JPH0668636B2 - Light receiving member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to light (here, light in a broad sense, ultraviolet light, visible light,
The present invention relates to a light receiving member sensitive to electromagnetic waves such as infrared rays, X rays, and γ rays). More specifically, it relates to a light receiving member suitable for using coherent light such as laser light.

[Description of Prior Art]

As a method of recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light receiving member with laser light modulated according to the digital image information, and then the latent image is developed, Further, a method of recording an image is known, in which transfer, fixing and the like are performed as necessary. In particular, in the image forming method by electrophotography, a small and inexpensive He-Ne laser or semiconductor laser ( It is common to carry out image recording using a light 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 the fact that the matching of the light sensitive region is superior to other types of light receiving members,
The Vickers hardness is high, and the problem of pollution is small. It is evaluated, for example, in JP-A-54-86341 and JP-A-56-837.
Attention has been paid to a light receiving member made of an amorphous material containing silicon atoms (hereinafter abbreviated as "a-Si") as disclosed in Japanese Patent No. 46.

However, in the above-mentioned light receiving member, when the light receiving layer is an a-Si layer having a single layer structure, it is possible to secure a dark resistance of 10 ¹² Ωcm or more required for electrophotography while maintaining its high photosensitivity. Is required to structurally contain a hydrogen atom, a halogen atom, or a boron atom in addition to them in a controlled amount in a specific amount range. Therefore, various conditions for forming a layer are required. There is a considerable limit to the tolerance of the design of the light receiving member, such as the need to strictly control the It has been proposed to improve the design tolerance by making the high photosensitivity effective even if the dark resistance is low to some extent. That is, for example, JP 54-121743 A, JP 57-
No. 4053, JP-A-57-4172, the light-receiving layer has a layered structure of two or more layers in which layers having different conductivity characteristics are laminated, and a depletion layer is formed inside the light-receiving layer, or JP-A-57-52178, 52179, 52180, 58159
No. 58160, No. 58161, each of which has a multilayer structure in which 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 having improved dark resistance has been proposed.

However, such a light-receiving layer having a multi-layered light-receiving layer has a variation in the layer thickness of each layer, and when laser recording is performed using this, the laser beam is a coherent monochromatic light. From the laser light irradiation side free surface, each layer constituting the light receiving layer and the layer interface between the support and the light receiving layer (hereinafter, both the free surface and the layer interface are collectively referred to as “interface”). Often, each of the reflected light that is reflected causes interference.

This interference phenomenon is a so-called
It appears as an interference fringe pattern, which causes a defective image. In particular, when forming a halftone image with high gradation, a blocking image with extremely poor discrimination is provided.

Another important point is that the absorption of the laser light in the light-receiving layer decreases as the wavelength region of the semiconductor laser light used becomes longer, which causes a problem that the interference phenomenon becomes remarkable. .

That is, for example, in a structure having two or more layers (multilayer), an interference effect occurs in each of these layers, and the respective interferences act synergistically to form an interference fringe pattern. However, if the interference fringes directly affect the transfer member, and the interference fringes corresponding to the interference fringe pattern are transferred and fixed on the member to appear on the visible image, resulting in a defective image.

As a measure to solve such a problem, (a) a diamond is cut on the surface of the support to form a light-scattering surface by providing irregularities of ± 500Å to ± 10000Å (see, for example, JP-A-58-162975), (b) a method of providing a light absorbing layer by black-anodizing the surface of an aluminum support, or dispersing carbon, a coloring pigment, or a dye in a resin (see, for example, JP-A-57-165845), (c) A method of providing a light-scattering and antireflection layer on the surface of an aluminum support by subjecting the surface of the aluminum support to a matte finish alumite treatment, or by providing sand-blasted fine irregularities in a grain shape (for example, JP-A-57-165).
Japanese Patent No. 54) is proposed.

Although these proposed methods bring some results, they are not sufficient to completely eliminate the interference fringe pattern appearing on the image.

That is, with respect to the method (a), a large number of specific irregularities are provided on the surface of the support, and although the appearance of an interference fringe pattern due to the light scattering effect is prevented for a while, it still remains as light scattering. Since the specular reflection light component remains, the interference fringe pattern due to the specular reflection light remains, and the irradiation spot spreads due to the light scattering effect on the surface of the support, resulting in a substantial reduction in resolution. Will end up.

With regard to the method (b), the black alumite treatment cannot completely absorb the light, and the reflected light on the surface of the support remains. When a color pigment dispersed resin layer is provided, a
-When the -Si layer is formed, the degassing phenomenon occurs in the resin layer, the layer quality of the formed light-receiving layer is significantly deteriorated, and the resin layer is damaged by the plasma during the formation of the a-Si layer. Then, there is a problem that the original absorption function is reduced and the subsequent formation of the a-Si layer is adversely affected by the deterioration of the surface state.

With regard to the method (c), for example, regarding incident light, a part of the incident light is reflected on the surface of the light-receiving layer to be reflected light, and the rest enters the light-receiving layer to be transmitted light. On the surface of the support, part of the transmitted light is scattered and becomes diffused light, and the rest is specularly reflected and becomes reflected light, and part of it becomes outgoing light and goes out. However, the emitted light is
Since it is a component that interferes with the reflected light and remains in any case, the interference fringe pattern still does not completely disappear.

By the way, in order to prevent interference in this case, there is an attempt to increase the diffusivity of the surface of the support so that multiple reflection inside the light-receiving layer does not occur. The light diffuses to cause halation, which eventually reduces the resolution.

In particular, in the light receiving member having a multilayer structure, even if the surface of the support is irregularly roughened, the light reflected by the first layer surface, the light reflected by the second layer, and the specular light reflected by the surface of the support are Interference results in an interference fringe pattern according to the thickness of each layer of the light receiving member. Therefore, in the light receiving member having a multilayer structure, it is impossible to completely prevent the interference fringes by irregularly roughening the surface of the support.

Also, when the surface of the support is irregularly roughened by a method such as sandblasting, the surface roughness varies widely among the lots, and even within the same lot, the surface roughness is uneven. , There is a problem in manufacturing control. In addition, relatively large projections are often formed randomly, and such large projections cause local breakdown of the photoreceptor layer.

Also, when the surface of the support is simply roughened,
Since the light receiving layer is deposited along the uneven shape of the surface of the support, the uneven surface of the uneven surface of the support and the uneven surface of the uneven surface of the light receiving layer are parallel to each other, and the incident light is bright In addition, a light and dark stripe pattern appears due to the non-uniformity of the layer thickness of the light receiving layer in the entire light receiving layer. Therefore, it is not possible to completely prevent the occurrence of interference fringe patterns only by regularly roughening the surface of the support.

Also, when a light-receiving layer having a multi-layered structure is deposited on a support whose surface is regularly roughened, regular reflection light on the support surface,
In addition to the interference with the reflected light on the surface of the light receiving layer, the interference due to the reflected light at the interface between the layers is added, so that the degree of appearance of the interference fringe pattern of the light receiving member having a further structure becomes more complicated.

[Object of the Invention]

An object of the present invention is to eliminate the above-mentioned problems and satisfy various requirements for a light-receiving member having a light-receiving layer mainly composed of a-Si.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially stable regardless of the use environment, are substantially stable to light, and have excellent light fatigue resistance, and even when repeatedly used, a deterioration phenomenon. To provide a light-receiving member having a light-receiving layer composed of a-Si, which is excellent in durability and moisture resistance, has no or almost no residual potential observed, and is easy to manage in production. is there.

Another object of the present invention is to provide a photoreceptive member having a photoreceptive layer composed of a-Si, which has a high photosensitivity in the entire visible light region, an excellent matching property with a semiconductor laser, and a fast photoresponse. To provide.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer composed of a-Si, which has high photosensitivity, high SN ratio characteristics, and high electrical withstand voltage.

Another object of the present invention is to provide excellent adhesion between the layer provided on the support and the support or between the layers of the laminated layers,
The structure is precise and stable, and the layer quality is high.
It is to provide a light receiving member having a light receiving layer composed of Si.

Still another object of the present invention is suitable for image formation using coherent monochromatic light, and even during long-term repeated use, there is no appearance of interference fringe patterns and spots during reversal development, and there are no image defects or images. To provide a light-receiving member having a light-receiving layer composed of a-Si, capable of obtaining a high-quality image with high density, high density, clear halftone, and no blurring. It is in.

[Structure of Invention]

The present inventors have earnestly studied to overcome the above-mentioned problems of the conventional light-receiving member and achieve the above-mentioned object, and as a result, have obtained the following findings, and based on the findings, the present invention Was completed.

That is, the light-receiving member of the present invention is a first member composed of an amorphous material containing a silicon atom and at least one selected from an oxygen atom, a carbon atom and a nitrogen atom on a support. A photoreceptive layer having a layer and a second layer, the atoms selected from the oxygen atoms, carbon atoms and nitrogen atoms contained in the constituent materials of the first layer and the second layer are different from each other. The width D of the depression is 500 μm or less and the radius of curvature R and the width D of the depression are on the surface of the support.
The present invention is characterized in that it has irregularities due to a plurality of spherical trace depressions with 0.035 ≦ D / R, and that minute irregularities of 0.5 to 20 μm are further formed in the spherical trace depressions.

By the way, the findings obtained by the inventors of the present invention as a result of earnest research are: outline, in a light-receiving member having a plurality of layers on a support, the support surface is provided with irregularities due to a plurality of spherical trace depressions, In addition, the problem of interference fringe patterns appearing during image formation is remarkably solved by providing a plurality of finer concavo-convex shapes in the spherical trace depressions.

This finding is based on the factual relations obtained by various experiments that the present inventors have tried.

This will be described below with reference to the drawings in order to facilitate understanding.

FIG. 1 is a schematic diagram showing a layer structure of the light receiving member 100 according to the present invention, which has an uneven shape due to a plurality of minute spherical trace dents, and further includes a plurality of finer spherical dents. 1 shows a light receiving member provided with a light receiving layer including a first layer 102 and a second layer 103 on a support 101 having an uneven shape along the inclined surface of the unevenness.

2 and 4 are views for explaining the problem of the interference fringe pattern in the light receiving member of the present invention.

FIG. 3 is an enlarged view showing a part of a conventional light receiving member in which a light receiving layer having a multilayer structure is deposited on a support whose surface is regularly roughened. In the figure, 301 is the first layer, 3
02 indicates the second layer, 303 indicates the free surface, and 304 indicates the interface between the first layer and the second layer. As shown in FIG.
When the surface of the support is simply roughened by a means such as cutting, the light-receiving layer is usually formed along the irregular shape of the surface of the support, and therefore the uneven surface of the surface of the support is uneven. And the inclined surface of the unevenness of the light receiving layer have a parallel relationship.

Due to this, for example, the light receiving layer is the first layer 301.
Then, in the light receiving member having a multilayer structure composed of two layers, that is, the second layer 302, for example, the following problems are constantly caused. That is, since the interface 304 between the first layer and the second layer and the free surface 303 are in a parallel relationship, the interface 30
The reflected light R ₂ of the reflected light R ₁ and the free surface in the four directions are coincident, the interference fringes occur in accordance with the thickness of the second layer.

FIG. 2 is an enlarged view showing a part of a light receiving member in which a light receiving layer having a multi-layered structure is deposited on a support having an uneven shape formed by a plurality of spherical trace dents. In the figure, 20
Reference numeral 1 is a first layer, 202 is a second layer, 203 is a free surface, and 204 is an interface between the first layer and the second layer. Second
As shown in the figure, in the case where the surface of the support is provided with an uneven shape by a plurality of minute spherical trace depressions, the light-receiving layer provided on the support is deposited along the uneven shape, and therefore the first layer Interface 204 between 201 and second layer 202 and free surface 203
Are formed in a concavo-convex shape by spherical trace dents along the concavo-convex shape of the surface of the support. When the curvature radius of the recess sphere-traced are formed at the interface 204 R _1, the curvature radius of the recess sphere-traced are formed on the free surface and R _2, R ₁ and R
_{Since 2} is R ₁ ≠ R ₂ , the reflected light at the interface 204,
The light reflected from the free surface 203 has a different reflection angle, that is, θ ₁ and θ ₂ in FIG. ₂ are θ ₁ ≠ θ ₂ and the directions are different, and ₁ shown in FIG. , ₂ ,
₃ with ₁ + ₂ - for changes not constant also the wavelength shift where represented by _3, occurred is Shiearingu interference corresponding to the so-called Niyu tons ring phenomenon, the interference fringes are dispersed in the recess It becomes a place. As a result, the image displayed through such a light receiving member is
Microscopically, even if interference fringes appear, they are invisible to the eye.

That is, the use of a support having a surface shape that becomes harder means that a light-receiving member formed by forming a multi-layered light-receiving layer on the support is such that the light passing through the light-receiving layer has a layer interface and a support. It is possible to effectively prevent the formed image from forming a striped pattern due to the reflection on the surface and the interference between them, and to obtain a light receiving member capable of forming an excellent image.

FIG. 4 is an enlarged view of a part of the surface of the support in the light receiving member of the present invention shown in FIG. As shown in FIG. 4, on the surface of the support in the light receiving member of the present invention, fine unevenness or unevenness group 404 is further formed on a part or the whole of the surface in the spherical trace depression 403. When such finer unevenness or unevenness group 404 is provided, in addition to the interference prevention effect described with reference to FIG.
Causes a scattering effect, which more reliably prevents the generation of interference fringe patterns.

By the way, in the prior art, as described above, the surface of the support is randomly roughened to cause irregular reflection, thereby preventing the occurrence of interference fringe patterns. However, in such a case, not only the effect of preventing the occurrence of the interference fringe pattern is not sufficiently obtained, but also a problem occurs in cleaning after the image transfer; for example, when cleaning is performed using a blade.
That is, the surface of the light-receiving layer has irregularities along the irregularities provided on the support, so that the blade mainly hits the convex portions of the irregularities of the light-receiving layer, the cleaning property is poor, and
The protrusions of the light-receiving layer and the blade surface are greatly worn, resulting in poor durability of the two and a problem.

On the other hand, in the light receiving member of the present invention, since the minute irregularities that cause the scattering effect are present in the spherical trace depressions (recesses), the blade is said to contact the recesses of the light receiving layer during cleaning. It also has the advantage that a large load is not applied to the blade or the surface of the light receiving layer.

By the way, the radius of curvature and width of the concavo-convex shape due to the spherical trace depressions provided on the surface of the support of the light receiving member of the present invention, and the height of the finer irregularities in the spherical trace depressions are such light receiving members of the present invention. It is important to efficiently obtain the effect of preventing the occurrence of interference fringes in the. The present inventors have made the following discoveries as a result of various experiments.

That is, when the radius of curvature of the uneven shape due to the spherical trace depression is R and the width is D, the following formula: If the above condition is satisfied, there are 0.5 or more Newton rings due to shear ring interference in each of the dents. Furthermore, the following formula: If the above condition is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

From this, the interference fringes generated in the entire light receiving member, dispersed in each trace depression, in order to prevent the occurrence of interference fringes in the light receiving member, the D / R 0.035,
It is preferably 0.055 or more.

The upper limit of D / R is preferably 0.5. This is because, if D / R is larger than 0.5, the width D of the depression becomes relatively large, which easily causes image unevenness.

In addition, the width D of the unevenness due to the trace depression is 500 μ at the maximum.
m, preferably less than 200 μm, more preferably 100 μm
It is desirable that the thickness is m or less. When D exceeds 500 μm,
Image unevenness is likely to occur, and the resolution may be exceeded. In such a case, it is difficult to obtain an efficient interference fringe prevention effect.

The height of the fine irregularities formed in the spherical trace depression, that is, the surface roughness γ _max in the spherical trace depression is preferably in the range of 0.5 to 20 μm. When γ _max is 0.5 μm or less, a sufficient scattering effect cannot be obtained, and when it exceeds 20 μm, minute irregularities in the spherical trace pit become too large as compared with the irregularities due to the spherical trace pit, and the trace Since the dents do not form a spherical shape, the effect of preventing the occurrence of interference fringe patterns cannot be sufficiently obtained. In addition, the non-uniformity of the light-receiving layer provided on such a support is increased, which easily causes image defects, which is not preferable.

The light-receiving layer formed on the support having a specific surface shape as described above has a first layer and a second layer, and the first layer and the second layer are silicon. Amorphous material containing atoms and at least one selected from oxygen atom, carbon atom and nitrogen atom, particularly preferably silicon atom (Si), oxygen atom (O), carbon atom ( C) and at least one selected from nitrogen atoms (N), and preferably at least one of a hydrogen atom (H) and a halogen atom (X) [hereinafter referred to as “a-Si ( O, C, N) (H, X) ". ], And those selected from oxygen atoms, carbon atoms and nitrogen atoms contained in the constituent materials of the first layer and the second layer are different from each other. The first layer may have a multi-layer structure, and particularly preferably has a charge injection blocking layer containing a substance that controls conductivity as one of the constituent layers, and / or a barrier layer. It is desirable to have it as one of the constituent layers.

Regarding the formation of the light-receiving layer of the light-receiving member of the present invention, it is necessary to accurately control the layer thickness at the optical level in order to efficiently achieve the above-mentioned object of the present invention. Vacuum deposition methods such as the sputtering method, the sputtering method, and the ion plating method are usually used.
A CVD method, a thermal CVD method or the like can also be adopted.

The specific contents of the light receiving member of the present invention will be described below with reference to the illustrated embodiments, but the light receiving member of the present invention is not limited to these embodiments.

FIG. 1 is a diagram schematically showing the layer structure of the light receiving member of the present invention, in which 100 is a light receiving member, 1
01 is a support, 102 is a first layer, 103 is a second layer, and 104 is a free surface.

Support 101 in the light receiving member of the present invention, the surface thereof has fine unevenness smaller than the resolution required for the light receiving member, and the unevenness is due to a plurality of spherical trace depressions, and Further, a plurality of minute irregularities are formed in the spherical trace depression.

Hereinafter, the shape of the surface of the support in the light receiving member of the present invention and a preferred production example thereof will be described with reference to FIGS. 4 and 5, but the surface shape of the support in the light receiving member of the present invention and the method for producing the same. Are not limited by these.

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

In FIG. 4, 401 is a support, 402 is the surface of the support, 403 is a concavo-convex shape due to the spherical trace depression, and 404 is a finer concavo-convex shape provided in the spherical trace depression.

Further, FIG. 4 also shows an example of a preferred manufacturing method for obtaining the surface shape of the support, and 403 'indicates a rigid sphere having fine irregularities 404' on the surface,
By causing the rigid sphere 403 'to naturally fall from a position of a predetermined height above the support surface 402 and colliding with the support surface 402, a fine uneven shape 404 is formed in the depression, thereby forming an uneven shape 403 by a spherical trace depression. It shows that it can be formed.
Then, using a plurality of rigid spheres 403 'having substantially the same diameter R',
By dropping them simultaneously or sequentially from the same height h, a plurality of spherical trace dents 40 having substantially the same radius of curvature R and substantially the same width D are formed on the support surface 402.
3 can be formed.

FIG. 5 shows some typical examples of the support body on the surface of which the uneven shape is formed by a plurality of spherical trace depressions as described above. In the figure, 501 is a support, 502
Is a surface of the support, and 503 is a spherical trace dent having a plurality of finer concave-convex shapes in the cavities (note that in FIG. 5, a plurality of finer concave-convex shapes formed in the spherical trace pits are illustrated. Although not present, it is assumed that each of the spherical trace dents 503 has a further minute uneven shape.), 503 'is a rigid sphere having a minute uneven shape on the surface (similarly, a minute uneven surface Although the shape is not shown, it is assumed that the surface of the hard sphere has minute irregularities.).

In the example shown in FIG. 5 (A), a plurality of spheres 503 ', 503', ... Of almost the same diameter are dropped regularly from almost the same height on different parts of the surface 502 of the support 501 to make them almost uniform. A plurality of trace depressions 503, 503, ... Having the same radius of curvature and substantially the same width are densely formed so as to overlap each other to form a regular uneven shape. In this case, in order to form the recesses 503, 503, ... Which overlap with each other, the spheres 503 'are arranged so that the collision timings of the spheres 503' with the support surface 502 deviate from each other.
Needless to say, it is necessary to let 03 ', 503', ... fall naturally.

Further, in the example shown in FIG. 5 (B), two types of spheres 503 ′, 503 ′, ... Having different diameters are dropped from substantially the same height or different heights, and the spheres 502 on the surface of the support 501 are dropped. , A plurality of recesses 503, 503, ... Having two kinds of curvature radii and two kinds of widths are densely formed so as to overlap each other, and the unevenness of the surface unevenness is formed. .

Furthermore, FIG. 5 (C) (front view and sectional view of the surface of the support)
In the example shown in (1), a plurality of spheres 503 ′, 503 ′, ... Of substantially the same diameter are dropped irregularly from the substantially same height on the surface 502 of the support 501, and the substantially same radius of curvature and plural kinds of widths are provided. , Are formed so as to overlap each other, and irregular irregularities are formed.

As described above, on the surface of the support of the light-receiving member of the present invention, the uneven shape due to the spherical trace dents is formed, and further, the fine unevenness is formed in the spherical trace dents. A preferable example is a method of dropping a rigid sphere having a minute uneven shape on the surface of a support. In this case, the diameter of the rigid sphere, the height of the drop, the hardness of the rigid sphere and the surface of the support, and the hardness of the rigid sphere. By appropriately selecting various conditions such as the shape and size of the surface irregularities, or the amount of rigid spheres that can be dropped, a spherical trace dent having a desired average curvature radius and average width on the support surface, or the spherical trace dent Irregularities having a desired size and shape can be formed therein with a predetermined density. That is, by selecting the above conditions, the height and pitch of the unevenness formed on the surface of the support, or the height and unevenness of the finer unevenness formed in the uneven recesses It is possible to freely adjust the pitch etc. according to the purpose,
It is possible to obtain a support having a desired uneven shape.

Then, regarding the support of the light receiving member to the surface of the uneven shape, a method of cutting and creating with a diamond tool using a lathe, a milling machine, etc. has been proposed and is an effective method as such, In this method, it is indispensable to use cutting oil, remove chips that are inevitably generated by cutting, and remove cutting oil that remains on the cutting surface, and in the end, processing is complicated and efficient. In the present invention, since the uneven surface shape of the support is formed by the spherical trace depressions as described above, the above problem is completely eliminated and a desired uneven surface support is obtained. It can be created efficiently and easily.

The support 101 used in the present invention may be either conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, A, Cr, M
Examples thereof include metals such as o, Au, Nb, Ta, V, Ti, Pt, and Pb, or alloys thereof.

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

For example, glass is NiCr, A, C on the surface.
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , S
Conductivity is imparted by providing a thin film made of nO ₂ , ITO (In ₂ O ₃ + SnO ₂ ) or the like, or NiCr, A, Ag, in the case of a synthetic resin film such as a polyester film.
A thin film of a metal such as Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, T, Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is formed by the metal. Is laminated to give conductivity to the surface. The shape of the support may be any shape such as a cylindrical shape, a belt shape, and a plate shape, but the shape can be appropriately determined depending on the application and the desire. For example, when the light receiving member 100 shown in FIG. 1 is used as an image forming member for electrophotography, it is desirable to have an endless belt shape or a cylindrical shape for continuous high speed copying. The thickness of the support is appropriately determined so that a desired light-receiving member can be formed, but when flexibility is required as the light-receiving member, a range in which the function as the support is sufficiently exhibited It can be made as thin as possible. However, in terms of mechanical strength and the like in terms of manufacturing and handling of the support, it is usually 10 μm or more.

Next, in the case of using the light receiving member of the present invention as a light receiving member for electrophotography, an example of a manufacturing apparatus for the surface of the support will be described with reference to FIGS. 6 (A) and 6 (B). However, the present invention is not limited thereby.

As a support for the light-receiving member for electrophotography, aluminum alloy or the like is subjected to ordinary extrusion processing to form a boathole tube or a mandrel tube, and a drawn tube obtained by further drawing is subjected to heat treatment or adjustment as necessary. A cylindrical (cylindrical) substrate that has been subjected to a treatment such as quality is used.
An uneven shape is formed on the surface of the support using the manufacturing apparatus shown in FIGS.

Examples of spheres used for forming the above-mentioned uneven shape on the surface of the support include metal such as stainless steel, aluminum, steel, nickel and brass, and various hard spheres such as ceramics and plastics. For reasons of cost reduction, stainless steel and steel rigid spheres are preferable. The hardness of such a hard sphere may be higher or lower than the hardness of the support, but when the sphere is repeatedly used, it is desirable that it is higher than the hardness of the support.

In order to form the specific shape as described above on the surface of the support of the present invention, it is necessary to use those having irregularities on the surface of various rigid spheres as described above, and a rigid sphere having irregularities on such a surface is, for example, Methods that apply plastic processing such as embossing and corrugation, roughening methods such as surface roughening (satin finish), methods that form irregularities by mechanical treatment, chemical methods such as etching treatment with acid or alkali It can be manufactured by treating a hard sphere by using a method of forming irregularities. In addition, electrolytic polishing, chemical polishing, finish polishing, etc., or anodic oxide film formation, chemical conversion film formation, plating, enameling, painting, vapor deposition film formation, film formation by the CVD method on the surface of a hard sphere on which irregularities are formed It is possible to appropriately adjust the uneven shape (height), hardness, etc. by performing surface treatment such as.

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

In the figure, 601 is an aluminum cylinder for making a support, and the surface of the cylinder 601 may be finished to an appropriate smoothness in advance. The cylinder 601 has a rotating shaft 602.
Is rotatably supported around the shaft and is driven by an appropriate driving means 603 such as a motor so as to be rotatable about an axis.
604 is a rotating container that is supported by a bearing 602 and rotates in the same direction as the cylinder 601. Inside the container 604,
A large number of hard spheres 605 having an uneven surface are housed. The rigid sphere 605 is carried by a plurality of protruding ribs 606 provided on the inner wall of the rotary container 604, and
By the rotation of the rotary container 604, it is transported to the upper part of the container.
When the rotating speed of the rotating container is a certain speed, the rigid sphere 605 transported to the upper part of the container with respect to the container wall drops onto the cylinder 601, collides with the cylinder surface, and forms a trace dent on the surface.

It should be noted that holes can be evenly formed in the wall of the rotary container 604, and a cleaning liquid can be sprayed from a shower tube 607 provided outside the container 604 at the time of rotation to clean the cylinder 601, the rigid sphere 605, and the rotary container 604. You can do the same. In this case, dust and the like attached due to static electricity caused by contact between the hard spheres or between the hard sphere and the rotating container,
By washing out to the outside of the rotary container 604, it is possible to form a desired support body free of dust and the like. As the cleaning liquid, it is necessary to use a cleaning liquid free from unevenness of drying and dripping. From this reason, it is preferable to use a non-volatile substance alone or a mixture with a cleaning liquid such as trichloroethane or trichlorethylene.

Light-Receiving Layer First Layer In the light-receiving member of the present invention, the first layer 102 is provided on the support 101, and the first layer is a silicon atom, an oxygen atom, a carbon atom. And at least one selected from the group consisting of nitrogen atoms and not contained in the second layer 103, preferably composed of an amorphous material further containing at least one of a hydrogen atom and a halogen atom, and If necessary, the first layer 102 can contain a substance that controls conductivity. The first layer may have a multi-layered structure, and preferably has a charge injection blocking layer or / and a barrier layer containing a relatively large amount of a substance controlling conductivity as a layer at the end portion on the support side. Is desirable.

In the present invention, specific examples of the halogen atom that can be contained in the first layer include fluorine, chlorine, bromine and iodine, but fluorine and chlorine are preferable. Then, the amount of hydrogen atoms (H) or halogen atoms (X) contained in the first layer of the present invention.
Or the sum of the amount of hydrogen atoms and halogen atoms (H +
X) is preferably 0.01 to 40 atomic%, more preferably
0.05 to 30 atomic%, optimally 0.1 to 25 atomic%.

In the present invention, the layer thickness of the first layer is one of the important factors for efficiently achieving the object of the present invention,
It is necessary to pay sufficient attention when designing the light-receiving member so that the light-receiving member may be provided with desired characteristics, and it is usually 1 to 100 μm, preferably 1 to 80 μm, and more preferably 2 μm. Set to ~ 50μ.

In the first layer of the light receiving member of the present invention, the purpose of incorporating at least one selected from oxygen atom, carbon atom and nitrogen atom is mainly to increase the photosensitivity and dark resistance of the light receiving member, And it is to improve the adhesion between the support and the first layer.

In the first layer of the present invention, when at least one selected from oxygen atom, carbon atom and nitrogen atom is contained, it is contained in a uniform distribution state in the layer thickness direction or is not contained in the layer thickness direction. Whether it is contained in a uniform distribution state depends on the above-mentioned purpose or expected effect, and accordingly, the amount to be contained also differs.

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

Further, when the purpose is to improve the adhesion between the support and the first layer, it is uniformly contained in a part of the layer region of the support-side end of the first layer, or At the end of the layer on the support side, at least one kind selected from carbon atom, oxygen atom, and nitrogen atom is contained in a distributed state such that the distribution concentration is high, and in this case, oxygen contained in the first layer is contained. The amount of at least one selected from the group consisting of atoms, carbon atoms, and nitrogen atoms is made relatively large so as to ensure the improvement of adhesion with the support.

In the light receiving member of the present invention, the amount of at least one selected from oxygen atom, carbon atom, and nitrogen atom contained in the first layer is, however, the characteristics required for the first layer as described above. In addition to the above, it is determined by taking into consideration the organic relevance such as the characteristics at the contact interface with the support, etc., usually 0.001 to 50 atomic%, preferably 0.002 to 40 atomic%, most preferably 0.003. ~ 30 atomic%

By the way, when it is contained in the whole layer region of the first layer, or when the ratio of the layer thickness of a part of the layer region to be contained in the layer thickness of the first layer is large, the above-mentioned contained amount The upper limit of is reduced. That is, in that case, for example, the layer thickness of the layer region to be contained is equal to the layer thickness of the first layer.
When it becomes 2/5, the amount to be contained is usually 30ato.
mic% or less, preferably 20atomic% or less, optimally 10ato
mic% or less.

Next, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms contained in the first layer of the present invention is relatively large on the support side, and from the end on the support side. Decrease toward the end on the second layer side, and in the vicinity of the end on the second layer side of the first layer, a relatively small amount, or it is distributed so as to be substantially close to zero. Some typical examples of the case will be described with reference to FIGS. 7 to 15. However, the invention is not limited by these examples. Hereinafter, at least one selected from carbon atom and oxygen atom is referred to as “atom (O, C, N)”.

In FIGS. 7 to 15, the horizontal axis represents the distribution concentration C of atoms (O, C, N), the vertical axis represents the layer thickness of the first layer, and t _B is the interface between the support and the first layer. The position, t _T , represents the position of the interface of the first layer with the second layer.

FIG. 7 shows a first typical example of the distribution state of atoms (O, C, N) contained in the first layer in the layer thickness direction. In such an example, atoms (O, C, N) to the position t ₁ from the interface position t _B between the first layer and the support containing the atom (O, C, N) distribution concentration C C ₁ And the distribution concentration C of atoms (O, C, N) is from the position t ₁ to the interface position t _T with the second layer.
Continuously decreases from the concentration C _2, and the distribution concentration of atoms (O, C, N) becomes substantially 0 at the position t _T.

In another typical example shown in FIG. 8, the distribution concentration C of the atoms (O, C, N) contained in the first layer is from the concentration C ₃ from the position t _B to the position t _T. It decreases continuously and becomes the concentration C ₄ at the position t _T.

In the example shown in FIG. 9, from the position t _B to the position t ₂ , the distribution concentration C of atoms (O, C, N) maintains a constant value of the concentration C ₅ ,
Atoms (O, C, N) from position t ₂ to position t _T
The distribution density C of the distribution concentration C is the concentration C 'at the position t _T gradually decreases continuously from ₅ atoms (O, C, N) becomes substantially zero.

In the example shown in FIG. 10, atoms (O, C, N) until the distribution concentration C of the lead to the position t _T to the position t _B, gradually decreases from the concentration C ₆ continuously atom in position t _T The distribution concentration C of (O, C, N) becomes substantially zero.

In the example shown in FIG. 11, the distribution concentration C of atoms (O, C, N) is
The density C ₇ is constant between the position t _B and the position t ₄ , and the density C ₇ is constant between the position t ₄ and the position t _T.
It decreases in a linear function from ₇ to substantially 0.

In the example shown in FIG. 12, the distribution concentration C of atoms (O, C, N) is
The density C ₈ is constant from the position t _B to the position t ₅ , and the density C ₇ is from the position t ₅ to the position t _T.
To a concentration C ₁₀ , the value decreases linearly.

In the example shown in FIG. 13, the distribution concentration C of atoms (O, C, N) decreases linearly from the position t _B to the position t _T, and from the concentration C ₁₄ to substantially zero. To do.

In the example shown in FIG. 14, the distribution concentration C of atoms (O, C, N) is
From the position t _B to the position t ₅ , the density C ₁₅ to the density C
It decreases linearly until it reaches _16, and from position t ₅ to position t
Until _T , the density C ₁₆ is kept constant.

Finally, in the example shown in FIG. 15, the distribution concentration C of the atoms (O, C, N) is the concentration C ₁₇ at position t _B, from the position t _B to the position t _6, starting from the concentration C ₁₇ Wayutsukuri decreases and decreases abruptly in the vicinity of the position t _6, the position t ₆ the density C _18. Then decreases from position t ₆ position to t ₇ is sharply at first, then decreases gradually or gently, the concentration C ₁₉ in the position t _7. Further at position t ₇
Gradually decreases extremely boiled made in between positions t ₈ and, a concentration C ₂₀ at position t _8. Furthermore, from the position t ₈ to the position t _T , the concentration C ₂₀ gradually decreases until it becomes substantially zero.

As in the example shown in FIGS. 7 to 15, the first layer has a portion having a high distribution concentration C of atoms (O, C, N) at the end on the support side of the first layer, At the end on the side of the second layer, in the case where the distribution concentration C has a portion where the distribution concentration C is considerably low, or when there is a concentration portion which is substantially close to zero, the end portion on the support side of the first layer Is provided with a localized region in which the distribution concentration of atoms (O, C, N) is relatively high, and the localized region is preferably 5 to 5 from the interface position t _B between the surface of the support and the first layer.
By setting the thickness within μ, it is possible to more efficiently improve the adhesion between the support and the first layer.

The localized region may be a part of the layer region at the end of the first layer containing the atom (O, C, N) on the support side, or may be a part thereof. Whether to do so is appropriately determined according to the characteristics required for the first layer to be formed.

The amount of atoms (O, C, N) contained in the localized region is such that the maximum amount of the distribution concentration C of atoms (O, C, N) is 500 atomic ppm or more,
Preferably 800 atomic ppm or higher, optimally 1000 atomic pp
It is desirable that the distribution state be m or more.

Further, in the light receiving member of the present invention, the substance for controlling the conductivity may be contained in the first layer in the entire layer region or a part of the layer region in a uniform or non-uniform distribution state, if necessary. .

Examples of the substance that controls the conductivity include so-called impurities in the field of semiconductors, and an atom belonging to Group III of the periodic table that gives P-type conductivity (hereinafter simply referred to as “I
Group II atom ”. ), Or an atom belonging to Group V of the periodic table that gives n-type conductivity (hereinafter simply referred to as “Group V atom”). Specific examples of the group III atom include B (boron), A (aluminum), Ga (gallium), In (indium), T (thallium), and the like. , Ga.
The group V atoms include P (phosphorus), As (arsenic), Sb.
(Antimony), Bi (bisman) and the like can be mentioned, but particularly preferable ones are P and Sb.

The first layer of the present invention is a conductivity controlling substance III
When a group atom or a group V atom is contained, it is contained in the whole layer region, or whether it is contained in a part of the layer region, depending on an intended place or an expected action and effect as described later, The amount to be contained also differs.

That is, when the main purpose is to control the conductivity type and / or the conductivity of the first layer, it should be contained in the entire layer region of the light-receiving layer. In this case, a group III atom or a group V atom should be contained. The content of atoms may be relatively small, usually 1 × 10 ^-3 ~
1 × 10 ³ atomic ppm, preferably 5 × 10 ^{−2 to} 5 × 1
0 ² atomic ppm, optimally 1 × 10 ^-1 to 2 × 10 ² atomic ppm
Is.

Further, a group III atom or a group V atom is 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 III atom or the group V atom in the layer thickness direction is In the case where it is contained so that the concentration is high on the side in contact with the support, such Group III atoms or V
The constituent layer containing a group atom or the layer region containing a high concentration of group III atom functions as a charge injection blocking layer.

That is, when the group III atom is contained, the movement of electrons injected from the support side into the photoreceptive layer is more efficiently performed when the free surface of the photoreceptive layer is subjected to a polar charging treatment. When the free surface of the photoreceptive layer is subjected to a polar electrification treatment, holes injected from the support side into the photoreceptive layer can be blocked. Can be prevented more efficiently. And, in such a case, the content is relatively large, and specifically,
30-5 × 10 ⁴ atomic ppm, preferably 50-1 × 10 ⁴ atomic ppm
ppm, optimally 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm. Further, in order to effectively exhibit the effect as the charge injection blocking layer, the layer thickness of the layer or the layer region provided at the end portion on the support side containing the group III atom is set to t, and the layer of the light receiving layer is set. When the thickness is T, it is desirable that the relationship of t / T ≦ 0.4 is satisfied, and more preferably the value of the relational expression is 0.35 or less, and optimally 0.3 or less. The layer thickness t of the layer or layer region is generally 3 × 10 ^{−3 to} 10 μ, preferably 4 × 10 ^{−3 to} 8 μ, and most preferably 5 × 10 ⁻³ .
It is desirable to set it to 5μ.

The amount of the group III atom or the group V atom contained in the first layer is relatively large on the support side and decreases from the support side to the second layer side. A typical example of the case where the group III atom or the group V atom is distributed in a relatively small amount or substantially close to zero near the end face of the is, The present invention can be explained with reference to the same examples as shown in FIGS. 7 to 15 in the case of containing at least one of atom, carbon atom and nitrogen atom, but the present invention is not limited to these examples. It is not limited to this.

Then, as in the example shown in FIGS. 7 to 15, a portion having a high concentration concentration C of group III atoms or group V atoms is provided on the side of the first layer close to the support, On the side of the layer closer to the second layer, in the case where the distributed concentration C has a considerably low concentration portion or a concentration portion substantially close to zero, the group III atom is present in the portion closer to the support side. Or the V
By providing a localized region in which the distribution concentration of the group atom is relatively high, preferably by providing the localized region within 5 μm from the interface position in contact with the surface of the support, the group III atom or the group V atom can be obtained. The above-described effect that the layer region having a high concentration concentration of atoms forms the charge injection blocking layer is more effectively exhibited.

As described above, the action and effect of each of the distribution states of the group III atoms or the group V atoms have been described individually. For obtaining the light receiving member having the characteristics capable of achieving the desired purpose,
It is said that the distribution state of these Group III atoms or Group V atoms and the amount of Group III atoms or Group V atoms contained in the first layer are used in an appropriate combination as necessary. There is no end. For example, in the case where a charge injection blocking layer is provided at the end of the first layer on the side of the support, in the first layer other than the charge injection blocking layer, the conductivity controlling substance contained in the charge injection blocking layer is contained. A substance that controls the conductivity of a polarity different from the polarity may be contained, or the substance that controls the conductivity of the same polarity may be contained in a much smaller amount than that contained in the charge injection blocking layer. You may ask.

Furthermore, in the light receiving member of the present invention, as the constituent layer provided at the end portion on the support side, instead of the charge injection blocking layer,
A so-called barrier layer made of an electrically insulating material may be provided, or both the barrier layer and the charge injection blocking layer may be constituent layers. Examples of the material forming the barrier layer include inorganic electrically insulating materials such as A ₂ O ₃ , SiO ₂ , and Si ₃ N _4, and organic electrically insulating materials such as polycarbonate.

Second Layer The second layer 103 of the light receiving member of the present invention is the above-mentioned first layer 1
A layer provided on 02 and having a free surface 104, that is, a surface layer, which is at least one selected from oxygen atoms, carbon atoms or nitrogen atoms and which is not contained in the first layer is uniformly distributed. Amorphous silicon contained in the state [hereinafter referred to as "a-Si (O, C, N) (H, X)". ] Is composed.

The purpose of providing the second layer 103 in the light receiving member of the present invention is to improve moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc. This can be achieved by containing the amorphous material forming the second layer with at least one of oxygen atom, carbon atom and nitrogen atom.

Further, in the light receiving member of the present invention, since each of the amorphous materials forming the first layer 102 and the second layer 103 has a common constituent atom of silicon atom, the first layer 102 Chemical stability can be ensured at the interface between the second layer 103 and the second layer 103.

Oxygen atoms, carbon atoms and nitrogen atoms are contained in the second layer 103 in a uniform distribution state, and the above-mentioned various characteristics are improved as the amount of these atoms contained is increased. However, too much leads to poor layer quality and poor electrical and mechanical properties. Therefore, the content of these atoms is usually 0.001 to 90 atomic%, preferably 1 to 90 atomic%, and most preferably 10 to 80 atomic%.

It is desirable that the second layer also contains at least one of a hydrogen atom and a halogen atom, and the amount of hydrogen atom (H) or the amount of halogen atom (X) contained in the second layer or The sum of the amounts of hydrogen atoms and halogen atoms (H + X) is usually 1 to 40 atomic%, preferably 5 to 30.
atomic%, optimally 5 to 25 atomic%.

The second layer 103 needs to be carefully formed to obtain the desired properties. That is, a silicon atom and at least one selected from an oxygen atom, a carbon atom and a nitrogen atom, or a substance having a hydrogen atom and / or a halogen atom as constituent atoms is used for the content of each constituent atom and other preparations. Depending on the conditions, the morphology changes from a crystalline state to an amorphous state, the electrical properties vary from conductive to semi-conductive and insulating, and the photoelectric property changes from photoconductive property to non-photoconductive property. In order to show each of the above, to form the second layer 103 having desired characteristics according to the purpose,
It is important to select the content of each constituent atom and the preparation conditions.

For example, when the second layer 103 is provided mainly for the purpose of improving electrical withstand voltage, the amorphous material forming the second layer 103 has a remarkable electrical insulating behavior under use conditions. Form. Further, when the second layer 103 is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the amorphous material forming the second layer 103 has a degree of electrical insulation described above. Although it is relaxed to some extent, it is formed so as to have some sensitivity to irradiation light.

Further, in the present invention, the layer thickness of the second layer is also one of the important factors for efficiently achieving the object of the present invention, and is appropriately determined according to the intended purpose. , The amount of oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, hydrogen atoms to be contained in the layer, or the characteristics required for the second layer, it is necessary to determine the mutual and organic relationship. is there. In addition, it is necessary to consider the economical aspect in consideration of productivity and mass productivity. From this, the layer thickness of the second layer is usually 3 × 10 ^{−5 to} 30 μ, more preferably 4 × 10 ^{−5 to} 20 μ, and particularly preferably 5 × 10 ⁻⁵ to 10 μ.
Let μ.

Since the light-receiving member of the present invention has the layer structure as described above, it can solve all of the problems of the light-receiving member having the light-receiving layer composed of amorphous silicon described above. Even when a monochromatic laser beam is used as a light source, the appearance of an interference fringe pattern in a formed image due to an interference phenomenon can be significantly prevented, and an extremely high-quality visible image can be formed.

Further, the light-receiving member of the present invention has a high photosensitivity in the entire visible light region, and is particularly excellent in the photosensitivity characteristic on the long wavelength side, so that it is particularly excellent in matching with a semiconductor laser, and has an optical response. It exhibits high electrical properties, excellent electrical, optical and photoconductive properties, electrical withstand voltage and use environment characteristics.

In particular, when it is applied as a photoreceptive member for electrophotography, it has no influence of residual potential on image formation, its electrical characteristics are stable, high sensitivity, and high SN ratio. Therefore, it is possible to stably and repeatedly obtain a high-quality image having excellent light fatigue resistance, repeated use characteristics, high density, clear halftone, and high resolution.

Next, a method for forming the light receiving layer of the present invention will be described.

Any of the amorphous materials forming the light receiving layer of the present invention is formed by a vacuum deposition method utilizing a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. These manufacturing methods are appropriately selected and adopted depending on factors such as the manufacturing conditions, the load level of capital investment, the manufacturing scale, and the desired characteristics of the light receiving member to be manufactured. Since it is relatively easy to control the conditions for producing the light receiving member having, and the carbon atom and the hydrogen atom can be easily introduced together with the silicon atom, the glow discharge method or the sputtering method is used. It is suitable. Then, the glow discharge method and the sputtering method may be used together in the same apparatus system.

In order to form a light-receiving layer composed of a-Si (H, X) by the glow discharge method, silicon atoms (Si) can be supplied.
The inside of the raw material gas for supplying Si and the raw material gas for supplying hydrogen atom (H) or / and halogen atom (X) capable of supplying hydrogen atom (H) and / or halogen atom (X) can be decompressed internally. It is introduced into the deposition chamber in a desired gas pressure state, causes a glow discharge in the deposition chamber, and is composed of a-Si (H, X) on the surface of a predetermined support previously installed at a predetermined position. Layer is formed.

The substance that can be the raw material gas for supplying Si is SiH.
_{4, Si 2 H 6, Si} 3 H 8, Si 4 H hydrogenation may or gasified gas state such as ₁₀ silicon (silanes). In particular, the layer created when working easy handling, Si supply efficiency From the viewpoint of goodness, etc., SiH ₄ and Si ₂ H ₆ are preferable.

Further, there are many halogen compounds as the substances that can be the raw material gas for supplying the halogen atoms, and for example, halogen gas, halides, interhalogen compounds, silane derivatives substituted with halogen, or the like in a gas state or gasifiable. A halogen compound can be used. Specifically, fluorine, chlorine, bromine, iodine halogen gas, Br
_{F, CF, CF 3, BrF} 3, BrF 5, IF 3, IF 7, IC
, IBr and other interhalogen compounds, and SiF ₄ , Si
Preferable examples are silicon halides such as ₂ F ₆ , SiC ₄ , and SiBr ₄ .

In the case where a silicon compound containing a halogen atom as described above in a gas state or a gasifiable substance is formed by a glow discharge method as a raw material gas, without using a silicon hydride gas as a raw material gas for supplying Si atoms. It is particularly effective because a layer composed of a-Si containing a halogen atom can be formed on a predetermined support.

When the light receiving layer is formed by using the glow discharge method, basically, a halogenated silicon which is a raw material gas for supplying Si and a gas such as Ar, H ₂ and He are mixed at a predetermined mixing ratio. The light receiving layer is formed on the support by introducing into the deposition chamber at a gas flow rate and causing a glow discharge to form a plasma atmosphere of these gases. In order to make it easier to control the content of hydrogen atoms (H), which is extremely effective in terms of control of photoelectric properties, it is necessary to further mix these gases with a raw material gas for supplying hydrogen atoms. You can also As the gas for supplying the hydrogen atoms, hydrogen gas, SiH ₄ , Si ₂ H ₆ , Si
A gas of silicon hydride such as ₃ H ₈ or Si ₄ H ₁₀ is used.
In addition, as a hydrogen atom supply gas, HF, HC, HBr, HI
Halides such as SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ C
_In the case of using a halogen-substituted silicon hydride or the like in a gas state such as ₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ or the like that can be gasified, a hydrogen atom (H) is introduced at the same time as the introduction of the halogen atom (X). Is also introduced, so it is effective.

To form the light-receiving layer composed of a-Si (H, X) by the sputtering method, a target made of silicon is used and these are sputtered in a desired gas atmosphere.

When the light receiving layer is formed by using the ion plating method, for example, single crystal silicon or single crystal silicon is housed in a vapor deposition boat as an evaporation source, and the evaporation source is subjected to a resistance heating method or an electron beam method (EB method). ) Or the like to heat and evaporate, and fly evaporate is passed through a desired gas plasma atmosphere.

In both cases of the sputtering method and the ion plating method, in order to allow the halogen atom to be contained in the layer to be formed, a gas of the above-mentioned halide or a silicon compound containing the halogen atom is introduced into the deposition chamber, and the gas is introduced. The plasma atmosphere may be formed. Further, when hydrogen atoms are introduced, a raw material gas for supplying hydrogen atoms, for example, H ₂ or a gas of the above-mentioned hydrogenated silanes is introduced into the deposition chamber for sputtering and the plasma atmosphere of these gases is changed. It may be formed. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen can be mentioned as effective ones.
Hydrogen halide such as HF, HC, HBr, HI, SiH ₂ F ₂ , Si
_{H 2 I 2, SiH 2 C} 2, SiHC 3, SiH 2 Br 2, SiHBr 3
Gaseous or gasifiable substances such as halogen-substituted hydrogen silicon and the like can also be used as effective starting materials.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms contained in the first layer constituting the light receiving layer to be formed. (H + X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 30 atomic%, most preferably 0.1 to 25 atomic
It is desirable to be set to%.

A-Si containing oxygen atom, carbon atom, or nitrogen atom
Regarding the formation of the layer composed of (H, X) or a part of the layer region, when it is carried out by the glow discharge method, when the layer composed of a-Si (H, X) is formed In addition, a starting material for introducing an atom (O, C, N) is used together with a starting material for forming a-Si (H, X), and the amount thereof is contained in the layer to be formed in a controlled manner. It is done by things.

As a starting material for introducing such an atom (O, C, N),
Almost any substance can be used as long as it is a gaseous substance or a substance that can be gasified and has at least atoms (O, C, N) as constituent atoms.

Specifically, as a starting material for introducing an oxygen atom (O), for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (N
O), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O),
Trinitrogen dioxide (N ₂ O ₃ ), Nitrogen dioxide (N
₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (NO
₃ ) having a silicon atom (Si), an oxygen atom (O), and a hydrogen atom (H) as constituent atoms, for example, disiloxane (H
₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).
Examples of the starting material for introducing a carbon atom (C) include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane ( n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ) and the like having 1 carbon atom
5 saturated hydrocarbons, ethylene _{(C 2 H} 4), propylene _{(C 3 H} 6), butene _-1 (C _{4 H} 8), butene-2
(C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), and other ethylene hydrocarbons having 2 to 5 carbon atoms,
Acetylene (C ₂ H ₂ ), Methylacetylene (C
₃ H ₄ ), butyne (C ₄ H ₆ ), and other acetylene hydrocarbons having 2 to 4 carbon atoms, and the like. Examples of the starting material for introducing a nitrogen atom (N) include nitrogen (N ₂ ), Ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (H
N ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N) and the like.

Further, when forming a layer composed of a-Si (H, X) containing atoms (O, C, N) by using the sputtering method, the starting point for introducing atoms (O, C, N) is used. As the substance, in addition to the above-mentioned gasifiable starting substances listed at the time of the glow discharge method, SiO ₂ , Si ₃ N ₄ , carbon black and the like can be cited as the solidified starting substance. These can be used in the form of a target such as Si.

To form a layer composed of a-Si (H, X) containing a group III atom or a group V atom by using a glow discharge method, a sputtering method or an ion plating method,
When forming the above-mentioned layer composed of a-Si (H, X),
A starting material for introducing a group II atom or a group V atom is a-Si.
It is carried out by using together with the starting materials for the formation of (H, X) and controlling their inclusion in the layers to be formed.

Specifically, as a starting material for introducing a group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B
_{5 H 11, B 6 H 10} , B 6 H 12, B 10 H 14 borohydride such as, BF _3, BC _3, BBr boron halides such as _3. In addition, AC ₃ , GaC ₃ , Ga (C
_{H 3) 3, InC 3,} TC 3 etc. can also be mentioned.

As a starting material for introducing a Group V atom, specifically, for introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ or the like, PH ₄ I,
Examples thereof include phosphorus halides such as PF ₃ , PF ₅ , PC ₃ , PC ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , As
_{C 3, AsBr 3, AsF 5} , SbH 3, SbF 3, SbF 5, SbC
₃ , SbC ₅ , BiH ₃ , BiC ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

At least one selected from oxygen atom, carbon atom and nitrogen atom not contained in the first layer, glow discharge method,
By using the sputtering method or the ion plating method, the second layer 103 is made to contain a-Si (O, C, N) (H,
The layer composed of X) is formed in the same manner as in the case of forming the above-mentioned first layer.

For example, in order to form a layer or layer region containing an oxygen atom by a glow discharge method, a source gas containing silicon atoms (Si) as constituent atoms and a source gas containing oxygen atoms (O) as constituent atoms are required. Accordingly, a raw material gas containing hydrogen atoms (H) or halogen atoms (X) as constituent atoms is mixed and used at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms is used. , A source gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms, which is also mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms, It is possible to mix and use a raw material gas having three constituent atoms of silicon atom (Si), oxygen atom (O) and hydrogen atom (H).

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

As the starting material for introducing such oxygen atoms, any material may be used as long as it is a gas in which oxygen atoms are constituent atoms or a gasifiable substance is gasified.

Specific examples of the starting material for introducing oxygen atoms include oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N ₂ O), Nitrogen trioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (NO ₃ ), silicon atom (Si) and oxygen atom (O) Examples thereof include lower siloxanes having a hydrogen atom (H) as a constituent atom, such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), and the like.

To form a layer containing oxygen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or SiO _{2 is used.}
It may be carried out by using a wafer or a wafer containing a mixture of Si and SiO ₂ as a target and sputtering these in various gas atmospheres.

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

In addition, separately, Si and SiO ₂ are used as separate targets.
Alternatively, by using a single target in which Si and SiO ₂ are mixed, in a diluting gas atmosphere as a gas for sputtering, or at least a hydrogen atom (H) or / and a halogen atom (X) is used as a constituent atom. It is made by spattering in a gas atmosphere containing it. 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 example of glow discharge described above can be used as an effective gas in the case of sputtering.

Further, for example, in order to form the second layer containing carbon atoms by the glow discharge method, a raw material gas containing silicon atoms (Si) as constituent atoms, and a raw material gas containing carbon atoms (C) as constituent atoms, If necessary, a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as a constituent atom is mixed and used at a desired mixing ratio, or a raw material containing silicon atoms (Si) as a constituent atom. A gas and a source gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms are mixed at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms. , A raw material gas containing silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) as constituent atoms, or a raw material containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms Raw material gas consisting of gas and carbon atoms (C) Mixed with each other.

What is effectively used as such a source gas is SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si containing Si and H as constituent atoms.
Silicon hydride gas such as silane (Silane) such as ₄ H ₁₀ , C
And H as constituent atoms, for example, saturated hydrocarbon having 1 to 4 carbon atoms, ethylene hydrocarbon having 2 to 4 carbon atoms, and 2 carbon atoms
~ 3 acetylene hydrocarbons and the like.

Specifically, saturated hydrocarbons include methane (CH ₄ ),
Ethane _{(C 2 H} 6), propane _{(C 3} H 8), n- butane _{(n-C 4 H 10)} , pentane _(C 5 H _12), as ethylenic hydrocarbons, ethylene _{(C 2 H} 4) , propylene _{(C 3 H} 6), butene _-1 (C _{4 H} 8), butene-2
(C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C). ₄ H ₆ ) and the like.

The source gas containing Si, C and H as constituent atoms is Si
Mention may be made of alkyl silicide such as (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . In addition to these source gases, H ₂ can of course be used as the source gas for introducing H.

In order to form the second layer composed of a-SiC (H, X) by the sputtering method, a monocrystalline or polycrystalline Si wafer or C (graphite) wafer, or Si and C are mixed. The wafer contained as a target is used as a target, and these are sputtered in a desired gas atmosphere.

For example, when using a Si wafer as a target, the raw material gas for introducing carbon atoms and / or hydrogen atoms and / or halogen atoms is diluted with a diluting gas such as Ar or He, if necessary, for sputtering. The Si wafer may be sputtered by introducing the gas plasma of these gases into the deposition chamber.

Also, Si and C should be different targets or Si
When used as a single target containing a mixture of C and C, a raw material gas for introducing hydrogen atoms and / or halogen atoms as a gas for sputtering is diluted with a diluting gas as needed, and deposited for spattering. Introduced in the room,
Gas plasma may be formed and sputtered. As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method can be used as it is.

Further, for example, to form a second layer composed of amorphous silicon containing nitrogen atoms by a glow discharge method, a source gas containing silicon atoms (Si) as constituent atoms,
Whether to use a raw material gas containing nitrogen atoms (N) as constituent atoms and a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms at a desired mixing ratio, if necessary Alternatively, a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing nitrogen atoms (N) and hydrogen atoms (H) as constituent atoms are mixed at a desired mixing ratio. Can be used.

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

As a starting material for introducing such a nitrogen atom, any material may be used as long as it is a gasified substance containing at least nitrogen atoms as constituent atoms or a gasifiable substance.

As the starting material for introducing a nitrogen atom, specifically, nitrogen (N ₂ ), ammonia (NH ₃ ), which has a nitrogen atom as a constituent atom or a nitrogen atom and a hydrogen atom as constituent atoms,
Examples thereof include nitrogen such as hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), and nitrogen compounds such as nitrides and azides. Besides this,
Nitrogen halides such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N) can be mentioned. When these halogenated nitrogen compounds are used, in addition to introduction of nitrogen atom (N) Then, a halogen atom (X) can be introduced.

To form a layer region containing nitrogen atoms by the sputtering method, a single crystal or polycrystalline Si wafer or Si is used.
_{The 3} N ₄ wafer or the wafer containing Si and Si ₃ N ₄ mixed therein may be used as a target, and these may be sputtered in various gas atmospheres.

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

Separately, by using Si and Si ₃ N ₄ as separate targets, or by using a single target in which Si and Si ₃ N ₄ are mixed, an atmosphere of diluted gas as a gas for sputtering is obtained. Or by sputtering in a gas atmosphere containing at least a hydrogen atom (H) or / and a halogen atom (X) as a constituent atom. 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 example of glow discharge described above can be used as an effective gas even in the case of sputtering.

As described above, the light-receiving layer of the light-receiving member of the present invention is formed by the glow discharge method, the sputtering method, or the like. The group III atom or the group V atom or the oxygen atom contained in the light-receiving layer is used. , Control of the content of each of carbon atom or nitrogen atom, or hydrogen atom and / or halogen atom,
It is carried out by controlling the gas flow rate of each atom supply starting material or the gas flow rate ratio between each atom supply starting material flowing into the deposition chamber.

Further, conditions such as the temperature of the support at the time of forming the first layer and the second layer, the gas pressure in the deposition chamber, and the discharge power are important factors for obtaining the light receiving member having desired characteristics, It is appropriately selected in consideration of the function of the layer to be formed. Further, these layer forming conditions may differ depending on the type and amount of each atom contained in the first layer and the second layer. It is also necessary to make a decision after careful consideration.

Specifically, the support temperature is usually 50 to 350 ° C.,
Particularly preferably, the temperature is 50 to 250 ° C. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, particularly preferably 0.1 to 1 Torr.
Set to 0.5 Torr. The discharge power is usually 0.005 to 50 W / cm ² , but more preferably 0.01 to 30 W / c.
m ² and particularly preferably 0.01 to 20 W / cm ² .

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

By the way, the atoms (O, C,
N), group III atoms or group V atoms, or hydrogen atoms and / or halogen atoms in order to make the distribution state uniform, it is necessary to keep the above conditions constant when forming the light-receiving layer. is necessary.

Further, in the present invention, when the light-receiving layer is formed, the distribution concentration of the atoms (O, C, N) or the group III atom or the group V atom contained in the layer is changed in the layer thickness direction. In order to form a photoreceptive layer having a desired distribution in the thickness direction, if a glow discharge method is used, atoms (O, C, N) or a group III atom or a group V atom for introducing The gas flow rate when introducing the starting material gas into the deposition chamber is appropriately changed according to the desired rate of change, and other conditions are kept constant. Then, in order to change the gas flow rate, concretely, for example, manually or by some commonly used method such as an external drive motor, the opening of a predetermined needle valve provided in the middle of the gas flow path system is gradually increased. It suffices to perform an operation to change. At this time, the rate of change of the flow rate does not have to be linear, and it is possible to obtain a desired content rate curve by controlling the flow rate according to a previously designed rate-of-change curve using, for example, a microcomputer.

Further, when the photoreceptive layer is formed by the sputtering method, the distribution concentration of atoms (O, C, N) or group III atoms or group V atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired value. In order to form a state of distribution in the layer thickness direction of, the starting material for introducing atoms (O, C, N) or Group III atoms or Group V atoms in the gas state is used as in the case of using the glow discharge method. Used in
The gas flow rate when introducing the gas into the deposition chamber is changed according to the desired rate of change.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples 1 to 12, but the present invention is not limited thereto.

In each of the examples, the light receiving layer was formed using the glow discharge method. FIG. 16 shows an apparatus for manufacturing the light receiving member of the present invention by the glow discharge method.

In the gas cylinders 1602, 1603, 1604, 1605, 1606 in the figure, the raw material gas for forming each layer of the present invention is sealed, and as an example thereof, 1602 is SiF ₄
Gas (purity 99.999%) cylinder, 1603 is B ₂ H ₆ gas diluted with H ₂ (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 1604 is CH ₄ gas (purity 99.999%) A cylinder, 1605 is an NH ₃ gas (purity 99.999%) cylinder, and 1606 is an inert gas (He) cylinder.

A gas cylinder is required to allow these gases to flow into the reaction chamber 1601.
Check that valves 1622-1626 of 1602-1606, leak valve 1635 are closed, and inflow valves 1612-1616,
After confirming that the outflow valves 1617 to 1621 and the auxiliary valves 1632 and 1633 are opened, the main valve 1634 is first opened to exhaust the reaction chamber 1601 and the gas pipe. Next, an example of forming the first layer and the second layer on the vacuum A cylinder 1637 will be described below.

First, SiF ₄ gas from gas cylinder 1602, gas cylinder 1603
B ₂ H ₆ / H ₂ gas and CH ₄ gas from the gas cylinder 1604 are opened by opening valves 1622, 1623 and 1624 respectively, and the outlet pressure gauge 16
Adjust the pressure of 27, 1628, 1629 to 1 kg / cm ² and inflow valve 1
The openings 612, 1613, 1614 are gradually opened, and the mass flow controllers 1607, 1608, 1609 are introduced. Subsequently, the outflow valves 1617, 1618, 1619 and the auxiliary valve 1632 are gradually opened to allow the gas to flow into the reaction chamber 1601. At this time, the outflow valves 1617, 1618, 1619 are adjusted so that the ratios of the SiF ₄ gas flow rate, the CH ₄ gas flow rate, and the B ₂ H ₆ / H ₂ gas flow rate become desired values, and the inside of the reaction chamber 1601 is adjusted. The opening of the main valve 1634 is adjusted while watching the reading of the vacuum gauge 1636 so that the pressure becomes a desired value. Then, after confirming that the temperature of the base cylinder 1637 is set in the range of 50 to 400 ° C. by the heater 1638, the power source 1640 is set to a desired electric power to cause glow discharge in the reaction chamber 1601. Using a microcomputer (not shown), according to the flow rate change rate line previously designed, SiF ₄ gas, CH ₄
Gas and B ₂ H ₆ / H ₂ gas while controlling the gas flow rate
First, a first layer containing silicon atoms, carbon atoms and boron atoms is formed on the base cylinder 1637.

In order to form the second layer on the first layer by the same operation as described above, for example, SiF ₄ gas and NH ₃ gas are respectively added,
It is formed by diluting with a diluting gas such as He, Ar or H _{2 as} necessary, flowing into the reaction chamber 1601 at a desired gas flow rate, and causing a glow discharge according to desired conditions. It

Needless to say, all of the outflow valves other than the gas outflow valves necessary for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the same as the reaction chamber.
Outflow valve in 1601 to avoid remaining in the gas pipe from outflow valve 1617 to 1621 to reaction chamber 1601
1617 to 1621 are closed, main valve 1634 is fully opened using auxiliary valves 1632 and 1633, and the system is once evacuated to a high vacuum, if necessary.

Test Example 1 A hard ball made of SUS stainless steel having a diameter of 0.6 mm was chemically treated to etch the surface to form irregularities. Examples of the treating agent used include acids such as hydrochloric acid, hydrofluoric acid, sulfuric acid and chromic acid, and alkalis such as caustic soda. In this test example, a hydrochloric acid solution prepared by mixing 1 to 4 volume ratio of pure water with 1 concentration of concentrated hydrochloric acid was used, and the immersion time of the hard sphere, the acid concentration and the like were changed to adjust the shape of the irregularities appropriately.

Test Example 2 Using a hard sphere (height of surface irregularities γ _max = 5 μm) treated by the method of Test Example 1 and using the apparatus shown in FIGS. 6 (A) and (B), an aluminum alloy Made cylinder (diameter 60mm,
The surface having a length of 298 mm) was treated to form irregularities.

The relationship between the radius R'of the true sphere, the drop height h, the radius of curvature R of the trace dent, and the width r was investigated. The radius of curvature R and the width r of the trace dent were found to be the radius R'of the true sphere and the drop height. It was confirmed that it was decided by the conditions such as h. In addition, it was confirmed that the pitch of the trace pits (density of trace pits and pitch of irregularities) can be adjusted to the desired pitch by controlling the rotation speed of the cylinder, the number of revolutions, or the drop amount of the rigid spherical body. Was done.
Furthermore, as a result of examining the sizes of R and D, R is
If it is less than 0.1 mm, it is necessary to secure the drop height by making the rigid sphere small and light, and it is difficult to control the formation of the trace dents. This is not preferable. If R exceeds 2.0 mm, the rigid sphere is In order to adjust the drop height by making it heavier and heavier, for example, it is necessary to make the drop height extremely low when D is to be made relatively small. It is difficult to control the formation of the trace depression, which is not preferable. , D
It has been confirmed that when the value is less than 0.02 mm, the rigid sphere must be made small and light to secure the drop height, which makes it difficult to control the formation of the trace depressions, which is not preferable.

Furthermore, when the formed trace dent was tried, it was confirmed that minute ruggedness corresponding to the surface ruggedness of the hard sphere was formed in the trace dent.

Example 1 The surface of an aluminum alloy cylinder was treated in the same manner as in Test Example 2 to obtain a cylindrical A support (cylinder Nos. 101 to 106) having D and D / R shown in the upper column of Table 1A. .

Next, a light-receiving layer was formed on the A support (cylinder Nos. 101 to 106) under the conditions shown in Table 1B below by the manufacturing apparatus shown in FIG. The boron atom contained in the first layer was introduced as much as possible so that about 200 ppm was doped in all the layers.

These light receiving members were subjected to image exposure by irradiating a laser beam having a wavelength of 780 nm and a spot diameter of 80 μm using the image exposure device shown in FIG. 17, and developed and transferred to obtain an image. The appearance of interference fringes in the obtained image is as shown in the lower column of Table 1A.

Note that FIG. 17 (A) is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 17 (B) is a side schematic view schematically showing the entire exposure apparatus. In the figure, 1701 is a light receiving member, 1702 is a semiconductor laser, 1703 is an fθ lens, and 1704 is a polygon mirror.

Next, for comparison, an aluminum alloy cylinder surface-treated with a conventional diamond tool (No.107)
(Diameter 60 mm, length 298 mm, concave / convex pitch 100 μm, concave / convex depth 3 μm) was used to manufacture a light receiving member in the same manner as described above. When the obtained light receiving member was observed with an electron microscope, the surface of the support was parallel to the layer interface of the light receiving layer and the surface of the light receiving layer. An image was formed in the same manner as described above using this light receiving member, and the obtained image was evaluated in the same manner as described above. The results are shown in the lower column of Table 1A.

Example 2 A light-receiving layer was formed on a support A (cylinder Nos. 101 to 107) in the same manner as in Example 1 except that the light-receiving layer was formed according to the layer forming conditions shown in Table 2B. .

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

Example 3 In the same manner as in Example 1 except that a hard sphere having a height (γ _max ) of surface irregularities shown in the upper column of Table 3A was used, a spherical trace depression (D = 450 ± 50 (μm), A support (cylinder Nos. 301 to 306) was obtained.

Next, a light-receiving layer was formed on the A support (cylinder Nos. 301 to 306) under the conditions shown in Table 3B below using the manufacturing apparatus shown in FIG. The gas flow rates of CH ₄ gas and B ₂ H ₆ / H ₂ gas at the time of forming the first layer were automatically adjusted by microcomputer control according to the gas flow rate change line shown in FIG. Further, the boron atom contained in the first layer was introduced under the same conditions as in Example 1.

An image was formed on the obtained light-receiving member in the same manner as in Example 1. The occurrence of interference fringes in the obtained image was as shown in the lower column of Table 3A.

Example 4 A light-receiving layer was formed on an A support (cylinder Nos. 301 to 306) in the same manner as in Example 3 except that the light-receiving layer was formed according to the layer forming conditions shown in Table 4B. did. In addition,
The gas flow rates of the B ₂ H ₆ / H ₂ gas and the H ₂ gas at the time of forming the first layer were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG. Further, the boron atom contained in the first layer was introduced under the same conditions as in Example 1.

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 12 The same as Example 1 except that the light receiving layer was formed on the A support (cylinder No. 103 to 106) of Example 1 according to the layer forming conditions shown in Tables 5 to 12. Then, a light receiving member was produced. In Examples 5 to 6 and 8 to 11, the flow rate of the gas used at the time of forming the light receiving layer was automatically adjusted by microcomputer control according to the flow rate change lines shown in FIGS. 20 to 25, respectively. . Also, in each example,
The boron atom contained in the first layer was introduced under the same conditions as in Example 1.

An image was formed on the obtained light receiving member in the same manner as in Example 1.

In each of the obtained images, no occurrence of interference fringes was observed,
And it was of very good quality.

[Outline of Effects of the Invention] The light-receiving member of the present invention has the above-mentioned layer structure, whereby all the problems of the light-receiving member having the light-receiving layer composed of amorphous silicon can be solved. In particular, even when a laser light which is a coherent monochromatic light is used as a light source, it is possible to remarkably prevent the appearance of an interference fringe pattern in a formed image due to an interference phenomenon and form a very high quality visible image. .

Further, the light-receiving member of the present invention has a high photosensitivity in the entire visible light region, and is particularly excellent in the photosensitivity characteristic on the long wavelength side, so that it is particularly excellent in matching with a semiconductor laser, and has an optical response. It exhibits high electrical properties, excellent electrical, optical and photoconductive properties, electrical withstand voltage and use environment characteristics.

In particular, when it is applied as a photoreceptive member for electrophotography, it has no influence of residual potential on image formation, its electrical characteristics are stable, high sensitivity, and high SN ratio. Therefore, it is possible to stably and repeatedly obtain a high-quality image having excellent light fatigue resistance, repeated use characteristics, high density, clear halftone, and high resolution.

[Brief description 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 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, FIG. 2 is a view showing that interference fringes can be prevented from being generated in a light receiving member in which irregularities due to spherical trace depressions are formed on the surface of a support, and FIG. 3 is a conventional surface. FIG. 6 is a diagram showing that interference fringes are generated in a light receiving member in which a light receiving layer is deposited on a support which is regularly roughened. FIGS. 4 and 5 are schematic diagrams for explaining the uneven shape of the surface of the support of the light receiving member of the present invention and a method for producing the uneven shape. FIG. 6 is a diagram schematically showing one structural example of an apparatus suitable for forming the uneven shape provided on the support of the light receiving member of the present invention, and FIG. 6 (A) is a front view. , 6th (B)
The figure is a longitudinal sectional view. FIGS. 7 to 15 show at least one selected from the group consisting of oxygen atom, carbon atom and nitrogen atom in the first layer of the light receiving member of the present invention, or group III atom or group V atom in the layer thickness direction. It is a figure showing a distribution state, and in each figure, the vertical axis shows the layer thickness of the first layer, and the horizontal axis shows the distribution concentration of each atom. FIG. 16 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 view of a manufacturing apparatus by a glow discharge method. FIG. 17 is a diagram for explaining an image exposure device using laser light. 18th to
FIG. 25 is a diagram showing changes in the gas flow rate ratio in forming the light receiving layer of the present invention, in which the vertical axis represents the layer thickness of the first layer and the horizontal axis represents the gas flow rate of the used gas. 1 to 3, 100 ... light receiving member, 101 ... support, 102, 201, 301 ...
First layer, 103,202,302 …… Second layer, 104,203,303 ……
Free surface, 204,304 ... Interface between first layer and second layer About Figures 4 and 5, 401,501 ... Support, 402,502 ... Support surface, 403,503
...... Spherical trace dents, 403 ', 503' ...... Rigid spheres with irregularities on the surface, 404 ...... Small irregularities formed in spherical dents, 404 '...... Roughness formed on the surface of rigid spheres Regarding FIG. 6, 601 ... Cylinder, 602 ... Rotating shaft (receiver), 603 ... Driving means, 604 ... Rotating container, 605 ... Rigid sphere with uneven surface, 606 ... Installed on inner wall of container Ribs, 607 ...
… Shower tube Regarding Fig. 16, 1601 …… Reaction chamber, 1602-1606 …… Gas cylinder, 1607-16
11 ...... mass flow controller, 1612 to 1616 ...... inflow valve, 1617 to 1621 …… outflow valve, 1622 to 1626 …… valve, 1627 to 1631 …… pressure regulator, 1632,1633 …… auxiliary valve, 1634 …… Main valve, 1635 ... Leak valve,
1636 ... vacuum gauge, 1637 ... base cylinder, 1638 ... heating heater, 1639 ... motor, 1640 ... high-frequency power supply About Fig. 17, 1701 ... light receiving member, 1702 ... semiconductor laser, 1703 ...
… Fθ lens, 1704 …… Polygon mirror.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Koike 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-60-31144 (JP, A) JP-A-59 -58436 (JP, A) JP-A-56-115573 (JP, A) JP-A-59-182461 (JP, A) US patent 4432220 (US, A) US patent 3269066 (US, A)

Claims (12)

[Claims] 1. A silicon atom, an oxygen atom, and
A photoreceptive layer having a first layer and a second layer each composed of an amorphous material containing at least one selected from carbon atoms and nitrogen atoms, the first layer and the Atoms selected from oxygen atoms, carbon atoms and nitrogen atoms contained in the constituent material of the second layer are different from each other, and the width D of the depression is 500 μm or less and the radius of curvature of the depression is formed on the surface of the support. R and width D have an unevenness due to a plurality of spherical trace dents with 0.035 ≦ D / R, and minute unevenness of 0.5 to 20 μm is further formed in the spherical trace dents. Light receiving member. 2. The amorphous layer, wherein the first layer or the second layer contains the silicon atom and at least one selected from the oxygen atom, the carbon atom and the nitrogen atom in a uniform distribution state. The light receiving member according to claim 1, which is made of a quality material. 3. The first layer contains an atom belonging to Group III or Group V of the periodic table.
Item 7. The light receiving member according to item. 4. The light receiving member according to claim 1, wherein the first layer has a multilayer structure. 5. The method according to claim 4, wherein the first layer has, as one of the constituent layers, a charge injection blocking layer containing an atom belonging to Group III or Group V of the periodic table. Light receiving member. 6. The light receiving member according to claim 4, wherein the first layer has a barrier layer as one of the constituent layers. 7. The light receiving member according to claim 1, wherein the concavities and convexities of the spherical trace dents are irregularities due to the spherical trace dents having the same radius of curvature. 8. The light receiving member according to claim 1, wherein the irregularities of the spherical trace depressions are irregularities of depressions having the same radius of curvature and width. 9. The light according to claim 1, wherein the spherical dents are unevenness due to the dents of the hard spheres obtained by naturally dropping a plurality of hard spheres on the surface of the support. Receiving member. 10. The spherical trace dent is an unevenness due to the trace dent of the hard sphere obtained by dropping a hard sphere having substantially the same diameter from substantially the same height. Light receiving member. 11. The light receiving member according to claim 1, wherein the radius of curvature R and the width D of the spherical trace indentations are values satisfying the following expression: 0.035 ≦ D / R ≦ 0.5. . 12. The light receiving member according to claim 1, wherein the support is a metal body.