JPH0690535B2 - 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 by performing transfer, fixing, and the like as required is known. Among them, 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,
It is evaluated from the viewpoint that it has a high hardness of Vitzkers and has little problem of pollution. For example, 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-
As disclosed in JP-A-4053 and JP-A-57-4172, the light-receiving layer has a layered structure of two or more layers in which conductive specific layers are laminated to form a depletion layer 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, there is a problem that the transfer fringes affect the transfer member, and the interference fringes corresponding to the interference fringes are transferred and fixed on the transfer member to appear on the visible image, resulting in a defective image.

As a measure for solving such a problem, (a) a method of diamond-cutting the surface of a support to form irregularities of ± 500Å to ± 10000Å to form a light-scattering surface (for example, JP-A-58-162975).
(See JP-A-57-165845), (b) A method of providing a light absorbing layer by black-anodizing the surface of an aluminum support or dispersing carbon, a coloring pigment, and a dye in a resin (for example, JP-A-57-165845). (C) A method of providing a light-scattering / antireflection layer on the surface of a support by subjecting the surface of the aluminum support to a satin-finished alumite treatment or providing sandblasted fine irregularities in the shape of a grain (for example, a special method). Kaisho
No. 57-16554) is proposed.

These proposed methods, although providing tentative results, are not sufficient to completely eliminate the interference fringe pattern appearing on the image.

That is, in the method of (a), a large number of specific irregularities are provided on the surface of the support, and although the appearance of the interference fringe pattern due to the light scattering effect is prevented for a while, the light scattering still remains. Since the specular reflection light component remains,
In addition to the interference fringe pattern due to the specular reflection light remaining, the irradiation spots spread due to the light scattering effect on the surface of the support, which causes a substantial reduction in resolution.

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. Further, when providing the color pigment dispersed resin layer,
When the a-Si layer is formed, the degassing phenomenon occurs from 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. However, there is a problem in 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.

Regarding the method of (c), for example, in terms of incident light, a part of the incident light is reflected on the surface of the light-receiving layer to become reflected light,
The remainder enters the inside of the light receiving layer and becomes 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, since the emitted light is a component that interferes with the reflected light and remains in any case, the interference fringe pattern 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 inclined surface of the unevenness of the support and the inclined surface of the unevenness of the light-receiving layer are parallel to each other, and the incident light has the brightness, In addition, it causes darkness, and the light-receiving layer as a whole has a non-uniform thickness of the light-receiving layer, so that a light striped pattern appears. 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, on the support, a silicon atom, a first layer composed of an amorphous material containing at least one of germanium atoms and tin atoms, and silicon atoms. A second layer composed of an amorphous material containing at least one selected from an oxygen atom, a carbon atom and a nitrogen atom, wherein a depression is formed on the surface of the support. Having a width D of 500 μm or less and a radius of curvature R of the dent and a width D of 0.035 ≦ D / R, the unevenness is caused by a plurality of spherical trace dimples, and the spherical trace dimples further have a fineness of 0.5 to 20 μm. It is characterized by having irregularities.

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 part 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. On a support 101 having an uneven shape, a second layer having a first layer 102 and a free surface 104 along the inclined surface of the unevenness.
10 shows a light receiving member provided with a light receiving layer composed of 103.

2 and 4 are views for explaining the problem of 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 Re ₂ of the reflected light Re 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 each formed in a concavo-convex shape by spherical trace depressions along the concavo-convex shape on 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 ₂ R ₁
Since ≠ R ₂ , the reflected light at the interface 204 and the reflected light at the free surface 203 have different reflection angles, that is, the second
Where θ ₁ and θ ₂ in the figure are θ ₁ ≠ θ ₂ and the directions are different, they are expressed by l ₁ + l ₂ -l ₃ using l ₁ , l ₂ and l ₃ shown in FIG. Since the wavelength shift of is also not constant and changes, shearing interference corresponding to a so-called Newton ring phenomenon occurs, and the interference fringes are dispersed in the depression. As a result, even if microscopic interference fringes appear, the images appearing through such a light receiving member are such that they are not visually perceptible.

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. Reflection on the surface and interference between them effectively prevent the formed image from becoming a striped pattern, leading to a light-receiving member capable of bristling 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 a sufficient interference fringe pattern cannot be obtained, but also a problem occurs in cleaning after image transfer, for example, when cleaning is performed using a blade.
That is, since the surface of the light-receiving layer has irregularities along the irregularities provided on the support, the blade mainly hits the convex portions of the irregularities of the light-receiving layer, the cleaning property is poor, and the light-receiving layer is The convex portions and the blade surface are greatly abraded, resulting in poor durability of the both 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, 0.5 or more Newton's rings due to shearing interference will be present in each trace dent. 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.

Therefore, in order to prevent the generation of the interference fringes in the light receiving member by dispersing the interference fringes generated in the entire light receiving member in the respective trace depressions, Is 0.035, preferably 0.055 or more.

Also, The upper limit of is preferably 0.5. I mean, Is larger than 0.5, the width D of the dent 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 or less, preferably 200 μm or less, more preferably 1
It is desirable to set it to 00 μm or less. If D exceeds 500 μm, image unevenness is likely to occur and 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 a support having a specific surface shape as described above is composed of a first layer and a second layer, and the first layer comprises a silicon atom and a germanium atom or a tin atom. Of an amorphous material containing at least one of the above, and particularly preferably a silicon atom (Si) and at least one of a germanium atom (Ge) or a tin atom (Sn), and preferably a hydrogen atom (H). And an amorphous material containing at least one of halogen atoms (X) [hereinafter referred to as "a-Si (Ge, Sn) (H, X)". ], And may further contain a substance that controls conductivity, if necessary. The first layer may have a multilayer 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. As one of the constituent layers.

Further, the second layer is composed of an amorphous material containing silicon atoms, oxygen atoms, at least one selected from carbon atoms and nitrogen atoms, particularly preferably silicon atoms (Si), Amorphous containing at least one selected from oxygen atom (O), carbon atom (C) and nitrogen atom (N), and preferably at least one of hydrogen atom (H) and halogen atom (X). The material [hereinafter referred to as "a-Si (O, C, N) (H, X)". ] Is composed.

Regarding the preparation 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 thereby.

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 from the same height h at the same time or one after another, a plurality of spherical trace depressions 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 depression (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 ′, ...
Are regularly dropped from substantially the same height to form a plurality of trace depressions 503, 503, ... Having substantially the same radius of curvature and substantially the same width.
Are formed densely so as to overlap with each other, and irregularities are regularly formed. In this case, in order to form the recesses 503, 503, ... Which overlap each other, it is necessary to let the spheres 503 ', 503' ,. It goes without saying that there are

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 then, on the surface 502 of the support 501. , A plurality of recesses 503, 503, ... Having two kinds of radiuses of curvature and two kinds of widths are densely formed so as to overlap each other, and unevenness of the surface unevenness is formed. .

Further, in the example shown in FIG. 5C (front view and sectional view of the surface of the support), a plurality of spheres 503 ', 503', ... Of substantially the same diameter are formed on the surface 502 of the support 501. Are irregularly dropped from the height of the above, and a plurality of depressions 503, 503, ... Having almost the same radius of curvature and a plurality of kinds of widths 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 to form an uneven shape due to the spherical trace dents, and to form a plurality of further minute uneven shapes 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 hard spheres that can be dropped, a spherical trace dent having a desired average radius of curvature and average width on the support surface, or the spherical trace dent It is possible to form irregularities having a desired size and shape therein and a predetermined density. That is, by selecting the above-mentioned conditions, the height of the unevenness and the pitch of the unevenness formed on the surface of the support, or the height and the unevenness of the finer unevenness formed in the recess of the unevenness. The pitch and the like can be freely adjusted according to the purpose, and a support having a desired uneven shape can be obtained.

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, Al, Cr, Mo,
Examples include metals such as Au, Nb, Ta, V, Ti, Pt, and Pb, and 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, if it is glass, NiCr, Al, Cr,
Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , I
TO (In ₂ O ₃ + SnO ₂ ) to provide conductivity by providing a thin film, or synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Zn, Ni, A
A thin film of a metal such as u, Cr, Mo, Ir, Nb, Ta, V, Tl or Pt is provided on the surface by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like, or the surface is laminated with the metal, Conductivity is given 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, the light receiving member 100 of FIG.
When used as an electrophotographic image forming member, in the case of continuous high speed copying, an endless belt shape or a cylindrical shape is desirable. 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 where the light receiving member of the present invention is used as a light receiving member for electrophotography, an example of an apparatus for manufacturing the surface of the support will be 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, an aluminum alloy or the like is subjected to a usual pressing process to form a boathole tube or a mandrel tube, and a drawn tube obtained by further drawing is subjected to heat treatment or adjustment if necessary. A cylindrical (cylindrical) substrate that has been subjected to a treatment such as quality is used.
Using the manufacturing apparatus shown in FIGS. (A) and (B), an uneven shape is formed on the surface of the support.

Examples of spheres used for forming the 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, and particularly durability. 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, plating, coating, vapor deposition film formation, film formation by the CVD method on the hard sphere surface with such irregularities It is possible to appropriately adjust the uneven shape (height), altitude, etc. by performing surface treatment such as.

6 (A) and 6 (B) are schematic cross-sectional views for explaining an example of a manufacturing apparatus. In the figure, 601 is an aluminum cylinder for making a support.
May have the surface finished in advance to a suitable smoothness. The cylinder 601 is rotatably supported by a rotary shaft 602, and is driven by an appropriate drive means 603 such as a motor so as to be rotatable about its axis. Reference numeral 604 denotes a rotating container that is supported by a bearing 602 and rotates in the same direction as the cylinder 601. Inside the container 604, a large number of rigid spheres 605 having an uneven surface are housed. The rigid sphere 605 includes a plurality of protruding ribs 6 provided on the inner wall of the rotary container 604.
It is carried by 06 and is transported to the upper part of the container by the rotation of the rotary container 604. 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, on the above-mentioned support 101, a silicon atom, at least one of a germanium atom and a tin atom, and preferably at least a hydrogen atom and a halogen atom. A first layer 102 made of an amorphous material containing either one of them is laminated, and the first layer 102 may further contain a substance for controlling conductivity, if necessary. It is desirable to have a charge injection blocking layer or / and a barrier layer containing a relatively large amount of a substance controlling conductivity at the end portion on the support side.

In the present invention, as the halogen atom that can be contained in the first layer, specifically, fluorine, chlorine,
Examples thereof include bromine and iodine, with fluorine and chlorine being particularly preferable. Then, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer or the sum of the amounts of hydrogen atoms and halogen atoms (H +
X) is preferably 0.01 to 40 atomic%, more preferably 0.
05-30 atomic%, optimally 0.1-25 atomic% is desirable.

Further, in the light receiving member of the present invention, the layer thickness of the first layer is one of important factors for efficiently achieving the object of the present invention, and the light receiving member is provided with desired characteristics. As described above, it is necessary to pay sufficient attention when designing the light receiving member, and usually 1 to 100 μm, but preferably 1 to 80 μm.
μ, and more preferably 2 to 50 μ.

By the way, the purpose of incorporating a germanium atom and / or a tin atom in the first layer of the light receiving member of the present invention is mainly to improve the absorption spectrum characteristics on the long wavelength side of the light receiving member.

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

In the first layer in the present invention, germanium atoms and / or tin atoms are contained in the entire layer region in a uniform distribution state or in a non-uniform distribution state. (Here, the uniform distribution state means that the distribution concentration of germanium atoms and / or tin atoms is uniform in the plane direction parallel to the support surface of the first layer, and also in the layer thickness direction of the first layer. It means that the distribution concentration of germanium atoms and / or tin atoms is uniform in the plane direction parallel to the surface of the support of the first layer. In the first layer of the present invention, in particular, a relatively large amount of germanium atoms and / or tin atoms are uniform in the end portion on the support side. It is desirable to provide a layer that is contained in a different distribution state, or to add a germanium atom and / or a tin atom so that the distribution is more on the support side than on the free surface side. Germanium at the edges When the distribution concentration of atoms and / or tin atoms is made extremely large, when a long-wavelength light source such as a semiconductor laser is used, almost all of the constituent layers or layer regions close to the free surface side of the light-receiving layer are exposed. Long-wavelength light that cannot be completely absorbed is substantially completely absorbed in the constituent layer or layer region of the light-receiving layer which is in contact with the support, so that interference due to light reflected from the support surface is prevented. .

As described above, in the first layer of the present invention, germanium atoms and / or tin atoms can be evenly distributed in all layers, or can be continuously and unevenly distributed in the layer thickness direction. However, some typical examples of the distribution state in the layer thickness direction will be described below with reference to FIGS. 7 to 15 by using germanium atoms as an example.

7 to 15, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer, and t _B represents the position of the end face of the first layer on the support side, t _T represents the position of the end surface on the second layer side opposite to the support side. That is, the first layer containing germanium atoms is formed toward the t _T side rather than the t _B side.

It should be noted that in each figure, the display of the layer thickness and the concentration is shown in an extreme form because the difference between the figures becomes unclear if the values are shown as they are. It is a schematic one for explaining to do.

FIG. 7 shows a first typical example of the distribution state of germanium atoms contained in the first layer in the layer thickness direction.

In the example shown in FIG. 7, the germanium atom distribution is from the position t _B to the position t ₁ where the interface between the surface of the support on which the first layer containing germanium atoms is formed and the first layer is in contact. concentration C is notwithstanding et germanium atoms make constant value consisting concentration C ₁ is contained in the first layer, rather than the position t ₁ is gradually reduced continuously up to the interface position t _T than the concentration C ₂ .
At the interface position t _T , the distribution concentration C of germanium atoms is substantially zero.

(Here, substantially zero is the case where the amount is less than the detection limit amount.) In the example shown in FIG. 8, the distribution concentration C of germanium atoms contained is from the position t _B to the position t _T.
A distribution state is formed in which the concentration gradually decreases continuously from C ₃ and the concentration becomes C ₄ at the position t _T.

In the case of FIG. 9, from the position t _B to the position t ₂ , the distribution concentration C of germanium atoms is a constant position with the concentration C ₅ ,
between t ₂ and position t _T , gradually and continuously reduced,
At the position t _T , the distribution density C is substantially zero.

In the case of FIG. 10, the distribution concentration C of germanium atoms gradually decreases continuously from the position t _B to the position t _T , starting from the concentration C _{6 and} rapidly decreasing from the position t _3. And is made substantially zero at the position t _T.

In the example shown in FIG. 11, the distribution concentration C of germanium atoms is a constant value C ₇ between position t _B and position t ₄ , and the distribution concentration C is constant at position t _T. It is zero. Position t ₄
In between the position t _T and the distribution density C is a linear function located t ₄
It is further reduced to the position t _T.

In the example shown in FIG. 12, the distribution density C takes a constant value of the density C ₈ from the position t _B to the position t ₅ , and the position from the position t ₅
At t _T , the distribution state is a linear function that decreases from concentration C ₉ to concentration C ₁₀ .

In the example shown in FIG. 13, from the position t _B to the position t _T , the distribution concentration C of germanium atoms is positionally reduced from the concentration C ₁₁ and reaches zero.

In FIG. 14, the distribution concentration C of germanium atoms from the position t _B to the position t ₆ is linearly reduced from the concentration C ₁₂ to the concentration C _13, and is between the positions t ₆ and t _T. In, an example in which the concentration C ₁₃ is set to a constant value is shown.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is the concentration C ₁₄ at the position t _B , and is gradually reduced from this concentration C ₁₄ until reaching the position t ₇ , and t
_In the vicinity of the position ₇ , the concentration is sharply reduced to the concentration C ₁₅ at the position t ₇ .

In between position t ₇ and position t _8, is reduced initially rapidly, then the concentration at the position t ₈ is gradually decreased gradually
It becomes C ₁₆ and is gradually reduced between the positions t ₈ and t ₉ to reach the concentration C ₁₇ at the position t ₉ . Position t ₉ and position t _T
In the range between and, the concentration is decreased according to the curve of the shape as shown in the figure such that the concentration becomes substantially zero than C ₁₇ .

As described above with reference to FIGS. 7 to 15, some of the typical examples of the distribution state of germanium atoms and / or tin atoms contained in the first layer in the layer thickness direction are explained. In the receiving member, the support side has a portion having a high distribution concentration C of germanium atoms and / or tin atoms,
On the interface t _T side, it is desirable that a distribution state of germanium atoms and / or tin atoms having a portion where the distribution concentration C is considerably lower than that on the support side is provided in the first layer.

That is, the first layer constituting the light receiving member in the present invention preferably has a local region containing a relatively high concentration of germanium atoms and / or tin atoms on the side of the support as described above. Is desirable.

In the light receiving member of the present invention, it is desirable that the local region is provided within 5 μm of the interface position t _B , as described using the symbols shown in FIGS. 7 to 15.

The localized region may be the entire layer region up to the thickness of 5 μm from the interface position t _B , or may be a part of the layer region.

Whether the localized region is a part or the whole of the layer region is
It is appropriately determined according to the characteristics required of the formed light receiving layer.

The localized region is a germanium atom contained in it or /
And, as the distribution state of the tin atoms in the layer thickness direction, the maximum value C _max of the distribution concentration of germanium atoms or / and tin atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more, most preferably to the silicon atom. 1 × 10 ⁴ atomi
It is desirable to form a layer so that a distribution state such as c ppm or more can be obtained.

That is, in the light receiving member of the present invention, the first layer containing germanium atoms and / or tin atoms has a distribution concentration within 5 μm (layer region of t _B to 5 μm layer) within the layer thickness from the support side. It is preferably formed such that there is a maximum value C _max of

In the light receiving member of the present invention, the content of germanium atom and / or tin atom to be contained in the first layer must be appropriately determined according to the desire so that the object of the present invention can be efficiently achieved. The amount is usually 1 to 6 × 10 ⁵ atomic ppm, preferably 10 to ³ × 10 ⁵ atomic ppm, more preferably 1 × 10 ² to 2 × 10 ⁵ atomic ppm.

In the light receiving member of the present invention, the substance for controlling the conductivity can 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.

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 implicitly referred to as “Group V atom”). Specific examples of the group III atom include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium), but the particularly preferable one is B. , Ga. Examples of the group V atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bisman), and the like.
Particularly preferred 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, whether it is contained in the whole layer region or a part of the layer region is different depending on the intended place or 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 is contained in the whole layer region of the first layer, and in this case, a group III atom or a group V atom is contained. The content of group 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
Constituent layer containing group atom or group III atom or group V
The layer region containing a high concentration of group atoms 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 can be more efficiently performed when the free surface of the photoreceptive layer is subjected to a polar electrification 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. The content of these cases shall apply a relatively large amount, specifically, 30~5~10 ⁴ atomic ppm, preferably 50~1 × 10 ⁴ atomic ppm, optimally 1 × 10 ² to 5
× 10 ³ atomic ppm Further, in order to efficiently exert the effect as the charge injection blocking layer, the layer thickness of the layer or layer region provided at the end portion on the support side containing the group III atom or the group V atom is t, When the layer thickness of the light receiving layer is T, it is desirable that the relationship of 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 the layer region is generally 3 × 10 ^{−3 to} 10 μ, preferably 4 × 10 ^{−3 to} 8 μ, and most preferably 5 × 10 ^{−3 to} 5 μ. Is desirable.

Next, 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. Some typical examples of the case where the group III atom or the group V atom is distributed in the vicinity of the interface with the layer so as to have a relatively small amount or substantially close to zero are shown in FIGS. First
Although illustrated with reference to FIG. 24, the present invention is not limited to these examples. In each figure, the horizontal axis is number III
The distribution concentration C of atoms or group V atoms to be placed, the vertical axis represents the layer thickness of the first layer, t _B is the interface position between the support and the first layer, and t _T is the first layer. The position of the interface with the second layer is shown.

FIG. 16 shows a first typical example of the distribution state of the group III atoms or the group V atoms contained in the first layer in the layer thickness direction. In this example, the distribution concentration of the group III atom or the group V atom is from the interface position t _B to the position t ₁ where the first layer containing the group III atom or the group V atom is in contact with the support surface. C
Is a constant value C ₁ and the distribution concentration C of the group III atoms or the group V atoms C is from the position t ₁ to the interface position t _T with the second layer.
Continuously decreases from the concentration C ₂ , and at the interface position t _T
The distribution concentration C of the group III atom or the group V atom becomes C ₃ .

FIG. 17 shows one of the other typical examples. In that example,
The distribution concentration C of the group III atom or the group V atom contained in the first layer is C ₄ from the position t _B to the position t _T.
It continuously decreases from and reaches the concentration C ₅ at the position t _T.

In the example shown in FIG. 18, from the position t _B to the position t ₂ , the distribution concentration C of the group III atoms or the group V atoms maintains a constant value of the concentration C ₆ , and from the position t ₂ to the position t _T. Indicates that the distribution concentration C of the group III atom or the group V atom gradually and continuously decreases from the concentration C _7, and the distribution concentration C of the group III atom or the group V atom is substantially reduced at the position t _T. It becomes zero. However, the term "substantially zero" here means that the amount is less than the detection limit amount.

In the example shown in FIG. 19, the distribution concentration C of the group III atom or the group V atom gradually decreases from the concentration C ₈ continuously from the position t _B to the position t _T, and at the position t _T. The distribution concentration C of group III atoms or group V atoms is substantially zero.

In the example shown in FIG. 20, the distribution concentration C of the group III atom or the group V atom is a constant value of the concentration C ₉ between the position t _B and the position t ₃ , and it is from the position t ₃ to the position t _T. Between the concentrations
It decreases in a linear function from C ₉ to the concentration C ₁₀ .

In the example shown in FIG. 21, the distribution concentration C of the group III atom or the group V atom is the concentration C ₁₁ from the position t _B to the position t _4.
Is constant and decreases from the position t ₄ to the position t _{T in} a linear function from the concentration C ₁₂ to the concentration C ₁₃ .

In the example shown in FIG. 22, the distribution concentration C of the group III atom or the group V atom is a linear function from the position t _B to the position t _T and from the concentration C ₁₄ to substantially zero. Decrease.

In the example shown in FIG. 23, the distribution concentration C of the group III atom or the group V atom decreases linearly from the position t _B to the position t ₅ until the concentration C ₁₅ to the concentration C ₁₆ . The constant value of the concentration C ₁₆ is maintained from the position t _B to the position t _T.

Finally, in the example shown in FIG. 24, the distribution concentration C of the group III atom or the group V atom is the concentration C ₁₇ at the position t _B ,
From the position t _B to the position t ₆ , the concentration C ₁₇ starts to decrease gradually, and then decreases sharply near the position t ₆ and reaches the concentration C ₁₈ at the position t ₆ . 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. Furthermore gradually decreases extremely boiled made in between positions t ₇ and position t _8, the 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. 16 to 24, the distribution concentration C of group III atoms or group V atoms C on the side of the first layer close to the support side.
Of the distribution concentration C on the side of the interface with the second layer, the distribution concentration C is close to the support side when the distribution concentration C has a considerably low concentration part or a concentration part substantially close to zero. By providing a localized region in which the distribution concentration of the group III atom or the group V 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. Further, the above-described effect that the layer region in which the distribution concentration of the group III atoms or the group V atoms is high forms the charge injection blocking layer is more efficiently achieved.

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 above. For obtaining a light receiving member having characteristics capable of achieving a 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 Al 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 which is provided on 02 and has a free surface 104, that is, a surface layer, which contains at least one selected from oxygen atoms, carbon atoms and nitrogen atoms in a uniform distribution 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 is achieved by incorporating at least one selected from oxygen atoms, carbon atoms and nitrogen atoms in the amorphous material forming the second layer.

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.

The second layer 103 contains at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms in a uniform distribution state, but as the amount of these atoms contained increases. Therefore, the above-mentioned characteristics are improved. But,
If it is too large, the layer quality deteriorates, and the electrical and mechanical properties also deteriorate. Therefore, the content of these atoms is usually 0.001 to 90 atomic%, preferably 1 to 90 atomic
%, Optimally 10 to 80 atomic%.

It is desirable that the second layer also contains at least one of a hydrogen atom and a halogen atom. The amount of hydrogen atom (H) or the amount of halogen atom (X) contained in the second layer, or hydrogen. The sum of the amount of 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 relationships. is there. In addition, it is necessary to consider the economical aspect in consideration of productivity and mass productivity. For this reason, the layer thickness of the second layer is usually 3 × 10 ^{−3 to} 30 μ, more preferably 4 × 10 ^{−3 to} 20 μ, and particularly preferably 5 × 10 ^{−3 to} 10 μ.
And

Since the light-receiving member of the present invention has the above-mentioned layer structure, it can solve all of the problems of the light-receiving member having the light-receiving layer composed of amorphous silicon as 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. Thus, it is possible to stably and repeatedly obtain a high-quality image having light fatigue resistance, repeated use configuration, high density, clear halftone, and high resolution.

Next, the 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 the first layer composed of a-SiGe (H, X) by the glow discharge method, a source gas for supplying Si that can supply silicon atoms (Si) and a germanium atom (Ge) are supplied. Possible source gas for Ge supply and hydrogen atom (H) or /
And a hydrogen atom (H) capable of supplying the halogen atom (X) or / and a source gas for supplying the halogen atom (X) are introduced into the deposition chamber capable of reducing the pressure in a desired gas pressure state, A glow discharge is generated on the surface of a-SiGe (H, X) on the surface of a predetermined support that is installed in a predetermined position in advance.
To form a layer.

The substance that can be the source gas for supplying Si is Si.
_{H 4, Si 2 H 6,} Si 3 H 8, Si 4 gas state of H _10, etc. or gasified may hydrogenated silicon (silanes). In particular, the layer created when working easy handling, Si supply In terms of efficiency, SiH ₄
And Si ₂ H ₆ are preferred.

Further, as the substance that can be the raw material gas for supplying Ge, GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , G
It is possible to use germanium hydride in the gas state or gasifiable such as e ₈ H ₁₈ , Ge ₉ H _{20 and the} like. In particular, GeH ₄ and Ge ₂ are easy to handle during layer formation work and Ge supply efficiency is good.
H ₆ and Ge ₃ H ₈ are preferred.

Further, as the substance that can be the source gas for supplying the halogen atom, there are many halogen compounds, for example, halogen gas, halogenide, interhalogen compound, halogen-substituted silane derivative, or the like in a gas state or gasifiable. Compounds can be used. In particular,
Fluorine, chlorine, bromine, iodine halogen gas, BrF, ClF,
Interhalogen compounds such as ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , IF ₇ , ICl, and IBr, and halogenated silicon compounds such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ are preferable. .

In the case of forming a gas state or a gasifiable substance of a silicon compound containing a halogen atom as described above by a glow discharge method as a raw material gas, use a hydrogenated silicon 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 first layer is formed using the glow discharge method, basically, a silicon halide and a raw material gas for supplying Si are used.
Germanium hydride as a raw material for supplying Ge and Ar, H ₂ , and He
The first layer is formed on the support by introducing a gas such as the above into the deposition chamber at a predetermined mixing ratio and a gas flow rate and causing a glow discharge to form a plasma atmosphere of these gases. However, in order to make it easier to control the content of hydrogen atoms (H), which is extremely effective in controlling the electrical or photoelectric properties, these gases are further added. A raw material gas for supplying hydrogen atoms can also be mixed. The gas for the hydrogen atom feed, hydrogen gas _{or, SiH 4, Si 2 6,} Si 3 H 8, Si 3 H of ₁₀ such silicon hydride gas is used. Also, as a gas for supplying hydrogen atoms,
Halides such as HF, HCl, HBr, HI, SiH ₂ F ₂ , SiH ₂ I ₂ , Si
When a gas or a gasifiable substance such as halogen-substituted silicon hydride such as H ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ and SiHBr ₃ is used, a hydrogen atom is simultaneously introduced with the halogen atom (X). Since (H) is also introduced, it is effective.

In order to form the first layer composed of a-SiGe (H, X) by the sputtering method, two pieces of a target made of silicon and a target made of germanium, or made of silicon and germanium are used. This is done by using targets and spattering them in a desired gas atmosphere.

When the first layer is formed by using the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a vapor deposition boat as evaporation sources, and Can be carried out by heating and evaporating by means of a resistance heating method or an electron beam method (EB method) or the like, and letting the flying evaporate pass through in 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 the above-mentioned hydrogenated silane flow rate and / or gases such as germanium hydride are introduced into the deposition chamber for spattering. It suffices to form a plasma atmosphere of gases such as. Further, as the source gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen can be mentioned as effective ones, but in addition, hydrogen halides such as HF, HCl, HBr and HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH
₂ Br ₂ , halogen-substituted silicon hydrides such as SiHBr ₃ , and GeH
_{F 3, GeH 2 F 2,} GeH 3 F, GeHCl 3, GeH 2 Cl 2, GeH 3 Cl, GeHBr 3, GeH 2 B
r ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc.Germanium hydrogen halide, etc., GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeB
Gaseous or gasifiable substances such as r ₂ , germanium halides such as GeI _2, etc. 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 set it as%.

Amorphous silicon containing tin atoms (hereinafter referred to as "a-SiSn (H, X)") by using a glow discharge method, a sputtering method, or an ion plating method.
In order to form a light receiving layer composed of
When forming a layer composed of (H, X), the starting material for supplying germanium atoms is used in place of the starting material for supplying tin atoms (Sn), and the amount thereof in the layer to be formed is changed. It is carried out by containing it while controlling it.

Examples of the tin atoms (Sn) can be a raw material gas for the feed material, tin hydride (SnH ₄₎ or _{SnF 2, SnF 4, SnCl 2} , SnCl 4,
SnBr ₂ , SnBr ₄ , SnI ₂ , SnI ₄ or the like can be used in a gas state or gasifiable such as tin halide, and when using tin halide, a halogen atom is provided on a predetermined support. This is particularly effective because a layer composed of a-Si contained can be formed. Of these, SnCl ₄ is preferable from the viewpoints of ease of handling during layer formation work and good Sn supply efficiency.

When SnCl ₄ is used as a starting material for supplying tin atoms (Sn), solid SnCl ₄ can be used for gasification.
It is desirable to boil an inert gas such as Ar and He while heating and bubbling using the inert gas.The gas thus generated is introduced into a deposition chamber whose inside pressure is reduced to a desired gas pressure state. To do.

Amorphous silicon containing at least one selected from oxygen atom, carbon atom, and nitrogen atom, that is, a-Si (O, C, N), by using glow discharge method, spattering method, or ion plating method. To form the second layer 103 composed of (H, X), a starting material for forming a-Si (O, C, N) (H, X) is used to form the above-mentioned atom (O , C, N) containing a-SiGe (H, X) or / and a-SiSn (H, X).

For example, in order to form the second layer containing oxygen atoms by the 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. Or a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms. And a source gas containing oxygen atoms (O) and hydrogen atoms (H) as constituent atoms, also at a desired mixing ratio, or a source gas containing silicon atoms (Si) as constituent atoms. It is possible to use a mixture of raw material gases having three constituent atoms of silicon, silicon atoms (Si), oxygen atoms (O) and hydrogen atoms (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 dioxide (N ₂
O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentaoxide (N ₂ O ₅ ),
Nitrogen trioxide (NO ₃ ), silicon atom (Si), oxygen atom (O) and hydrogen atom (H) as constituent atoms, for example,
Disiloxane (H ₃ SiOSiH _3), trisiloxane (H ₃ SiOSi
And lower siloxanes such as H ₂ OSiH ₃ ) and the like.

According to the sputtering method, in order to form a layer containing oxygen atoms, a single crystal or polycrystalline Si wafer or SiO ₂ wafer, or a wafer containing Si and SiO ₂ as a mixture is used as a target. Etc. may be sputtered 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 introduced into the inside to form a gas plasma of these gases and the Si wafer may be sputtered.

Alternatively, Si and SiO ₂ are used as separate targets, or by using one target that is a mixture of Si and SiO ₂ , in an atmosphere of diluting gas as a gas for sputtering or at least hydrogen. It is formed by sputtering in a gas atmosphere containing atoms (H) and / or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the example of the glow discharge described above,
It can also be used as an effective gas for spattering.

Further, for example, to form a second layer composed of amorphous silicon containing carbon atoms by a glow discharge method, a source gas containing silicon atoms (Si) as constituent atoms,
A raw material gas containing carbon atoms (C) as constituent atoms and, if necessary, a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms are mixed at a desired mixing ratio and used. Alternatively, a raw material gas containing silicon atoms (Si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms are also mixed at a desired mixing ratio. Alternatively, a source gas containing silicon atoms (Si) as constituent atoms is mixed with a source gas containing silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) as constituent atoms, or further, silicon atoms ( A raw material gas containing Si) and hydrogen atoms (H) as constituent atoms and a raw material gas containing carbon atoms (C) as constituent atoms are mixed and used.

Effectively used as such a source gas is hydrogen such as silane (Silane) having Si and H as constituent atoms such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H _10. Silicon gas, C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, 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 ), ethylene hydrocarbons include 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 ), butene (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Mention may be made of alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . In addition to these raw material gases, H ₂ can of course be used as the raw material 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 diluent 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 may be 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.

Specific examples of the starting material for introducing a nitrogen atom include nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ ) having a nitrogen atom as a constituent atom or a nitrogen atom and a hydrogen atom as constituent atoms. ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ) and the like nitrogen, and nitrogen compounds such as nitrides and azides. In addition to these, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N ₂ ) can be cited. When these halogenated nitrogen compounds are used, the nitrogen atom (N In addition to the introduction of (), 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.
_{A 3} N ₄ wafer or a 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, Si and Si ₃ N ₄ are used as separate targets.
Alternatively, by using a single target in which Si and Si ₃ N ₄ are mixed, at least hydrogen atom (H) or / and halogen atom (X) are contained in an atmosphere of a diluting gas as a gas for sputtering. It is formed by sputtering in a gas atmosphere containing the constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the 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 using the glow discharge method, the sputtering method, or the like.
And controlling the content of tin atom, group III atom or group V atom, oxygen atom, carbon atom or nitrogen atom, or hydrogen atom and / or halogen atom, supply of each atom flowing into the deposition chamber. It is carried out by controlling the gas flow rate of the starting materials or the gas flow rate ratio between the respective atom supplying starting materials.

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

Specifically, when forming the second layer made of a-Si (H, X) containing nitrogen atoms, oxygen atoms, carbon atoms, etc., the support temperature is usually 50 to 350 ° C. However, the temperature is particularly preferably 50 to 250 ° C. Gas pressure in the deposition chamber is typically 0.0
It is 1 to 1 Torr, and particularly preferably 0.1 to 0.5 Torr. The discharge power is usually 0.005 to 50 W / cm ² , more preferably 0.01 to 3 W / cm ² , and particularly preferably 0.01 to 20 W / cm ² .

When forming the first layer of a-SiGe (H, X), or a-S containing a group III atom or a group V atom
When forming the first layer made of iGe (H, X), the support temperature is usually 50 to 350 ° C, more preferably 50 to 300 ° C, and particularly preferably 100 to 300 ° C. .
The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, particularly preferably 0.
Set 1 to 1 Torr. The discharge power is usually 0.005 to 50 W / cm ² , but preferably 0.01 to 30 W / cm ^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.

The light-receiving member of the present invention requires that the light-receiving layer be formed so as to have at least a pair of non-parallel interfaces in the short range as described above, and therefore the light-receiving layer is formed on the support. The surface of the layer to be formed is formed so as not to be parallel to the surface of the support. To do so, the discharge power and gas pressure should be kept relatively high during the film formation operation. It will be done. The discharge power and gas pressure differ depending on the type of gas used, the material of the support, the shape of the support surface, the support temperature, etc., and are determined in consideration of these various conditions.

By the way, the distribution state of the germanium atom or / and the tin atom, the group III atom or the group V atom, or the hydrogen atom and / or the halogen atom contained in the first layer of the present invention is made uniform, or In order to form the first layer, it is necessary to keep the above conditions constant when forming the first layer or the second layer.

Further, in the present invention, at the time of forming the first layer, a germanium atom or / and a tin atom contained in the layer,
Alternatively, in order to form a layer having a desired distribution state in the layer thickness direction by changing the distribution concentration of the group III atom or the group V atom in the layer thickness direction, if a glow discharge method is used,
The gas flow rate at the time of introducing the germanium atom and / or tin atom or the starting material gas for introducing the group III atom or the group V atom into the deposition chamber is appropriately changed according to a desired rate of change, and other conditions Is formed while keeping a constant value. 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.

When the photoreceptive layer is formed by the sputtering method, the distribution concentration of germanium atom, tin atom, group III atom or group V atom in the layer thickness direction is changed in the layer thickness direction to obtain a desired layer thickness direction. In order to form the distribution state of, as in the case of using the glow discharge method, a starting material for introducing a germanium atom, a tin atom, a group III atom or a group V atom is used in a gas state, and the gas is The gas flow rate when introduced 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 11, 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. 25 shows an apparatus for manufacturing the light receiving member of the present invention by the glow discharge method.

The gas cylinders 2502, 2503, 2504, 2505, and 2506 in the figure are sealed with the raw material gas for forming each layer of the present invention. As an example, 2502 is SiF ₄ gas (purity 99.999%) cylinder, 2503 diluted with H ₂ B ₂ H ₆
Gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 2
504 is a CH ₄ gas (purity 99.999%) cylinder, 2505 is a GeF ₄ gas (purity 99.999%) cylinder, and 2506 is an inert gas (He) cylinder. 2506 ′ is a closed container containing SnCl ₄ .

A gas cylinder is required to allow these gases to flow into the reaction chamber 2501.
Make sure that valves 2522 to 2526 and leak valves 2535 of 2502 to 2506 are closed, and inflow valves 2512 to 2516,
After confirming that the outflow valves 2517 to 2521 and the auxiliary valves 2532 and 2533 are opened, the main valve 2534 is first opened to exhaust the reaction chamber 2501 and the gas pipe. Next, when forming the first layer and the second layer on the vacuum Al cylinder 2537, 1
An example is given below.

First, SiF ₄ gas from the gas cylinder 2502, B ₂ H ₆ / H ₂ gas from the gas cylinder 2503, and GeF ₄ gas from the gas cylinder 2505 are opened by opening valves 2522, 2523, 2525 and outlet pressure gauges 2527, 25.
Adjust the pressure of 28, 2530 to 1 kg / cm ^2, and adjust the inflow valves 2512, 251.
Gradually open 3, 2515, mass flow controller 2507, 2
Flow into 508 and 2510. Continued outflow valve 251
7, 2518, 2520 and auxiliary valve 2532 are gradually opened to allow the gas to flow into the reaction chamber 2501. SiF ₄ gas flow rate at this time,
Adjust the outflow valves 2517, 2518, 2520 so that the ratio of the GeF ₄ gas flow rate and the B ₂ H ₆ / H ₂ gas flow rate becomes the desired value, and also adjust the pressure in the reaction chamber 2501 to the desired value. Adjust the opening of the main valve 2534 while watching the reading of the vacuum gauge 2536. And the temperature of the basic cylinder 2537 is changed by the heater 2538.
After confirming that the temperature is set in the range of 50 to 400 ° C., the power supply 2540 is set to a desired electric power to cause glow discharge in the reaction chamber 2501 and a microcomputer (not shown) is connected. According to the predesigned flow rate change rate line, use SiF ₄ gas, GeF ₄ gas and B ₂ H ₆ / H
Basic cylinder 2537 while controlling the gas flow rate of ₂ gases
First, a first layer containing silicon atoms, germanium atoms and boron atoms is formed on top.

By the same operation as described above, in order to form the second layer on the first layer, for example, each of SiF ₄ gas and CH ₄ gas is diluted with He, Ar, H ₂ or the like, if necessary. And then flow into the reaction chamber 2501 at a desired gas flow rate to cause glow discharge according to desired conditions.

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.
In order to avoid remaining in the gas pipe inside the 2501 and the outflow valves 2517-2521 to the reaction chamber 2501, the outflow valve
2517 to 2521 are closed, auxiliary valves 2532 and 2533 are opened, the main valve 2534 is fully opened, and the system is temporarily evacuated to a high vacuum, if necessary.

Further, in the case where tin atoms are contained in the first layer, when a gas starting from SnCl ₄ is used as a raw material gas, the solid SnCl ₄ contained in 2506 ′ is heated by a heating means (see FIG. While heating with (not shown), an inert gas such as Ar or He is blown into the SnCl ₄ from an inert gas cylinder 2506 such as Ar or He for bubbling. Generated SnCl ₄
This gas is made to flow into the reaction chamber by the same procedure as the above-mentioned SiF ₄ gas, GeF ₄ gas, B ₂ H ₆ / H ₂ gas and the like.

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 concentrated hydrochloric acid with pure water at a volume ratio of 1 to 4 was used, and the immersion time of the hard sphere, the acid concentration, and the like were changed to appropriately adjust the shape of the unevenness.

Test Example 2 Using a hard sphere (height of surface irregularities λ _max = 5 μm) treated by the method of Test Example 1, and using the apparatus shown in FIGS. 6 (A) and 6 (B), an aluminum alloy The surface of a cylinder (60 mm in diameter, 298 mm in length) 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
However, if it is less than 0.1 mm, it is necessary to secure the drop height by making the rigid sphere small and light, which makes it difficult to control the formation of trace pits, which is not preferable, and R is 2.0 mm.
If it exceeds, the height of the hard sphere is made heavy and the fall height is adjusted. Therefore, for example, when the D is relatively small, it is necessary to make the fall height extremely low. In addition, if D is less than 0.02 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. confirmed.

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, and D shown in the upper column of Table 1A, and Cylindrical Al support with cylinders (Cylinder No. 101-10
6) got.

Next, a light receiving layer was formed on the Al support (cylinder Nos. 101 to 106) under the conditions shown in Table 1B below by the manufacturing apparatus shown in FIG.

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 apparatus shown in FIG. 26, 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. 26 (A) is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 26 (B) is a schematic side view schematically showing the entire exposure apparatus. In the figure, 2601 is a light receiving member, 2062
Is a semiconductor laser, 2603 is an fθ lens, and 2604 is a polygon mirror.

Next, as a comparison, an aluminum alloy cylinder (No. 107) surface-treated with a conventional diamond tool.
(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 an Al support (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. . The gas flow rates of the GrF ₄ gas and the SiF ₄ gas at the time of forming the first layer were automatically adjusted by microcomputer control according to the flow rate change lines shown in FIGS. 27 and 28.

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 (λ _max ) of surface irregularities shown in the upper column of Table 3A was used, a spherical trace depression (D = 450 ± 50 (μm), To obtain an Al support (cylinder Nos. 301 to 306).

Next, a light-receiving layer was formed on the Al support (cylinder Nos. 301 to 306) under the conditions shown in Table 3B below, using the manufacturing apparatus shown in FIG.

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 Al 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.

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.

Example 5 An Al support (Sample No. 1) was prepared 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 5.
03-106), and a light-receiving layer was formed thereon. At this time, the gas flow rates of H ₂ gas and PH ₃ / H ₂ gas at the time of forming the first layer were respectively
According to the flow rate change line shown in FIG. 29 and FIG. 30, it was automatically adjusted by microcomputer control.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

Example 6 An Al support (Sample No. 1) was prepared 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 6.
03-106), and a light-receiving layer was formed thereon. At this time, GeF ₄ gas, S
The gas flow rates of iF ₄ gas, H ₂ gas, and B ₂ H ₆ / H ₂ gas are each 31st.
According to the flow rate change curves shown in Fig. 32, Fig. 33 and Fig. 34, it was automatically adjusted by microcomputer control.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

Example 7 An Al support (Sample No. 103) was prepared 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 7.
~ 106) on top of which a photoreceptor layer was formed.

An image was formed on the obtained light-receiving member in the same manner as in Example 1, and the same good results as in Example 1 were obtained.

Example 8 Al support (Sample No. 1) was prepared 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 8.
03-106), and a light-receiving layer was formed thereon. At this time, the gas flow rates of GeH ₄ gas, SiH ₄ gas and B ₂ H ₆ / H ₂ gas at the time of forming the first layer are in accordance with the flow rate change curves shown in FIGS. 35, 36 and 37, respectively. Automatically adjusted by microcomputer control.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

Example 9 An Al support (Sample No. 1) was prepared 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 9.
03-106), and a light-receiving layer was formed thereon. At this time, the gas flow rates of SiH ₄ gas, GeF ₄ gas and B ₂ H ₆ / H ₂ gas at the time of forming the first layer are in accordance with the flow rate change curves shown in FIGS. 38, 39 and 37, respectively. Automatically adjusted by microcomputer control.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

Example 10 Al support (Sample No. 1) was prepared 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 10.
03-106), and a light-receiving layer was formed thereon. At this time, the gas flow rate of the B ₂ H ₆ / H ₂ gas during the formation of the first layer was automatically adjusted by microcomputer control according to the flow rate change curve shown in FIG.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

Example 11 An Al support (Sample No. 1) was prepared 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 11.
03-106), and a light-receiving layer was formed thereon. At this time, the gas flow rates of SiH ₄ gas, GeH ₄ gas (or SnCl ₄ / He gas) and B ₂ H ₆ / H ₂ gas at the time of forming the first layer are respectively FIG. 41, FIG. 42 and FIG. 43. According to the flow rate change curve shown in, it was automatically adjusted by microcomputer control.

Images were formed on these light receiving members in the same manner as in Example 1, and the same favorable results as in Example 1 were obtained.

[Outline of Effects of the Invention] The light-receiving member of the present invention is capable of solving all the problems of the light-receiving member having a light-receiving layer composed of amorphous silicon by forming the layers as described above. 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. it can.

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. , Sixth
(B) is a vertical sectional view. 7 to 15 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the light receiving layer of the present invention, and FIGS. 16 to 24 are oxygen atoms and carbon in the light receiving layer of the present invention. Atoms and nitrogen atoms,
FIG. 3 is a diagram showing the distribution state of group III atoms or group V atoms in the layer thickness direction, in each of which the vertical axis represents the layer thickness of the light-receiving layer and the horizontal axis represents the distribution concentration of each atom. There is. FIG. 25 is an example of an apparatus for producing the light receiving layer of the light receiving member of the present invention, and is a schematic explanatory view of a production apparatus by a glow discharge method. FIG. 26 is a diagram for explaining an image exposure device using laser light. FIGS. 27 to 43 are diagrams 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 light receiving 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, 104,204,3
03 ... Free surface, 204, 304 ... Interface between the first layer and the second layer About FIGS. 4 and 5, 401, 501 ... Support, 402, 502 ... Support surface, 403, 5
03 ... Spherical trace dents, 403 ', 503' ... Rigid spheres with irregularities on the surface, 404 ... Small irregularities formed in spherical trace dents, 404 '... Roughness formed on the surface of rigid spheres Shape Regarding Fig. 6, 601 ... Cylinder, 602 ... Rotating shaft (receiver), 603 ... Driving means, 604 ... Rotating container, 605 ... Rigid sphere with uneven surface, 606 ... Inner wall of container Ribs provided, 607 ...
… Shower tube Regarding Fig. 25, 2501 …… Reaction chamber, 2502 to 2506 …… Gas cylinder, 2506 ′…
… SnCl ₄ tank, 2507 to 2511 …… Mass flow controller, 251
2 to 2516 …… Inflow valve, 2517 to 2521 …… Outflow valve, 2
522 to 2526 …… Valve, 2527 to 2531 …… Pressure regulator, 253
2, 2533 …… Auxiliary valve, 2584 …… Main valve, 2535
...... Leak valve, 2536 …… Vacuum gauge, 2537 …… Base cylinder, 2538 …… Heating heater, 2539 …… Motor, 25
40 …… High-frequency power supply About Fig. 26, 2601 …… Light receiving member, 2602 …… Semiconductor laser, 2603…
… Fθ lens, 2604… Borgon mirror.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Koike 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-58-187943 (JP, A) JP-A-59 -58436 (JP, A) JP-A-60-31144 (JP, A) JP-A-60-68345 (JP, A) JP-A-60-35740 (JP, A) U.S. Patent 4432220 (US, A) U.S. Patent 3269066 (US, A)

Claims (11)

[Claims] 1. A first layer made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms on a support, silicon atoms, oxygen atoms and carbon. And a second layer composed of an amorphous material containing at least one selected from the group consisting of atoms and nitrogen atoms, wherein the width D of the recess is 500 μm on the surface of the support. In the following, the radius of curvature R and the width D of the depression have an unevenness due to a plurality of spherical trace depressions with 0.035 ≦ D / R, and 0.5 to 20 μm is further present in the spherical trace depression.
A light-receiving member characterized by having minute irregularities of m. 2. The second layer is composed of an amorphous material containing silicon atoms and at least one selected from oxygen atoms, carbon atoms and nitrogen atoms in a uniform distribution state. The light-receiving member described in the first item of the range. 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 concavo-convex shape of the spherical trace dent has an irregular shape due to the spherical trace dent having the same radius of curvature. 8. The light receiving member according to claim 1, wherein the unevenness of the spherical trace dent has an uneven shape formed by dents having the same radius of curvature and width. 9. The scope of claim 1, wherein the spherical dents have an uneven shape due to the dents of the rigid spheres obtained by spontaneously dropping a plurality of rigid spheres on the surface of the support. Light receiving member. 10. The spherical trace dent has a concavo-convex shape due to the trace dent of the hard sphere obtained by dropping hard spheres having substantially the same diameter from substantially the same height. Light receiving member. 11. The light receiving member according to claim 1, wherein the support is a metal body.