mentioned effect that the layer region forms a charge injection blocking layer can be achieved even more efficiently.

As mentioned above, regarding the distribution state of Group Ⅰ atoms or Group V 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 II atoms or group V atoms and the number of groups to be contained in the photosensitive layer are important. It goes without saying that the amounts of Group (2) atoms or Group V atoms may be used in appropriate combinations as necessary. For example, when a charge injection blocking layer is provided at the end of the photosensitive layer on the support side, the polarity of the substance that controls conductivity contained in the charge injection blocking layer is different from the polarity of the substance contained in the charge injection blocking layer in the photosensitive layer other than the charge injection blocking layer. The charge blocking layer may contain a substance that controls the conductivity of the same polarity, or may contain a substance that controls the conductivity of the same polarity in an amount much smaller than that contained in the charge blocking layer.

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. Examples of materials constituting such a barrier layer include inorganic electrically insulating materials such as At203.5in2 and Si3N, and organic electrically insulating materials such as polycarbonate.

Surface layer The surface layer 103 of the light-receiving member of the present invention is the photosensitive layer 1 described above.
02 and has a free surface 104. The surface layer contains at least one selected from oxygen atoms (0), carbon atoms (C), and nitrogen atoms (N), and preferably at least one of hydrogen atoms (H) and halogen atoms (X). Containing a-8i [hereinafter referred to as "a-8
It is written as i(0,C,N)(H,X)J. ], which functions to reduce the reflection of incident light on the free surface 104 of the light-receiving member and increase transmittance, and also improves the moisture resistance, continuous repeated use characteristics, electrical pressure resistance, and usage of the light-receiving member. It functions to improve various properties such as environmental properties and durability.

And, in the light receiving member of the present invention, the surface layer 10
3 and the photosensitive layer 102, the optical bandgap Eopt of the surface layer and the optical bandgap E of the photosensitive layer 102 on which the surface layer is directly provided.
Opt must be matched or matched to such an extent that reflection of incident light at the interface between the surface layer 103 and the photosensitive layer 102 can be substantially prevented.

Furthermore, in addition to the above-mentioned conditions, at the end of the surface layer 103 on the free surface side, it is necessary to ensure that a sufficient amount of incident light reaches the photosensitive layer 102 provided below the surface layer. It is desirable that the end of the surface layer 103 on the free surface side be configured to sufficiently widen the optical bandgap Eopt of the surface layer. The optical band gap Eopt is configured to match at the interface between the surface layer 103 and the photosensitive layer 102, and the optical band gap Eopt is sufficiently increased at the end of the surface layer on the free surface side. In this case, the optical bandgap of the surface layer is configured to change continuously in the layer thickness direction of the surface layer.

In order to control the value of the optical bandgap Eopt of the surface layer in the layer thickness direction as described above, oxygen atom (0), carbon atom (C) and nitrogen atom (N ) by controlling the amount of at least one selected from the group consisting of:

Specifically, at least one type selected from oxygen atoms (0), carbon atoms (C), and nitrogen atoms (N) [hereinafter referred to as "atoms (0,
, N ) J. ] is not contained, atoms (0,
The content of atoms (0, C, N ) is zero or close to zero, and the content of atoms (0, C, N
) is contained, the content of atoms (0, C, N ) at the end of the surface layer in contact with the photosensitive layer and the content of atoms (0, C, N ) at the end of the photosensitive layer in contact with the surface layer are
○, C, N) content should be the same or have no substantial difference. Then, from the end of the surface layer on the photosensitive layer side to the end on the free surface side, atoms (o, C2N)
The amount of atoms (0, C, N 2 ) is continuously increased to contain atoms (0, C, N 2 ) near the end on the free surface side in an amount sufficient to prevent reflection of incident light on the free surface. below,
Some typical examples of the distribution state of atoms (0, C, N 2 ) in the surface layer will be explained with reference to FIGS. 20 to 22, but the present invention is not limited to these examples.

In Figures 16 to 18, the horizontal axis represents atoms (0, C, N
) and distribution concentration C1 of silicon atoms. The vertical axis indicates the layer thickness t of the surface layer. In the figure, tT is the interface position between the photosensitive layer and the surface layer, 1F is the free surface position, and the solid line is the concentration of atoms (0,C ,N
), and the broken line shows the change in the distributed concentration of silicon atoms (Sl).

Figure 16 shows atoms (○, C, N) contained in the surface layer.
) and silicon pudding (Sl) in the layer thickness direction. In this layer, from the interface position tT to the position t1, the distributed concentration C of atoms (0, C, N) increases linearly from zero to the concentration C1, while the distributed concentration of silicon atoms increases as the concentration C2 The concentration decreases in a linear manner from position 11 to position 1. Until , the distribution concentrations C of atoms (0, C, N) and silicon atoms maintain constant values of concentration C1 and concentration C3, respectively.

In the example shown in FIG. 17, the distribution concentration C of atoms (0, C2N) is from zero to the concentration C4 from the interface position tT to the position t3.
The concentration C4 increases in a linear function up to the point C4, and maintains a constant value of the concentration C4 from the position t3 to the position 1F.

On the other hand, the distribution concentration C of silicon atoms decreases linearly from the concentration C5 to the concentration C6 from the position tT to the position t2, and from the concentration C6 to the concentration C6 from the position t2 to the position t3.
7 in a linear function, and maintains a constant value of concentration C7 from position t3 to position 1F. If the concentration of silicon atoms is high at the beginning of the formation of the surface layer, the deposition rate becomes faster; however, as in this example, the deposition rate can be corrected by decreasing the distributed concentration of silicon atoms in two steps. I can do it.

In the example shown in FIG. 18, from position 1T to position t4,
The distribution concentration of atoms (0, C, N) is from zero to concentration Ce'
On the other hand, the distributed concentration C of silicon atoms (Sl) continuously decreases from the concentration C9 to the concentration CIO4, and from the position t4 to the position 1. Up to , atoms (0,
The distributed concentration of C, N 2 ) and the distributed concentration of silicon atoms (Sl) are maintained at constant values of the concentration C8 and the concentration CIO, respectively. As in this example, when the distribution concentration of atoms (0, C, N 2 ) is gradually and continuously increased, the rate of change in the refractive index in the layer thickness direction of the surface layer can be made almost constant.

As shown in FIGS. 16 to 18, the surface layer of the light-receiving member of the present invention has atoms (
0, C, N) is substantially close to zero and increases continuously toward the free surface, and at the end of the surface layer on the free surface side, the concentration is relatively high. It is desirable to provide an area. In this case, the layer thickness of the layer region is usually 0.1 μm in order to function as an antireflection layer and a protective layer.
The above is made.

It is desirable that the surface layer also contain at least one of hydrogen atoms or halogen atoms, and the amount of hydrogen atoms (I()) or the amount of halogen atoms (X) to be contained, or the sum of the amounts of hydrogen atoms and halogen atoms ( H+X) is usually 1
~40 atomic%, preferably 5-3Q at
omic ql, optimally 5 to 25 atomic ql.

In addition, in the present invention, the layer thickness of the surface layer is one of the important factors for efficiently achieving the purpose of the present invention, and is determined as appropriate depending on the intended purpose. It is necessary to determine the amount of oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms to be included in the layer, or the characteristics required for the surface layer, 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 surface layer is usually 3X10-3
~30μ, more preferably 4 x 10-3~
20μ, particularly preferably 5XIO-3 to 10μ.

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.

Furthermore, 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. 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, level of equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be manufactured. The glow discharge method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the receiving member, and carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. be.

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

For example, in the glow discharge method, to form a layer composed of a-8i (H, A raw material gas for (H) introduction and/or halogen atom (X) introduction is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber, and a glow discharge is generated in the deposition chamber. a-8i(H,X) on the support surface of
form a layer consisting of

As the raw material gas for supplying S1, Sin, Eli
Examples include silicon hydride (silanes) in a gaseous state or that can be gasified, such as 2H6, Eli3HB, Si, and Hlo. In particular, SiH4,5i2H , is preferable.

Further, as the raw material gas for introducing halogen atoms, there are many halogen compounds, such as evaporative halogen gas,
Gaseous or gasifiable halogen compounds are preferred, such as halides, interhalogen compounds, and halogen-substituted 7-rane derivatives. Specifically, fluorine, chlorine, bromine,
Iodine halogen gas, BrF, C7F, C6
F6, BrF5, BrF3. IP,7,ICz,
Interhalogen compounds such as r, Oyobi S i F,
, Sl. Examples include silicon halides such as F6.5ICLc, 5iBr, and the like. When using a gaseous silicon halide or one that can be gasified as described above, i3
This is particularly effective because a layer composed of a-8i containing halogen atoms can be formed without using a separate raw material gas for supplying i.

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, HF, HO2, HBr, etc.
Genide, SiH4, Si2H6, 5i3HB, 5i
Silicon hydride such as 4H1o, aluminum is SiH2F2.5i
H2I2.5iH2C72, 5iHCum, 5iH2Br
2.8iHBr3 etc. (7) Gaseous or gasifiable materials such as halogen-substituted silicon hydride can be used, and when these raw material gases are used, it is difficult to control electrical or photoelectric properties. It is effective because the content of hydrogen atoms (I(), which is extremely effective) can be easily controlled.And when the above-mentioned hydrogen halide or the above-mentioned halogen-substituted silicon hydride is used, halogen This method is particularly effective because hydrogen atoms (H) are also introduced simultaneously with the introduction of atoms.

In addition, the amount of hydrogen atoms (H) and/or halogen atoms (X) to be contained in the a-8i layer can be controlled, for example, by controlling the support temperature, introducing hydrogen atoms (H) and/or halogen atoms (X), etc. This is done by controlling the amount of starting material used for this purpose introduced into the deposition chamber, the discharge power, etc.

To form a layer consisting of a-8i(H,X) by reactive sputtering or ion blating,
For example, in the case of the sputtering method, in order to introduce halogen atoms, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned no-rodene atoms is introduced into the deposition chamber to form a plasma atmosphere of the gas. good.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, N2 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 gas for introducing nitrogen atoms and H2 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to generate plasma. An atmosphere is formed, and the S
A layer consisting of a-8i(H,X) is formed on the support by sputtering the i target.

Using a glow discharge method, sputtering method, or ion blating method, a-8i(H, In order to form a layer composed of a quality material, when forming a layer of a-8i (H, The substance, the starting material for introducing oxygen atoms, or the starting material for introducing carbon atoms is the a-8i (H,
X) by their use in conjunction with the starting materials for the formation and their controlled inclusion in the layer to be formed.

For example, a layer or layer region composed of a-8i (H, In order to form a layer composed of a-8i (H, This is accomplished by controlling the amount of these starting materials into the layer being formed.

Specifically, starting materials for introducing m-group atoms include B2H6, B, and Ho for boron atom introduction. ,B5H9,B
Examples include boron hydrides such as 5H11, B6H10, B6H12, and B6H14, and boron halides such as BF3, BCL3, and BBr3.

In addition, ALC4a, GaCj! ,l,Ga(CH3)
2, Engineering, CL3, T2C, etc. can also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, hydrogen north neighbors such as PH3, P2H6, PH,
Engineering, PF3, PF5, PC43, PC&, PBr3, P
Examples include halogen ratios such as Br3 and P3. In addition, A8H3, A8F3, ABC, A3Br3, AEI
F5.81) N3, SbF3.81) N5.5bC43
,81) C45, BiH3, B1C73, B1Br3
etc. can also be mentioned as effective starting materials for introducing Group V atoms.

When a glow discharge method is used to form a layer or layer region containing oxygen atoms, a starting material for introducing oxygen atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. is added. As such a starting material for introducing oxygen atoms, almost any gaseous substance or substance that can be gasified can be used as long as it has at least an oxygen atom as a constituent atom.

For example, a raw material gas containing silicon atoms (Sl), a raw material gas containing oxygen atoms (0), hydrogen atoms (H) or/and halogen atoms (X
) as constituent atoms at a desired mixing ratio, or a raw material gas containing silicon atoms (Sl) as constituent atoms and oxygen atoms (0) and hydrogen atoms (H).
A raw material gas having constituent atoms is mixed at a desired mixing ratio, or a raw material gas having silicon atoms (Si), oxygen atoms (0), and It can be used in combination with a raw material gas having three hydrogen atoms (H) as its constituent atoms.

Alternatively, a raw material gas having oxygen atoms (◯) as constituent atoms may be mixed with a raw material gas having silicon atoms (Sl) and hydrogen atoms (H) as constituent atoms.

Specifically, for example, oxygen (02), ozone (03), -
Nitrogen oxide (No), nitrogen dioxide (No2), -nitrogen dioxide (N20), nitrogen sesquioxide (N2O3), trinitrogen tetroxide (N204), nitrogen sesquioxide (N205), nitrogen trioxide (1103), silicon atom (Sl), oxygen atom (○), and hydrogen atom (H) as constituent atoms, for example,
Examples include lower siloxanes such as disiloxane (H3SiO3iH3) and trisiloxane (H3SiO8iH20SiH3).

To form a layer or a layer region containing oxygen atoms by sputtering, a monocrystalline or polycrystalline Si wafer or a 5102 wafer, or a wafer containing a mixture of Sl and 5102 is used as a target. This can be done by performing S-R stumbling in various gas atmospheres.

For example, if a Si wafer is used as a tarded material, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluting gas as necessary, and the material gas is diluted with a diluting gas as necessary to create a deposition chamber for sputtering. The above 81 way...- by forming a gas plasma of these gases
can be sputtered.

Alternatively, by using Sl and 8102 as separate targets or by using a single mixed target of Sl and 5i02, 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 also be used as an effective gas in the case of S-Q Tsuttering.

When a glow discharge method is used to form a layer or layer region containing nitrogen atoms, a starting material for introducing nitrogen atoms is added to a starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. Add substance. As the starting material for introducing nitrogen atoms, almost any gaseous substance or gasifiable substance having at least nitrogen atoms as a constituent atom can be used.

For example, a raw material gas containing silicon atoms (Sl), a raw material gas containing nitrogen atoms (N), and hydrogen atoms (H) or/and rodene atoms (X
) with a raw material gas having constituent atoms at a desired mixing ratio, or a raw material gas having silicon atoms (Si) with nitrogen atoms (N) and hydrogen atoms (H).
This can also be used by mixing it with a raw material gas having constituent atoms at a desired mixing ratio.

Alternatively, a raw material gas having nitrogen atoms (N) as constituent atoms may be mixed with a raw material gas having silicon atoms (Sl) and hydrogen atoms (H) as constituent atoms.

A starting material that is effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming a layer or layer region containing nitrogen atoms is one that has N as a constituent atom or a mixture of N and H.
For example, nitrogen (N2), ammonia (
NH3), Todora, ) :, t (H2NNH2), hydrogen azide (IJH3), ammonium azide (NH,N
Gaseous or gasifiable nitrogen, such as 3), and nitrogen compounds such as nitrides and azides can be mentioned. In addition to the above, halogenated nitrogen compounds such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N2) are listed, since in addition to introducing nitrogen atoms, halogen atoms (X) can also be introduced. be able to.

To form layers or layer regions containing nitrogen atoms by sputtering methods, monocrystalline or polycrystalline Si wafers or Si3N4 wafers, or Si and Si3
This may be carried out by sputtering a wafer containing a mixture of N as tarded in one type of gas atmosphere.

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

Alternatively, by using Si and Si3N4 as separate targets, or by using a single glue target containing a mixture of Sl and Si3N, a dilution gas atmosphere can be created as a gas for the star. or by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms.

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

For example, in order to form a layer or a layer region containing carbon atoms by a glow discharge method, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (C), Hydrogen atom (H) or / as necessary
and a raw material gas whose constituent atoms are halogen atoms (X) at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Sl) and carbon atoms (C).
and a raw material gas whose constituent atoms are hydrogen atoms (H) are also mixed at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and /licon atoms (
SL), carbon atoms (C), and hydrogen atoms (H) as constituent atoms, or furthermore, a raw material gas containing silicon atoms (SL) and hydrogen atoms (H) as constituent atoms and carbon atoms. A mixture of raw material gases containing (C) as constituent atoms is used.

To form a layer region composed of a-6iC (H, The wafers that have been prepared are treated as terdead, and the wafers are cleaned in the desired gas atmosphere. This is done by tutarinda.

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 changed to Ar, H, or
S is diluted with a diluent gas such as S.
It is enough to sputter one wafer.

In addition, when using Sl and C as separate targets, or when using a mixed target of Sl and C, hydrogen atoms or /
The raw material gas for introducing halogen atoms may be diluted with a diluent gas if necessary, and introduced into the deposition chamber for SQ 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.

Si is effectively used as such raw material gas.
SiH4, 512H6, Si3 whose constituent atoms are and H
Silicon hydride gas such as silanes such as H8, Si, HlO, etc., saturated hydrocarbons having 1 to 4 carbon atoms containing C and H as constituent atoms, ethylene-based carbonization having 2 to 4 carbon atoms Examples include hydrogen and acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2H6), pro-ξn (C3H[]), ]
n-butane n'4H1,O), Takutontan (C5H12
), ethylene hydrocarbons include ethylene (C2H4
), propylene (C3H6), butene-L (C,H
8), butene-2 (C4H8), inbutylene (C4
Examples of acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), and butyne (C4H6).

As a raw material gas containing Sl, C, and H as constituent atoms, S
Examples include alkyl silicides such as i(CH3)4.5i(C2H5). In addition to these raw material gases, H2 can of course also be used as the raw material gas for H introduction.

When forming the photosensitive layer and surface layer of the present invention by a glow discharge method, a sputtering method, or a Louis ion blating method, a group Ⅰ atom or a group Ⅰ atom or atom introduced into a-6i(H,X) The content of (0, C, N 2 ) is determined by controlling the gas flow rate and gas flow rate ratio of the starting material introduced into the deposition chamber.

In addition, conditions such as support temperature, gas pressure in the deposition chamber, and discharge power during formation of the photoreceptive layer are important factors in obtaining a photoreceptor with desired characteristics, and the conditions of the layer to be formed include It is selected appropriately taking into consideration the function. Furthermore, since these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be contained in the photoreceptive layer, it is necessary to determine them by taking into consideration the type and amount of the atoms to be contained. There is also.

Specifically, the support temperature is usually 50 to 350'C, particularly preferably 50 to 250'C.

The gas pressure inside the deposition chamber is normally 0. (11% I Tor
r, particularly preferably 0.5 to Q, 5 TOrr
shall be.

In addition, discharge, e-war is 0.005 to 50 W/crr
Usually it is 12, but more preferably 0. (1
1-30 W 7cm2, particularly preferably 0. (11~
20 W/crX.

However, the specific conditions for layer formation, such as support temperature, electric discharge, e-warning, 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 oxygen atoms contained in the photoreceptive layer of the present invention,
To make the distribution of carbon atoms, nitrogen atoms, Group I atoms or Group V atoms, or hydrogen atoms and/or halogen atoms uniform, the above-mentioned conditions must be kept constant when forming the photoreceptive layer. It is necessary to maintain it.

Furthermore, in the present invention, in addition to forming the photoreceptive layer, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or Group I atoms or Group V atoms contained in the layer may be changed in the layer thickness direction. In order to form a photoreceptive layer having a desired distribution state in the layer thickness direction, if a glow discharge method is used, oxygen atoms, carbon atoms, nitrogen atoms, or group Ⅰ or group V atoms may be introduced. appropriately changing the gas flow rate when introducing the starting material gas into the deposition chamber according to the desired rate of change;
Formed while keeping other conditions constant. Specifically, in order to change the gas flow rate, the opening of a predetermined needle valve provided in the middle of the gas flow path system is gradually opened by some commonly used method, such as manually or by an externally driven motor. All you have to do is perform an operation to change it. 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 oxygen atoms, carbon atoms, nitrogen atoms, Group I atoms, or Group V atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired value. To form the distribution state in the layer thickness direction, oxygen atoms, carbon atoms,
The starting material for introducing nitrogen atoms, Group I atoms, or Group V atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is varied according to the desired rate of change.

〔Example〕

Hereinafter, the present invention will be explained in detail according to Examples 1 to 10, but the present invention is not limited thereto.

In each example, the photoreceptive layer was formed using a glow discharge method. FIG. 19 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

1902.1903.1904.1905.19 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the gas cylinder No. 06, and as an example,
For example, 1902 is EliH, gas (purity 99.99
9ch) cylinder, 1903 contains B21 (6
Gas (purity 99.999%, hereinafter abbreviated as B2 H6/H2) cylinder, 1904 is CH, gas (purity 99.9
99%) cylinder, work 905 is NH3 gas (purity 99.9
99%) cylinder, 1906 is H2 gas (purity 99.
999%) Al in a cylinder.

In order to flow these gases into the reaction chamber 19 (11), valves 1922 to 1926 of gas cylinders 1902 to 1906 are used.
, make sure that the leak valve 1935 is closed, and also check that the inlet 7e valves 1912 to 1916 and the outlet valve 19
17-1921, confirm that the auxiliary valves 1932 and 1933 are open, and first open the main valve 1934.
Open the reaction chamber 19 (11) and evacuate the inside of the gas pipe. Next, the vacuum gauge 1936 reads approximately 5 X, 10 = torr.
At this point, close the auxiliary valves 1932, 1933 and the outflow valves 1917-1921.

An example of forming a light-receiving layer on the base cylinder 1937 will be given. Gas cylinder 1902 Yosu SiH4 gas,
Open the valves 1922 and 1923 to supply B2 H6/H2 gas from the gas cylinder 1903 to the outlet pressure gauge 19.
The pressure of 27.1928 is adjusted to 1 klil 7 cm2, and the inflow valves 1912 and 1913 are gradually opened to allow the flow into the mass flow controllers 1907 and 1908. Subsequently, the outflow valves 1917, 1918 and the auxiliary valve 1932 are gradually opened to supply the gas to the reaction chamber 19 (11).
Let it flow inside. At this time, Sin, gas flow rate, B2H
6/Adjust the outflow valves 1917 and 1918 so that the ratio of H2 gas flow rate becomes the desired value, and also adjust the reaction chamber 19 (1
While checking the reading on the vacuum gauge 1936, adjust the opening of the main valve 1934 so that the pressure inside the main valve 1934 reaches the desired value.

Then, the temperature of the base cylinder 1937 becomes the heating heater 1.
938 confirms that the temperature is set in the range of 50 to 400°C, the power supply 1940 is set to the desired power to generate a glow discharge in the reaction chamber 19 (11), and the microcomputer (not shown) according to the pre-designed rate of change line.
H6/H2 gas flow rate and SiH.

First, a photosensitive layer composed of a-8i(H,X) containing boron atoms is formed on the base cylinder 1937 while controlling the gas flow rate.

To form a surface layer on the photosensitive layer, following the above operation, for example, each of SiH4 gas and CH4 gas is diluted with a diluent gas such as He, Ar, H2, etc. as necessary, and the desired gas flow rate is adjusted. The SiH4 gas and the CH4 gas flow into the reaction chamber 19 (11), and the gas containing carbon atoms is controlled using a microcomputer (not shown) to control the gas flow rates of the SiH4 gas and the CH4 gas according to a pre-designed rate of change line. a-8i (
A surface layer composed of H, X) is formed.

When forming the photosensitive layer and the surface layer, the flow rate of the raw material gas is controlled using a microcomputer, etc.
By using a diluent gas together with the raw material gas for each atom introduction, the gas pressure in the reaction chamber 19 (11) can be stabilized, and stable film forming conditions can be ensured.

Needless to say, all outflow valves other than the gas outflow valves required when forming each layer are closed.
In addition, when forming each layer, in order to avoid that the gas used to form the previous layer remains in the reaction chamber 19 (11) and in the gas piping leading from the outflow valves 1917 to 1921 to the reaction chamber 19 (11). , close the outflow valves 1917 to 1921, open the auxiliary valves 1932 and 1933, and close the main valve 1.
934 is fully opened and the system is once evacuated to high vacuum, as necessary.

Test Example 1 A SUS stainless steel rigid sphere with a diameter of 0.6M was chemically treated to etch the surface to form irregularities. Treatment agents used include acids such as hydrochloric acid, hydrofluoric acid, sulfuric acid, and chromic acid;
Examples include 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 γmax = 5 μm) treated by the method of Test Example 1, No. 6 (A),
(B) Using the apparatus shown in the figure, the surface of an aluminum alloy cylinder (diameter 60 wtr, length 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 size of R and D, it was found that if R is less than 0.1 g, the rigid sphere must be made small and light to secure the falling height, making it difficult to control the formation of dents. This is not preferable because R is 2. O
If M is exceeded, the rigid sphere will be made heavier and the falling height will be adjusted. For example, if D becomes relatively small, the falling height will need to be made extremely low, thereby controlling the formation of dents. Furthermore, if D is less than 0.02 m, the rigid sphere must be made small and light to secure the falling height, which is undesirable because it becomes difficult to control the formation of dents. , respectively, were confirmed.

Furthermore, when the formed trace depressions were examined, it was confirmed that minute irregularities corresponding to the surface irregularities of the rigid sphere were formed within the trace depressions.

Example 1 The surface of an aluminum alloy cylinder was treated in the same manner as Test Example 2, and D and -Nα1 (11 to 1
06) got it.

Next, a light-receiving layer was formed on the At support (sample Nα1 (11-106) using the manufacturing apparatus shown in FIG. 19 under the conditions shown in Table 1B below. At this time, the surface layer was formed The gas flow rates of CH, gas, H2 gas, and SiF4 gas at this time were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG.

Furthermore, these light-receiving members were exposed to light with a wavelength of 780 nm and a spot diameter of 80 nm using the image exposure apparatus shown in
Image exposure was performed by irradiating with a μm laser, and development and transfer were performed to obtain an image.

No interference fringe pattern was observed in any of the images obtained, and they were of extremely good quality.

Note that FIG. 20 (A) is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 20 (B1) is a schematic side view schematically showing the entire exposure apparatus. is a light receiving member, 2002 is a semiconductor laser, and 2003 is fθ
A lens 2004 indicates a polygon mirror.

Next, as a comparison, an aluminum alloy cylinder (Nn10
7) (Diameter 60M, length 298mm, uneven pitch 100μm
A light-receiving member was produced in the same manner as described above, using an uneven surface having a depth of 3 μm. 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 obtained 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 a d support (Nrindar Nn 1 (11-107)) 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 the boron atoms contained in the photosensitive layer are B2H6
/SiF, = 100 ppm, and K was introduced as much as possible so that the entire layer was coated with about 200 pI) m The gas flow rate 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 2A.

Example 3 The same procedure as in Example 1 was carried out except that a rigid sphere with the surface unevenness height γmaX shown in the upper column of Table 3A was used, and a spherical trace depression (D = 450 ± 50 (μm), -fl = o,
os) with At support (cylinder positive 3 (11-3
06) was obtained.

Next, the At support (cylinder NcL3 (11-306
), a light-receiving layer was formed thereon under the conditions shown in Table 3B below using the manufacturing apparatus shown in Figure A.

In addition, B2H6/H2 gas, H
2 gas, and NO gas during surface layer formation, SiF
'.

The gas flow rates of gas and H2 gas are shown in Figure n and Figure 24, respectively.
According to the flow rate change line shown in the figure, the microcomputer
Adjusted automatically by control. Further, boron atoms contained in the photosensitive layer were introduced under the same conditions as in Example 2.

When images were formed on the obtained light-receiving member in the same manner as in Example 1, the occurrence of interference fringes in the obtained images was as shown in the lower column of Table 3A.

Shell Example 4 A photoreceptive layer was formed on the At support (cylinder Nn3. (11 to 306)) in the same manner as in Example 3, except that the photoreceptive layer was formed according to the layer formation conditions shown in Table 4B. In addition, when forming the photosensitive layer,
The gas flow rates of gas and H2 gas, and the gas flow rates of NH3 gas, SiF, gas 2, and H2 gas during surface layer formation are controlled by a microcomputer according to the flow rate change lines shown in FIGS. 5 and 26, respectively. Yes, it was automatically adjusted.

In addition, the boron atoms contained in the photosensitive layer are
was introduced under the same conditions.

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 to 10 At support of Example 1 (cylinder Nn 103 to 1σ
6) 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 Tables 5 to 10. In each example, the changes in the gas flow rate of the gas used during the formation of the photosensitive layer and the formation of the surface layer were controlled by a microcomputer according to the flow rate change line shown in the flow rate change chart written in Table 11. automatically adjusted. Further, boron atoms to be contained in the photosensitive layer were introduced under the same conditions as in Example 2.

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 good quality.

Table 11 [Summary of Effects of the Invention] The light-receiving member of the present invention has the above-described layer structure, thereby solving all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when laser light, which is coherent monochromatic light, is used as a light source, the appearance of interference fringes in images formed due to interference phenomena can be significantly prevented, resulting in extremely high-quality visible images. 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 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.

[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 an example of the configuration 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
(B) is a longitudinal sectional view. 7 to 15 are diagrams showing the distribution state of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and group (I) or group V atoms in the layer thickness direction in the photosensitive layer of the present invention, 16th to 1st
Figure 8 is a diagram showing the distribution state of at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in the layer thickness direction in the surface layer of the present invention, and in each figure, the vertical axis represents the layer thickness of the photoreceptive layer. The thickness is shown, and the horizontal axis represents the distribution concentration of each atom. FIG. 19 is an example of an apparatus for manufacturing the light-receiving layer of the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. FIG. 3 is a diagram illustrating an image exposure apparatus using laser light. Figures 21 to 21A are diagrams showing changes in gas flow rate in forming the photoreceptive layer of the present invention, in which the vertical axis represents the gas flow rate and the horizontal axis represents the gas flow rate. Regarding Figures 1 to 3. 100... Light receiving member, 1 (11... Support, 10
2.2 (11.3 (11... photosensitive layer, 103.202
．． 302...Surface layer, 1o4.203.303...
Free surface, 204.304... Regarding the interface between the photosensitive layer and the surface layer in Figure 4.5, 4 (11.5 (11... Support, 402.502...
・Support surface, 403.503... Spherical trace depression, 4
03', 503'...Rigid sphere with uneven surface shape,
404...Micro uneven shape formed in the spherical trace depression, 404'...Irregular shape formed on the surface of the rigid sphere Regarding FIG. 6, 6 (11... Cylinder, 602... Rotating shaft ( (reception)
, 603... Drive means, 604... Rotating container, 60
5... Rigid sphere with uneven surface shape, 606...
Regarding the ribs provided on the inner wall of the container, 607... Shower pipe in Fig. 19, 19 (11... Reaction chamber, 1902-1906... Gas cylinder, 1907-1911... Mass flow controller, 1912-1916. ...Inflow valve, 1917
~1921...Outflow valve, 1922~1926...
・Valve, 1927-1931...Pressure regulator, 19
32.1933...Auxiliary valve, 1934...Main no 9 lube, 1935...Leak valve, 1936...
...Vacuum gauge, 1937...Base cylinder, 1938
...heater, 1939...motor, 194
0... Regarding the addition of high frequency power supply. 20 (11...Light receiving member, 2002...Semiconductor laser, 2003...Fθ lens, 2004...Polygon mirror. Applicant Canon Co., Ltd. None) No. 6 [A
3 Figure 6 [80 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure □C Figure 13 Figure 14 Figure 15 Figure □C SCCM SCC
MH2 is Su B2H, /H2 Gas Figure 25 H2 Gas B2H6/H2 Gas Procedure Amendment (Method) January 20, 1985 Director General of the Patent Office Uga Michibe Tono Tsuyoshi 1, Indication of Case 1985 Patent Application No. 242786 No. 2, Name of the invention Light-receiving member 3, Relationship to the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name
(100) Canon Co., Ltd. 4, Agent Address: Kojimachi Green Pill 6, 3-12-6 Kojimachi, Chiyoda-ku, Tokyo, Specification and drawings to be amended 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 photosensitive layer made of an amorphous material having silicon atoms as a matrix, silicon atoms, oxygen atoms,
A light-receiving member comprising a light-receiving layer having a surface layer made of an amorphous material containing at least one selected from carbon atoms and nitrogen atoms, wherein the photosensitive layer and the surface layer The optical band gap is matched at the interface, the surface of the support has an uneven shape formed by a plurality of spherical trace depressions, and further has a plurality of minute unevenness shapes within the spherical trace depressions. A light-receiving member characterized in that: (2) The light-receiving member according to claim (1), wherein the photosensitive layer contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms. (3) The light-receiving member according to claim (1), wherein the photosensitive layer contains a substance that controls conductivity. (4) Claim No. (1) in which the photosensitive layer has a multilayer structure
The light-receiving member described in 2. (5) The light-receiving member according to claim (4), wherein the photosensitive layer has, as one of its constituent layers, a charge injection blocking layer containing a substance that controls conductivity. (6) The light-receiving member according to claim (4), wherein the photosensitive layer has a barrier layer as one of the constituent layers. (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. (8) 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. (9) 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). (10) The uneven shape of the surface of the support body is an uneven shape due to 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 (9). (11) 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). (12) The light-receiving member according to claim (11), wherein the width D of the spherical trace depression satisfies the following formula: D≦0.5 mm. (13) The light-receiving member according to claim (1), wherein the height r of the minute irregularities within the spherical trace depressions is a value that satisfies the following formula: 0.5 μm≦r≦20 μm. (14) Claim No. 1, wherein the support is a metal body.
) The light-receiving member according to item 1.