JPH0668631B2 - 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, there are known methods for recording an image by carrying out processing such as transfer and fixing according to need. Among them, in the image forming method by electrophotography, as a laser, 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 Vickers hardness and has little problem of pollution. For example, it is disclosed in JP-A-54-86341 and JP-A-56-8.
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. 3746.

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. Is required to be strictly controlled, and there are considerable restrictions on the tolerance of the design of the light receiving member. 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
-4053, JP-A-57-4172, the light-receiving layer has a layered structure of two or more layers in which layers having different conduction characteristics are laminated to form a depletion layer inside the light-receiving layer, Alternatively, JP-A-57-52178, 52179, 52180 and 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 to solve such a problem, (a) a diamond is cut on the surface of the support to form a light scattering surface by providing irregularities of ± 500Å to ± 10000Å (see, for example, JP-A-58-162975). (b) A method for providing a light absorbing layer by black-anodizing the surface of an aluminum support, or dispersing carbon, a coloring pigment, or a dye in a resin (see, for example, JP-A-57-165845), (c) A method of providing a light-scattering antireflection layer on the surface of an aluminum support by subjecting the surface of the aluminum support to a satin-like alumite treatment or providing sandblasted fine irregularities in a grain shape (for example, JP-A-57-
16554 gazette), etc. have been proposed.

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

That is, in the method (a), a large number of irregularities of specific t 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 is Since the specular reflection light component still remains,
In addition to the interference fringe pattern due to the specular reflection light remaining, the light scattering effect on the surface of the support causes the irradiation spots to spread, resulting in 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. When a color pigment dispersed resin layer is provided, a
-When the -Si layer is formed, the degassing phenomenon occurs in the resin layer, the layer quality of the formed light-receiving layer is significantly deteriorated, and the resin layer is damaged by the plasma during the formation of the a-Si layer. Then, there is a problem that the original absorption function is reduced and the subsequent formation of the a-Si layer is adversely affected by the deterioration of the surface state.

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

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

In particular, in the light receiving member having a multi-layered structure, even if the surface of the support is irregularly roughened, the light reflected by the surface of the first layer, the second light
The reflected light from the layer and the specularly reflected light from the surface of the support interfere with each other to form an interference fringe pattern according to the thickness of each layer of the light receiving member. Therefore, in the light receiving member having a multilayer structure, it is impossible to completely prevent the interference fringes by irregularly roughening the surface of the support.

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

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

In addition, even when a multi-layered light-receiving layer is deposited on a support whose surface is regulated to be rough, 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,
Structure-strict and stable, high layer quality, a-
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 comprises a support, a first layer made of an amorphous material having a silicon atom as a base, and an inorganic fluoride, an inorganic oxide and an inorganic material which have an antireflection function. What is claimed is: 1. A light-receiving member having a light-receiving layer having a second layer composed of at least one selected from sulfides, wherein the surface of the support has a recess width D of 500 μm or less and a curvature of the recess. It is characterized in that it has irregularities due to a plurality of spherical trace dents with a radius R and a width D of 0.035 ≦ D / R.

By the way, the findings obtained by the inventors of the present invention as a result of their earnest studies are an outline, in a light-receiving member having a plurality of layers on a support, the surface of the support is provided with irregularities due to a plurality of spherical trace depressions. As a result, the problem of the interference fringe pattern that appears during image formation is solved.

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

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

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

2 and 3 are views for explaining the problem of the interference fringe pattern in the light receiving member of the present invention.

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

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

FIG. 2 is an enlarged view of a part of FIG. 1, and as shown in FIG. 2, the light receiving member of the present invention has an uneven shape formed by a plurality of minute spherical trace dents on the surface of the support. Since the light-receiving layer thereon is deposited along the uneven shape, for example, the light-receiving layer is a multilayer light-receiving member having a first layer 201 and a second layer 202. That is, the interface 204 between the first layer 201 and the second layer 202, and the free surface 203 are
Each is formed into an uneven shape due to a spherical trace dent along the uneven shape of the support surface. Assuming that the radius of curvature of the spherical trace depression formed on the interface 204 is R ₁ and the radius of curvature of the spherical trace depression formed on the free surface is R ₂ , R ₁ and R ₂ are R ₁ ≠ R ₂
Therefore, the reflected light at the interface 204 and the reflected light at the free surface 203 have different reflection angles, that is, θ ₁ and θ ₂ in FIG. ₂ are θ ₁ ≠ θ _2. , The directions are different, and ₁ + ₂ using ₁ and _{2 3} shown in FIG.
Since the wavelength shift represented by ₋₃ is not constant and changes, the shear ring interference corresponding to the 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 that appear through such a light receiving member will not be 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. It is possible to effectively prevent the formed image from forming a striped pattern due to the reflection on the surface and the interference between them, and to obtain a light receiving member capable of forming an excellent image.

By the way, the radius of curvature R and the width D of the uneven shape due to the spherical trace dents on the surface of the support of the light receiving member of the present invention efficiently achieve the effect of preventing the occurrence of interference fringes in the light receiving member of the present invention. It is an important factor to do.
The present inventors have made the following discoveries as a result of various experiments. That is, the radius of curvature R and the width D are as follows: If the above condition is satisfied, there are 0.5 or more Newton rings due to shear ring interference in each of the dents. Furthermore, the following formula: If the above condition is satisfied, there will be one or more Newton rings due to shear ring interference in each of the dent depressions.

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

In addition, the width D of the unevenness due to the trace depression is 500 μ at the maximum.
m, preferably less than 200 μm, more preferably 100 μm
It is desirable that the thickness is m or less.

The light-receiving layer of the light-receiving member of the present invention formed on a support having a specific surface shape as described above comprises a first layer and a second layer, and the first layer is a silicon atom. Amorphous material having a matrix of, particularly preferably silicon atoms (Si),
An amorphous material containing at least one of a hydrogen atom (H) and a halogen atom (X) [hereinafter referred to as "a-Si (H, X)". ] Or a-Si containing at least one selected from oxygen atom, carbon atom and nitrogen atom
It is composed of (H, X), and the first layer may contain a substance that controls conductivity. The first layer may have a multi-layer structure, and particularly preferably, a charge injection blocking layer containing a substance that controls the conductivity or / and a so-called barrier layer made of an electrically insulating material. As one of the constituent layers.

The second layer is composed of at least one selected from inorganic fluorides, inorganic oxides and inorganic sulfides, and has an antireflection function.

Regarding the production of the first layer and the second layer of the present invention, in order to efficiently achieve the aforementioned objects of the present invention, it is necessary to precisely control the layer thickness at an optical level, Vacuum deposition methods such as glow discharge method, spattering method and ion plating method are usually used.
A CVD method, a thermal CVD method or the like can also be adopted.

Hereinafter, the specific structure of the light receiving member of the present invention will be described in detail with reference to FIG.

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 The surface of the support 101 in the light receiving member of the present invention has unevenness smaller than the resolving power required for the light receiving member, and the unevenness is due to a plurality of spherical dents.

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 shape of the support in the light-receiving member of the present invention and a method for producing the same will be described. However, they are not limited to these.

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

In FIG. 4, 401 is a support, 402 is the surface of the support, 403 is a rigid spherical body, and 404 is a spherical dent.

Further, FIG. 4 also shows an example of a preferable manufacturing method for obtaining the surface shape of the support. That is, a rigid true sphere
It is shown that the spherical depression 404 can be formed by causing the 403 to naturally fall from a position of a predetermined height above the support surface 402 and colliding with the support surface 402. Then, by using a plurality of rigid true spheres 403 having substantially the same diameter R ′ and dropping them from the same height h at the same time or at the same time, the support surface 402 has substantially the same radius of curvature R and the same width. A plurality of spherical trace dimples 404 having D can be formed.

As described above, FIG. 5 shows some typical examples of the support body having the uneven shape formed by the plurality of spherical trace depressions on the surface.

In the example shown in FIG. 5 (A), a plurality of spheres 503, 503, ... Having substantially the same diameter are regularly dropped from substantially the same height on different parts of the surface 502 of the support 501, and are almost the same. A plurality of trace dents 504, 504, ... Having a radius of curvature and substantially the same width are densely formed so as to overlap each other to form a regular uneven shape. In this case, in order to form the recesses 504, 504, ... Which overlap each other, the spheres 503, 50 are arranged so that the collision times of the sphere 503 on the support surface 502 are shifted from each other.
Needless to say, it is necessary to let 3, ... fall naturally.

Further, in the example shown in FIG. 5 (B), two types of spheres 503, 503 '... Having different diameters are dropped from substantially the same height or different heights, and the two spheres 503, 503' ... A plurality of indentations 504, 504 '... Having two kinds of curvature radii and two different widths are densely formed so as to overlap each other to form unevenness having irregular surface heights.

Furthermore, FIG. 5 (C) (front view and sectional view of the surface of the support)
In the example shown in (1), a plurality of spheres 503, 503, ... Having substantially the same diameter are randomly dropped from the substantially same height on the surface 502 of the support 501, and have substantially the same radius of curvature and plural kinds of widths. A plurality of depressions 504, 504, ... Are formed so as to overlap each other, and irregular irregularities are formed.

As described above, by dropping the rigid true sphere on the surface of the support, it is possible to form an uneven shape due to the spherical trace depression, but in this case, the diameter of the rigid true sphere, the height to be dropped,
By selecting various conditions such as the hardness of the rigid true sphere and the surface of the support, or the amount of spheres to be dropped, a plurality of spherical trace depressions having a desired radius of curvature and width can be formed on the surface of the support with a predetermined density. Can be formed with. That is, by selecting the above conditions, the height and pitch of the unevenness formed on the surface of the support can be freely adjusted according to the purpose, and a support having a desired unevenness on the surface can be obtained. Obtainable.

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

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

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

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

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

As a support for electrophotographic and light-receiving members, aluminum alloy or the like is subjected to ordinary extrusion processing to form a boathole tube or mandrel tube, and a drawn tube obtained by further drawing is heat treated or adjusted as necessary. A cylindrical (cylindrical) substrate that has been subjected to a treatment such as quality is used.
An uneven shape is formed on the surface of the support using the manufacturing apparatus shown in FIGS. Examples of spheres used for forming the above-mentioned uneven shape on the surface of the support include metal such as stainless steel, aluminum, steel, nickel and brass, and various hard spheres such as ceramics and plastics. For reasons of cost reduction, stainless steel and steel rigid spheres are preferable. And even if the hardness of such a sphere is higher than the hardness of the support,
Alternatively, the hardness may be lower, but when the sphere is repeatedly used, it is preferably higher than the hardness of the support.

6 (A) and 6 (B) are schematic sectional views of the entire manufacturing apparatus,
601 is an aluminum cylinder for making a support,
The surface of the cylinder 601 may be finished to have an appropriate smoothness in advance. The cylinder 601 is rotatably supported by a rotary shaft 602, and is driven by an appropriate driving means 603 such as a motor so as to be rotatable about its axis.
The rotation speed is appropriately determined and controlled in consideration of the density of the spherical trace depressions to be formed, the supply amount of the rigid true sphere, and the like.

Reference numeral 604 denotes a drop device for naturally dropping the rigid true sphere 605. The ball feeder 606 for storing and dropping the rigid true sphere 605 swings so that the rigid true sphere 605 easily falls from the feeder 606. A vibrating machine 607, a collection tank 60 for collecting the rigid spherical body 605 that collides with the cylinder and falls.
8. Feeder 606 with rigid spherical body 605 collected in collection tank 608
Ball feeder 609, feeder 609 for pipe transport to
A cleaning device 610 for cleaning the rigid spherical body in the middle of the process, a liquid reservoir 611 for supplying cleaning liquid (solvent etc.) to the cleaning device 610 via a nozzle, etc., a recovery tank 612 for recovering the liquid used for cleaning, etc. It is configured.

The amount of the rigid spherical body that naturally falls from the feeder 606 is appropriately adjusted depending on the degree of opening / closing of the drop opening 613, the degree of rocking by the vibrator 607, and the like.

First Layer In the light receiving member of the present invention, a-Si (H, X) or at least one selected from oxygen atom, carbon atom and nitrogen atom is contained on the support 101 described above. a
-The first layer 102 composed of Si (H, X) is laminated,
The first layer 102 may further contain a substance that controls conductivity.

As the halogen atom (X) contained in the first layer,
Specific examples thereof include fluorine, chlorine, bromine and iodine, and particularly preferable examples include fluorine and chlorine. Then, a hydrogen atom (H) contained in the first layer 102.
Or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) is usually 1 to 40 atomic%, preferably 5 to 30 atomic%.

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 at least one kind selected from oxygen atom, carbon atom and nitrogen atom in the first layer of the light receiving member of the present invention is mainly to increase the photosensitivity and high dark resistance of the light receiving member. And improving the adhesion between the support and the first layer.

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

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

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

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

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

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

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

FIG. 7 shows a first typical example of the distribution state of atoms (O, C, N) contained in the first layer in the layer thickness direction. In this example, the distribution concentration C of the atoms (O, C, N) is C from the interface position t _B between the first layer containing the atoms (O, C, N) and the support to the position t _{1.
1 is} a constant value, and the position t of the interface with the second layer is greater than position t ₁ .
_T Until atoms (O, C, N) distribution concentration C of continuously decreases from the concentration C _2, atoms in position _{t T (O, C, N} ) distribution concentration of C ₃
Becomes

In another typical example shown in FIG. 8, the distribution concentration C of atoms (O, C, N) contained in the first layer is from the position t _B to the position t _T.
Up to, and decreases continuously from the concentration C _4, a concentration of C ₅ at position t _T.

In the example shown in FIG. 9, from the position t _B to the position t ₂ an atom (O,
The distribution concentration C of C, N) keeps a constant value of the concentration C ₆ , and the distribution concentration C of atoms (O, C, N) gradually continues from the concentration C ₇ from the position t ₂ to the position t _T. And the distribution concentration C of the atoms (O, C, N) becomes substantially zero at the position t _T.

In the example shown in FIG. 10, the distribution concentration C of atoms (O, C, N) is at the position t
_The concentration C ₈ gradually decreases from _B to the position t _T, and the distribution concentration C of atoms (O, C, N) becomes substantially zero at the position t _T.

In the example shown in FIG. 11, the distribution concentration C of atoms (O, C, N) is at a constant value of the concentration C ₉ between the position t _B and the position t ₃ ,
Between the position t ₃ and the position t _T , the concentration C ₉ to the concentration C ₁₀
Until it becomes a linear function.

In the example shown in FIG. 12, the distribution concentration C of atoms (O, C, N) is at a constant value of the concentration C ₁₁ from the position t _B to the position t _4, and from the position t ₄ to the position t _T. From concentration C ₁₂ to concentration C
It decreases linearly until it reaches ₁₃ .

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

In the example shown in FIG. 14, the distribution concentration C of atoms (O, C, N) decreases linearly from the position t _B to the position t ₅ until the concentration changes from C ₁₅ to C _16. Concentration from t ₅ to position t _T
Keep a constant value of C ₁₆ .

Finally, in the example shown in FIG. 15, the distribution concentration C of atoms (O, C, N) is the concentration C ₁₇ at the position t _B , and the distribution concentration C from the position t ₅ to the position t _5.
Up to ₆ , the density decreased from C ₁₇ to the beginning, and the position decreased.
The concentration decreases sharply around t ₆ and reaches the concentration C ₁₈ at the position t _T.
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
Decrease from ₂₀ to virtually zero.

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

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

The amount of atoms (O, C, N) contained in the localized region is
It is desirable to make the distribution state such that the maximum value of the distribution concentration C of N) is 500 atomic ppm or more, preferably 800 atomic ppm or more, and optimally 1000 atomic ppm or more.

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

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

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

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

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

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

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

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

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

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

Next, the method for forming the first layer of the present invention will be described.

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

In order to form a light-receiving layer composed of a-Si (H, X) by the glow discharge method, a raw material gas for supplying Si capable of supplying silicon atoms (Si) and hydrogen atoms (H) or Hydrogen atom (H) or / and halogen atom capable of supplying halogen atom (X)
(X) A raw material gas for supply is introduced into a deposition chamber capable of reducing the pressure in a desired gas pressure state, a glow discharge is caused in the deposition chamber, and a predetermined support installed in a predetermined position in advance. A layer composed of a-Si (H, X) is formed on the surface.

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 H hydrogenation may or gasified gas state such as ₁₀ silicon (silanes). In particular, SiH _4,
Si ₂ H ₆ is preferred.

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

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

When the first layer is formed by using the glow discharge method, basically, a silicon halide, which is a raw material gas for supplying Si, and a gas such as Ar, H ₂ or He has a predetermined mixing ratio. And a gas flow rate so that the gas is introduced into the deposition chamber and a glow discharge is generated to form a plasma atmosphere of these gases,
Although a light-receiving layer is formed on a support, in order to more easily control the content of hydrogen atom (H), which is extremely effective in terms of control of electrical or photoelectric properties, It is also possible to further mix a raw material gas for supplying hydrogen atoms with these gases. As the gas for supplying the hydrogen atoms, hydrogen gas, SiH ₄ , Si ₂ H ₆ , Si
A gas of silicon hydride such as ₃ H ₈ or Si ₄ H ₁₀ is used.
Further, as a gas for supplying hydrogen atoms, halides such as HF, HC, HBr, HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ C
_In the case of using a halogen-substituted silicon hydride such as ₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ or the like in a gas state or capable of being gasified, at the same time as the introduction of the halogen atom (X), the hydrogen atom (H ) Is also introduced, so it is effective.

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

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

In any of the sputtering method and the ion plating method, in order to make the layer to contain a halogen atom, a gas of the above-mentioned halide or a silicon compound containing a halogen atom is introduced into the deposition chamber, and the gas of A plasma atmosphere may be formed. Further, when hydrogen atoms are introduced, a raw material gas for supplying hydrogen atoms, for example, H ₂ or a gas of the above-mentioned hydrogenated silanes is introduced into a deposition chamber for sputtering and a plasma atmosphere of these gases is introduced. Should be formed. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are mentioned as effective ones.
Hydrogen halide such as F, HC, HBr, HI, SiH ₂ F ₂ , SiH
₂ I ₂ , SiH ₂ C ₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃
Halogen-substituted silicon hydrides such as and the like, and substances in the gas state or capable of being gasified such as can also be effectively used as starting materials.

A-Si containing oxygen atom, carbon atom, or nitrogen atom
Regarding the formation of the layer composed of (H, X) or a part of the layer region, when it is performed by the glow discharge method,
-When forming a layer composed of Si (H, X), atoms (O, C, N)
This is done by using the starting materials for introduction together with the starting materials for the formation of a-Si (H, X) so as to controllably incorporate their amounts in the layer to be formed.

As the starting material for introducing such an atom (O, C, N), most of them are gaseous substances having at least the atom (O, C, N) as constituent atoms or substances that can be gasified. Can be used.

Specifically, as a starting material for introducing an oxygen atom (O), for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monoxide (N _2). O), nitrogen trioxide (N ₂ O ₃ ), tetranitrogen dioxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitric oxide (N
O ₃ ), a silicon atom (Si), an oxygen atom (O), and a hydrogen atom (H) as constituent atoms, for example, disiloxane (H ₃ SiOSi
H _3), lower siloxanes and the like birds such as a siloxane _{(H 3 SiOSiH 2 OSiH 3)} , as the starting material of carbon atoms (C) for introducing, for example, methane (CH _4), ethane (C ₂ H ₆ ),propane
(C ₃ H _8), n- butane (nC ₄ H _10), pentane (C ₅ H ₁₂₎ saturated hydrocarbons having 1 to 5 carbon atoms such as 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 ), etc., an ethylene hydrocarbon having 2 to 5 carbon atoms, Acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ) and other acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Examples of the substance include nitrogen (N ₂ ), ammonia (NH ₃ ),
Examples thereof include hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N).

In the case of forming a layer composed of a-Si (H, X) containing atoms (O, C, N) using the sputtering method, the atoms are
(O, C, N) as a starting material for introducing, in addition to the above-mentioned gasifiable starting materials listed in the glow discharge method, as a solidified starting material, SiO ₂ , Si ₃ N ₄ , carbon Black can be mentioned. These can be used in the form of a target such as Si.

To form a layer composed of a-Si (H, X) containing a group III atom or a group V atom or a partial layer region by using a glow discharge method, a sputtering method or an ion plating method. Is a starting material for introducing a Group III atom or a Group V atom during formation of the layer composed of a-Si (H, X), which is used for forming a-Si (H, X). Use with starting material,
It is carried out by controlling their amounts in the layer to be formed.

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

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

When the first layer of the present invention is formed by a glow discharge method, a sputtering method, or an ion plating method,
The content of oxygen atoms, carbon atoms and nitrogen atoms, or group III atoms or group V atoms introduced into a-Si (H, X) is controlled by controlling the gas flow rate of the starting material flowing into the deposition chamber and the gas. This is done by controlling the flow rate ratio.

In addition, conditions such as the temperature of the support at the time of forming the first layer, the gas pressure in the deposition chamber, and the discharge power are important factors for obtaining the light receiving member having desired characteristics, and the function of the layer to be formed. It will be appropriately selected in consideration of the above. Further, 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.Therefore, the type of the contained atoms or the amount thereof should be taken into consideration. You also need to decide.

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

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

By the way, an oxygen atom contained in the first layer of the present invention,
In order to make the distribution of carbon atoms, nitrogen atoms, group III atoms or group V atoms, or hydrogen atoms and / or halogen atoms uniform, the above-mentioned various conditions should be kept constant when forming the light-receiving layer. It is necessary to keep.

Further, in the present invention, when forming the first layer, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or Group III atoms or Group V atoms contained in the layer is changed in the layer thickness direction. In order to form the first layer having a desired state of distribution in the layer thickness direction, if the glow discharge method is used,
The gas flow rate when introducing the oxygen atom, carbon atom, nitrogen 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 the desired rate of change, and It is formed while keeping the conditions constant. And
In order to change the gas flow rate, specifically, the opening of a predetermined needle valve provided in the middle of the gas flow path system is gradually changed by some commonly used method such as manual operation or an external drive motor. All you have to do is operate.
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 first layer is formed by the sputtering method, the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or group III atoms or group V atoms in the layer thickness direction is changed in the layer thickness direction. To form a desired distribution in the layer thickness direction,
As in the case of using the glow discharge method, a starting material for introducing an oxygen atom, a carbon atom, a nitrogen atom, or a group III atom or a group V atom is used in a gas state, and the gas is introduced into the deposition chamber. The actual gas flow rate is changed according to the desired rate of change.

Second Layer The second layer 103 of the light receiving member of the present invention is the above-mentioned first layer 1
A layer provided on 02 and having a free surface 104, that is, a surface layer, which has a function of reducing reflection on the free surface 104 of the light receiving layer and increasing the transmittance, that is, an antireflection function, and a light It has a function of improving various characteristics such as moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment resistance and durability of the receiving member.

The material for forming the second layer is, in addition to the condition that the layer having the second layer has an excellent antireflection function and also has the function of improving the above-mentioned various properties, in addition to the light receiving member. Not adversely affect the photoconductivity of, electrophotographic characteristics, for example, having a certain degree of resistance,
When adopting the liquid development method, conditions such as excellent solvent resistance and not deteriorating various properties of the first layer formed immediately are required. And those that can be effectively used are, for example, MgF ₂ , A ₂ O ₃ , ZrO ₂ , TiO ₂ , ZnS, GeO ₂ , and C.
At least one selected from inorganic fluorides such as eF ₃ , Ta ₂ O ₅ , AF ₃ , and NaF, inorganic oxides, and inorganic sulfides.

Further, in order to effectively achieve antireflection, the refractive index of the second layer forming material is n, as the second layer forming material,
The refractive index of the constituent layers of the first layer, where the second layer is directly laminated,
If n _a , then the following formula: It is desirable to select and use materials that satisfy the conditions of.

Hereinafter, the above-mentioned inorganic fluoride, inorganic oxide and inorganic sulfide,
Or, some examples of the refractive index of the mixture thereof will be given, but it goes without saying that the refractive index thereof may vary somewhat depending on the type of layer to be formed, conditions and the like. In addition, the numbers written in a square shape represent the refractive index.

ZrO ₂ (2.00), TiO ₂ (2.26), ZrO ₂ / TiO ₂ = 6/1 (2.09),
TiO ₂ / ZrO ₂ = 3/1 (2.20), GeO ₂ (2.23), ZnS (2.24), A
₂ O ₃ (1.63), CeF ₃ (1.60), A ₂ O ₃ / ZrO ₂ = 1/1
(1.68), MgF ₂ (1.38) Further, the thickness of the second layer is such that the layer thickness of the second layer is d, the refractive index of the material forming the second layer is n, and the wavelength of irradiation light is λ
Then, the following formula: It is desirable to satisfy the condition of. Specifically, when the wavelength of the exposure light is in the wavelength range from near infrared to visible light, the layer thickness of the second layer is preferably 0.05 to 2 μm.

Regarding the formation of the second layer, in order to efficiently achieve the object of the present invention, it is necessary to control the layer thickness at an optical level, and therefore, the vapor deposition method, the sputtering method, the plasma vapor phase method. , Optical CVD method, thermal CVD method, etc. are used. These forming methods include the type of surface layer forming material, manufacturing conditions,
Needless to say, it is appropriately selected and used in consideration of factors such as the load of capital investment and manufacturing scale.

By the way, from the viewpoint of easiness of operation, easiness of setting conditions, etc., when forming the surface layer, it is preferable to adopt the sputtering method when the above-mentioned inorganic compound is used. That is, using an inorganic compound for forming the surface layer as a target, using Ar gas as the sputtering gas, causing a glow discharge, and by sputtering the inorganic compound, the support on which the first layer is formed. On top, deposit a second layer.

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

〔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 example, the first layer was formed by using the glow discharge method and the second layer was formed by using the sputtering method. FIG. 16 shows an apparatus for manufacturing a light receiving member of the present invention.

The gas cylinders 1602, 1603, 1604, 1605, and 1606 in the figure are sealed with the raw material gas for forming the respective layers of the present invention. As an example, 1602 is SiH ₄ gas (purity 99.999%) cylinder, 1603 diluted with H ₂ B ₂ H ₆
Gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder,
1604 is a CH ₄ gas (purity 99.999%) cylinder, 1605 is an NH ₃ gas (purity 99.999%) cylinder, and 1606 is an inert gas (He) cylinder. Then, 1606 'is SnC ₄ is NyuTsuta closed container.

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

First, open SiH ₄ gas from the gas cylinder 1602, B ₂ H ₆ / H ₂ gas from the gas cylinder 1603, and CH ₄ gas from the gas cylinder 1604 by opening valves 1622, 1623, 1624, and outlet pressure gauges 1627, 16
Adjust the pressure of 28, 1629 to 1kg / cm ^2, and adjust the inlet valves 1612, 1
Gradually open 613 and 1614 to open the mass flow controller 160
It flows into 7, 1608 and 1609. Continuing outflow valve 1
617, 1618, 1619 and the auxiliary valve 1632 are gradually opened to allow gas to flow into the reaction chamber 1601. At this time, the outflow valves 1617, 1618, 1619 are adjusted so that the ratio of the SiH ₄ gas flow rate, the CH ₄ gas flow rate, and the B ₂ H ₆ / H ₂ gas flow rate becomes a desired value.
Vacuum gauge 1636 so that the pressure in the reaction chamber 1601 becomes the desired value.
Adjust the opening of the main valve 1634 while watching the reading.
After it is confirmed by the heater 1638 that the temperature of the base cylinder 1637 is set in the range of 50 to 400 ° C., the power source 1640 is set to a desired power and the reaction chamber 16
A glow discharge is generated in 01, and a SiF ₄ gas, CH ₄ gas, and B ₂ H gas are used in accordance with a predesigned flow rate change rate line using a micro computer (not shown).
Base cylinder 1 while controlling the gas flow rate of ₆ / H ₂ gas
First, a first layer containing silicon atoms, carbon atoms, and boron atoms is formed over 637.

After forming the first layer by the glow discharge method as described above, after closing the valves of the source gas and the dilution gas used to form the first layer, the leak valve 1635 is gradually opened. The inside of the deposition apparatus is returned to atmospheric pressure, and then the inside of the deposition chamber is cleaned using argon gas.

Next, on the cathode electrode (not shown), a target made of an inorganic compound for forming the second layer is attached on one surface, the leak valve 1635 is closed to reduce the pressure inside the deposition apparatus, and then argon gas is discharged inside the deposition apparatus. Introduce until about 0.015-0.02 Torr. High frequency power (150-170W)
To generate a glow discharge, the inorganic compound is sputtered, and the second layer is deposited on the already formed first layer.

Test example Using a rigid sphere made of SUS stainless steel with a diameter of 2 mm,
The surface of an aluminum alloy cylinder (diameter 60 mm, length 298 mm) was treated using the apparatus shown in the figure 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 D was found to be that the radius of curvature R and the width D of the trace dent are the radius R'of the 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.

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

Next, on the A support (cylinder No. 101 to 106),
With the manufacturing apparatus shown in FIG. 6, under the conditions shown in the following 1B,
Forming the first layer, then as the forming material of the second layer
A second layer having a layer thickness of 0.293 μm was formed using ZrO ₂ (refractive index 2.00).

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

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

Next, as a comparison, an aluminum alloy cylinder (N
O.107) (diameter 60 mm, length 298 mm, uneven pitch 100 μm, uneven 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 result is
The results are shown in the lower column of Table 1A.

Example 2 A light-receiving layer was formed on the A support (cylinders No. 101 to 107) in the same manner as in Example 1 except that the first layer was formed according to the layer forming conditions shown in Table 2B. did.

The boron atom contained in the first layer is B ₂ H ₆ / Si.
F ₄ ≈100 ppm was introduced so that all layers were doped with about 200 ppm.

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 The first layer was formed on the A support (cylinder NO. 105) used in Example 1 under the layer forming conditions shown in Table 3A. The boron atom contained in the first layer was introduced under the same conditions as in Example 2. Further, the gas flow rates of the B ₂ H ₆ / H ₂ gas and the H ₂ gas at the time of forming the first layer were automatically adjusted by the micro computer control according to the flow rate change curve shown in FIG. After the formation of the first layer, the second layer constituent materials (301 to 320) shown in the upper column of the 3B table are used, and the second layer is sputtered to have the layer thickness shown in the lower column of the 3B table. Formed by.

Image formation was performed on the obtained light receiving members (301 to 320) in the same manner as in Example 1.

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

Example 4 On the A support (cylinder No. 105) of Example 1,
A light-receiving layer was formed in the same manner as in Example 3 except that the first layer was formed under the layer forming conditions shown in the table.
The flow rates of the B ₂ H ₆ / H ₂ gas and the H ₂ gas during the formation of the first layer were automatically adjusted by the micro computer control according to the flow rate change line shown in FIG. Also,
The boron atoms contained in the first layer were under the same conditions as in Example 2.

Image formation was performed on the obtained light receiving members (401 to 420) in the same manner as in Example 1.

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

Examples 5-11 A support used in Example 1 (cylinder No. 103-10
6) The first layer is formed on each of the layers according to the layer forming conditions shown in Tables 5 to 11, and then the layer-constituting materials shown in the upper column of each Table 12 are used. The second layer having the layer thickness shown in the lower column was formed by the sputtering method.

In Examples 7, 8, 10 and 11, the gas used during the formation of the first layer was automatically adjusted by the micro computer control according to the flow rate change lines shown in FIGS. The boron atoms contained in the first layer were set to the same conditions as in Example 2 in each Example.

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 has the above-mentioned layer structure, whereby all the problems of the light-receiving member having the light-receiving layer composed of amorphous silicon can be solved. In particular, even when a laser light which is a coherent monochromatic light is used as a light source, it is possible to remarkably prevent the appearance of an interference fringe pattern in a formed image due to an interference phenomenon and form a very high quality visible image. 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. , 6th (B)
The figure is a longitudinal sectional view. FIGS. 7 to 15 are views showing the distribution state of group III atoms or group V atoms in the layer thickness direction in the first layer of the light receiving member of the present invention, and the vertical axis in each figure is the first Shows the layer thickness of the layer, and the horizontal axis represents the distribution concentration of each atom. FIG. 16 is an example of an apparatus for manufacturing the light receiving layer of the light receiving member of the present invention, and is a schematic explanatory view of a manufacturing apparatus by a glow discharge method. FIG. 17 is a diagram for explaining an image exposure device using laser light. FIGS. 18 to 23 are diagrams showing the change state of the gas flow rate ratio in the formation of the light receiving layer of the present invention, in which the vertical axis represents the layer thickness of the first layer and the horizontal axis represents the gas flow rate of the used gas. . 1 to 3, 100 ... Light receiving member, 101 ... Support, 102, 201, 301 ...
… First layer, 103, 202, 302 …… Second layer, 104, 203, 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, 503 '…… Rigid sphere, 404, 504 …… Spherical trace depression About the Fig. 6, 601 …… Cylinder, 602 …… Rotation axis, 603 …… Driving means, 604 …… Dropping device, 605 …… Rigid body True sphere, 606 ... Ball feeder, 607 ... Vibrator, 608 ... Collection tank, 609 ...
… Ball feed device, 610 …… Cleaning device, 611 …… Cleaning liquid reservoir, 612 …… Cleaning liquid recovery tank, 613 …… Fall port
11 …… Mass flow controller, 1612 to 1616 …… Inflow valve, 1617 to 1621 …… Outflow valve, 1622 to 1626 …… Valve, 1627 to 1631 …… Pressure regulator, 1632, 1633 …… Auxiliary valve, 1634 …… Main valve, 1635 ... Leak valve,
1636 ... vacuum gauge, 1637 ... base cylinder, 1638 ... heating heater, 1639 ... motor, 1640 ... high frequency power supply, about Fig. 17, 1701 ... light receiving member, 1702 ... semiconductor laser, 1703 ...
… Fθ lens, 1704 …… Polygon mirror.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Koike 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-60-31144 (JP, A) JP-A-59 -58436 (JP, A) JP-A-54-121743 (JP, A) JP-A-60-212768 (JP, A) US Patent 4432220 (US, A) US Patent 3269066 (US, A)

Claims (13)

[Claims] 1. A first layer composed of an amorphous material having a silicon atom as a base material, and an inorganic fluoride, an inorganic oxide and an inorganic sulfide having an antireflection function on a support. A light-receiving member comprising a light-receiving layer having a second layer composed of at least one selected, wherein the surface of the support has a recess width D of 500 μm or less and a curvature radius R and width of the recess. A light-receiving member characterized in that it has irregularities due to a plurality of spherical trace depressions in which D and 0.035 ≦ D / R. 2. The light-receiving member according to claim 1, wherein the first layer contains at least one selected from oxygen atoms, carbon atoms and nitrogen atoms. 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 thickness d of the second layer is expressed by the following formula, where n is the refractive index of the substance forming the second layer and λ is the wavelength of the irradiation light. The light receiving member according to claim 1, which satisfies the following. 8. The refractive index of the material forming the second layer is n.
And the refractive index of the amorphous material forming the first layer in contact with the second layer is n _a , the following formula: The light receiving member according to claim 1, which satisfies the following. 9. The light receiving member according to claim 1, wherein the irregularities of the spherical trace depressions are irregularities due to the spherical trace depressions having the same radius of curvature. 10. The concavo-convex pattern of the spherical trace dent is a concave-convex pattern having the same curvature radius and width.
Item 7. The light receiving member according to item. 11. The scope of claim 1, wherein the spherical dents are irregularities due to the dents of the rigid true spheres obtained by naturally dropping a plurality of rigid true spheres on the surface of the support. Light receiving member. 12. The spherical trace depression is an unevenness due to the trace depression of the rigid spherical body obtained by dropping a rigid spherical body having substantially the same diameter from substantially the same height. The light receiving member described. 13. The light receiving member according to claim 1, wherein the support is a metal body.