JPH0476103B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field to Which the Invention Pertains] The present invention relates to a light-receiving member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet rays, visible light, infrared rays, X-rays, R-rays, etc.). More specifically, the present invention relates to a light receiving member suitable for using coherent light such as laser light. [Description of the Prior Art] As a method for recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is Develop the image or
Furthermore, there are known methods of recording images that perform processes such as transfer and fixing as necessary. Among them, in image forming methods using electrophotography, small and inexpensive He-Ne lasers or semiconductor lasers ( It is common practice to record an image using a light emitting wavelength (usually having an emission wavelength of 650 to 820 nm). By the way, as a light-receiving member for electrophotography that is suitable when using a semiconductor laser, in addition to having better consistency in the photosensitivity region than other types of light-receiving members, it also has a high Vickers hardness. , amorphous materials containing silicon atoms (hereinafter referred to as "a-Si A light-receiving member consisting of the following is attracting attention. However, in the light receiving member, if the light receiving layer is a single-layer a-Si layer, it will maintain its high photosensitivity and meet the requirements for electrophotography.
In order to ensure a dark resistance of ^10-12 Ωcm or more, it is necessary to structurally contain hydrogen atoms, halogen atoms, or boron atoms in addition to these atoms in a controlled manner in a specific amount range. Therefore, there are considerable restrictions on the design tolerance of the light-receiving member, such as the need to strictly control various conditions during layer formation. Proposals have been made to improve such design tolerance problems by making it possible to effectively utilize the high light sensitivity even if the dark resistance is low to some extent. That is, for example, as seen in JP-A-54-121743, JP-A-57-4053, and JP-A-57-4172, the photoreceptive layer is formed by laminating two or more layers having different conductive properties. As the layer structure, a depletion layer is formed inside the photoreceptor layer, or as disclosed in JP-A-57-52178, JP-A-57-52179, JP-A-52180,
As seen in the publications of No. 58159, No. 58160, and No. 58161, 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 is used. Light-receiving members with increased apparent dark resistance have been proposed. However, in such a light-receiving member in which the light-receiving layer has a multilayer structure, the thickness of each layer varies, and when performing laser recording using this material, since the laser light is coherent monochromatic light, the light-receiving layer The free surface on the laser beam irradiation side of
It is called. ) The reflected light beams that are reflected from each other often cause interference. This interference phenomenon appears as a so-called interference fringe pattern in the formed visible image, causing image defects. Particularly in the case of forming a half-tone image with high gradation, this results in a blurred image with significantly poor distinguishability. Another important point is that as the wavelength range of the semiconductor laser light used becomes longer, the absorption of the laser light in the photoreceptive layer decreases, so there is a problem that the above-mentioned interference phenomenon becomes more noticeable. . i.e., e.g. two or more layers (multilayer)
In the case of a transfer member, an interference effect occurs in each of these layers, and each interference acts synergistically to create an interference fringe pattern, which directly affects the transfer member, and the member Another problem is that interference fringes corresponding to the interference fringe pattern are transferred and fixed and appear in a visible image, resulting in a defective image. As a measure to solve these problems, (a) the support surface is diamond-cut to a width of ±500Å to ±10,000Å.
(b) The surface of the aluminum support is treated with black alumite, or carbon, colored pigments, or dyes are added to the resin. A method of providing a light absorption layer by dispersing
(c) A method of providing a light-scattering anti-reflection layer on the surface of an aluminum support by subjecting the surface of the aluminum support to satin-like alumite treatment or sandblasting to provide fine grain-like irregularities ( For example, see Japanese Unexamined Patent Publication No. 16554/1983). Although these proposed methods provide some results, they are not sufficient to completely eliminate the interference fringe pattern that appears on images. That is, in method (a), a large number of irregularities of a specific t are provided on the surface of the support, and although this prevents the appearance of interference fringes due to the light scattering effect to a certain extent, the light scattering Since the specularly reflected light component still remains, in addition to the interference fringe pattern caused by the specularly reflected light remaining, the irradiation spot spreads due to the light scattering effect on the support surface, resulting in a substantial decrease in resolution. It will happen. Regarding method (b), complete absorption is not possible with black alumite treatment, and the reflected light on the support surface remains. In addition, when a colored pigment-dispersed resin layer is provided, when forming the a-Si layer, a degassing phenomenon occurs from the resin layer, resulting in a significant deterioration in the layer quality of the formed light-receiving layer. It is damaged by plasma during the formation of the Si layer, reducing its original absorption function, and has problems such as deterioration of the surface condition, which adversely affects the subsequent formation of the a-Si layer. Regarding the method (c), for example, when considering incident light, part of it is reflected on the surface of the photoreceptive layer and becomes reflected light, and the rest enters the inside of the photoreceptive layer and becomes transmitted light. At the surface of the support, the transmitted light
Part of it is scattered and becomes diffused light, the rest is specularly reflected and becomes reflected light, and part of it becomes emitted light and goes outside, but the emitted light contains components that interfere with the reflected light. However, since the interference fringe pattern remains in any case, it still does not completely disappear. By the way, in order to prevent interference in this case, some attempts have been made to increase the diffusivity of the surface of the support so that multiple reflections do not occur inside the photoreceptive layer. The light diffuses and causes halation, which ultimately reduces resolution. In particular, in a light-receiving member with a multilayer structure, even if the surface of the support is irregularly roughened, the light reflected from the first layer, the light reflected from the second layer, and the regular reflection from the surface of the support are interference, producing an interference fringe pattern according to the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it is impossible to completely prevent interference fringes by irregularly roughening the surface of the support. Furthermore, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies greatly between lots, and even within the same lot, the degree of roughness is uneven. , there is a problem in manufacturing control. In addition, relatively large protrusions are often formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer. Furthermore, even if the surface of the support is simply roughened regularly, the light-receiving layer is usually deposited along the uneven shape of the surface of the support. The incident light becomes parallel to the inclined surface, and the incident light produces bright and dark areas in that area.Also, because the thickness of the photoreceptive layer is non-uniform throughout the photoreceptive layer, a striped pattern of light and darkness appears. I end up. Therefore, simply by regularly roughening the surface of the support, it is not possible to completely prevent the occurrence of interference fringes. Furthermore, even when a multilayered light-receiving layer is deposited on a support whose surface is regularly roughened, there will be interference between specularly reflected light on the surface of the support and light reflected on the surface of the light-receiving layer. In addition, since interference due to reflected light at the interface between each layer is added, the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member having a single layer structure. [Object of the Invention] The purpose of the present invention is to eliminate the above-mentioned problems and to satisfy various requirements regarding a light-receiving member having a light-receiving layer mainly composed of a-Si. . That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent light fatigue resistance, and exhibit no deterioration phenomenon even after repeated use. a-Si, which has excellent durability and moisture resistance, no or almost no residual potential, and easy manufacturing control.
An object of the present invention is to provide a light-receiving member having a light-receiving layer comprising: Another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si, which has high photosensitivity in the entire visible light range, has excellent matching properties with a semiconductor laser, and has a fast photoresponse. It is about providing. Still another object of the present invention is to provide high photosensitivity and high SN.
An object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si and having specific characteristics and high electrical voltage resistance. Another object of the present invention is to provide excellent adhesion between layers provided on a support and the support and between laminated layers, strict and stable structural arrangement, and layer quality. An object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-Si with high a-Si. Still another object of the present invention is to be suitable for image formation using coherent monochromatic light, to be free of interference fringes and spots during reversal development even after long-term repeated use, and to be free from image defects and image formation. To provide a light-receiving member having a light-receiving layer made of a-Si and capable of obtaining a high-quality image with no blur, high density, clear halftones, and high resolution. It is in. [Structure of the Invention] As a result of intensive research to overcome the above-mentioned problems with conventional light-receiving members and achieve the above-mentioned purpose, the present inventors have obtained the following knowledge, and the present inventors have achieved the following findings. Based on this, the present invention was completed. That is, the present invention provides a layer made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms on a support, and a layer containing silicon atoms and containing germanium atoms and tin atoms. A light-receiving member comprising a light-receiving layer having a multi-layered structure including a layer made of an amorphous material containing no atoms in order from the support side, wherein the surface of the support has a plurality of spherical trace depressions. The present invention relates to a light receiving member having an uneven shape according to the present invention. By the way, the findings obtained by the present inventors as a result of extensive research are summarized as follows: In a light-receiving member having a plurality of layers on a support, the surface of the support is provided with irregularities formed by a plurality of spherical trace depressions. This eliminates the problem of interference fringes that appear during image formation. This knowledge is based on facts obtained through various experiments conducted by the present inventors. This will be explained below using drawings to facilitate understanding. FIG. 1 is a schematic diagram showing the layer structure of a light-receiving member 100 according to the present invention.
A layer 102' containing silicon atoms and at least one of germanium atoms and tin atoms and a layer 102' containing silicon atoms and neither germanium atoms nor tin atoms are formed along the uneven slopes. A photoreceptive layer 1 consisting of
02 shows a light-receiving member. FIGS. 2 and 3 are diagrams for explaining how the problem of interference fringes is solved in the light-receiving member of the present invention. Figure 3 shows a support with a regularly roughened surface.
1 is an enlarged view of a part of a conventional light-receiving member having a multi-layered light-receiving layer deposited thereon; FIG. In the figure, 301 is the first layer, 302 is the second layer, 30
3 indicates a free surface, and 304 indicates an interface between the first layer and the second layer. As shown in Figure 3,
When the surface of the support is simply roughened regularly by means such as cutting, the light-receiving layer is usually formed along the uneven shape of the surface of the support, so the slope of the unevenness of the surface of the support is and the inclined surface of the unevenness of the photoreceptive layer are in a parallel relationship. For this reason, for example, in a light receiving member in which the light receiving layer has a multilayer structure consisting of two layers, a first layer 301 and a second layer 302,
For example, the following problems are regularly encountered. 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 304
The reflected light R ₁ at the free surface and the reflected light R ₂ at the free surface coincide in direction, and interference fringes are generated depending on the layer 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 depressions on the surface of the support. and the photoreceptive layer on it is
In order to deposit along the uneven shape, for example, in the case of a light receiving member having a multilayer structure in which the light receiving layer is composed of two layers, the first layer 201 and the second layer 202, the first layer 201 and the second layer 202 are deposited. The interface 204 with the second layer 202 and the free surface 203 are each formed into an uneven shape with spherical trace depressions along the uneven shape of the support surface. If the curvature of the spherical trace depression formed at the interface 204 is R ₁ and the curvature of the spherical trace depression formed on the free surface is R ₂ , then R ₁ and R ₂ satisfy R ₁ ≠ R ₂ , so the interface 204 and the free surface 20
The reflected light at 3 has different reflection angles,
That is, θ ₁ and θ 2 in FIG. ₂ are θ ₁ ≠ θ ₂ , and
₁ , ₂ , ₃ shown in Fig. 2.
Since the wavelength shift, expressed as ₁ + ₂ - ₃ using By the way. As a result, even if interference fringes appear microscopically in the image appearing through such a light-receiving member, they are of such a degree that they cannot be visually perceived. In other words, the use of a support having such a surface shape means that in the case of a light-receiving member having a multilayered light-receiving layer formed thereon, the light that has passed through the light-receiving layer can reach the layer interface and the support. Reflection on the surface and their interference effectively prevent the formed image from having a striped pattern, leading to a light-receiving member capable of forming an excellent image. By the way, the curvature R and width D of the uneven shape due to the spherical trace depressions on the support surface of the light receiving member of the present invention
is an important factor in order to efficiently achieve the effect of preventing the occurrence of interference fringes in the light receiving member of the present invention. The present inventors have investigated the following points as a result of various experiments. That is, when the curvature R and the width D satisfy the following formula: D/R≧0.035, 0.5 or more Newton rings due to shearing interference are present in each trace depression. Furthermore, if the following formula: D/R≧0.055 is satisfied, one or more Newton rings due to shear ring interference are present in each trace depression. For this reason, in order to disperse the interference fringes occurring throughout the light receiving member into each trace depression and preventing the occurrence of interference fringes in the light receiving member, the D/R should be 0.035, preferably 0.055. It is desirable to set the above. Further, it is desirable that the width D of the unevenness due to the trace depression is at most about 500 μm, preferably 200 μm or less, and more preferably 100 μm or less. The present invention is based on the above-described findings, and the light receiving member provided by the present invention has the following structure as its main structure. That is, a layer made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms on a support;
A light-receiving member comprising a light-receiving layer having a multi-layered structure including, in order from the support side, layers made of an amorphous material containing silicon atoms and containing neither germanium atoms nor tin atoms, the light-receiving member comprising: A light-receiving member characterized in that the surface of the support has an unevenness formed by a plurality of spherical trace depressions in which the width D of the depression is 500 μm or less and the radius of curvature R and the width D of the depression are 0.035≦D/R. be. The unevenness caused by the plurality of spherical trace depressions on the surface of the support in the light receiving member of the present invention having the above configuration is as follows:
They may have the same radius of curvature, or may be formed by depressions having approximately the same radius of curvature and width. The light-receiving layer in the light-receiving member of the present invention having the above structure may contain atoms belonging to Group 1 or Group 3 of the periodic table. In this case, the distribution concentration of atoms belonging to Group 3 or Group 3 of the periodic table contained in the photoreceptive layer is relatively high on the support side, and is considerably low or substantially zero on the surface side. It can be distributed non-uniformly in the layer thickness direction so that the concentration is close to . In the light-receiving member of the present invention having the above structure, the distribution concentration of germanium atoms or tin atoms contained in layer A is relatively high on the support side, and the germanium atoms or tin atoms contained in layer A are relatively high in concentration on the support side. and a layer containing neither tin atoms)
It can be distributed non-uniformly in the layer thickness direction with a considerably lower concentration on the side than on the support side. The light-receiving layer in the light-receiving member of the present invention having the above structure can have a charge injection prevention layer containing an atom belonging to Group 1 or Group 3 of the periodic table as one of the constituent layers. The light-receiving layer in the light-receiving member of the present invention having the above structure can have a barrier layer as one of the constituent layers. Regarding the preparation of the light-receiving layer of the light-receiving member of the present invention, in order to efficiently achieve the above-mentioned object of the present invention, it is necessary to accurately control the layer thickness at an optical level. Vacuum deposition methods such as method, sputtering method, and ion plating method are usually used;
It is also possible to adopt a CVD method or the like. Hereinafter, the specific structure of the light receiving member of the present invention shown in FIG. 1 will be explained in detail. FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention.
0 represents a light-receiving member, 101 represents a support, 102 represents a light-receiving layer, and 103 represents a free surface. Support The support 101 in the light receiving member of the present invention is
The surface has irregularities smaller than the resolving power required for the light-receiving member, and the irregularities are caused by a plurality of spherical trace depressions. Hereinafter, examples of the shape of the surface of the support and a preferable manufacturing method thereof will be explained in detail with reference to FIGS. 4 and 5, but the shape of the support in the light receiving member of the present invention and the manufacturing method thereof are limited thereby. It is not something that will be done. FIG. 4 schematically shows a typical example of the shape of the support surface in the light-receiving member of the present invention, partially enlarging a part of the uneven shape. In FIG. 4, 401 is a support, 402 is a support surface, 403 is a rigid true sphere, and 404 is a spherical trace depression. Furthermore, FIG. 4 also shows one example of a preferred manufacturing method for obtaining the surface shape of the support.
That is, the rigid true sphere 403 is allowed to fall naturally from a position at a predetermined height from the support surface 402 and
02, a spherical depression 404 can be formed. Then, by using a plurality of rigid true spheres 403 with approximately the same diameter R' and dropping them simultaneously or sequentially from the same height h, the support surface 402 has approximately the same curvature R and the same width D. A plurality of spherical trace depressions 4
04 can be formed. FIG. 5 shows some typical examples of supports having an uneven shape formed by a plurality of spherical trace depressions on the surface as described above. In the example shown in FIG. 5A, the surface 5 of the support 501
A plurality of spheres 503, 503, . . . . are formed densely so as to overlap each other to form a regularly uneven shape. In this case, in order to form the recesses 504, 504, . . . that overlap with each other, the spheres 503, 503, .
It goes without saying that it is necessary to allow ... to fall naturally. In the example shown in FIG. 5B, two types of spheres 503, 503'... having different diameters are dropped from approximately the same height or different heights, and
On the surface 502 of 01, a plurality of depressions 504, 504' with two types of curvature and two types of width are formed densely so as to overlap with each other, and the height of the unevenness of the surface is irregular. It was formed. Furthermore, in the example shown in FIG. 5C (front view and cross-sectional view of the surface of the support), the surface 502 of the support 501
A plurality of spheres 503, 503', having approximately the same diameter,
... is irregularly dropped from approximately the same height, and a plurality of depressions 504, 504, ... having approximately the same curvature and multiple types of widths are formed so as to overlap with each other, thereby creating irregular unevenness. It was formed. As described above, by dropping a rigid true sphere onto the support surface, it is possible to form an uneven shape with spherical trace depressions, but in this case, the diameter of the rigid true sphere, the height at which it is dropped, By appropriately selecting various conditions such as the hardness of the support surface or the amount of spheres to be dropped, it is possible to form a plurality of spherical trace depressions having a desired curvature and width on the support surface at a predetermined density. can. 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 the support having the desired unevenness on the surface can be adjusted. Obtainable. In order to make the support of the light-receiving member have an uneven surface, a method has been proposed in which cutting is performed using a diamond cutting tool using a lathe, milling machine, etc., and although this is a reasonably effective method, In this method, the use of cutting oil,
It is essential to remove the chips that inevitably occur during cutting and the cutting oil that remains on the cutting surface.
In the end, processing is complicated and inefficient, but in the present invention, since the uneven surface shape of the support is formed by spherical trace depressions as described above, the above-mentioned problems can be solved. A support body having a desired uneven surface can be produced efficiently and easily without using any of the above methods. The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A, Cr, Mo, Au, Nb, Ta, V,
Examples include metals such as Ti, Pt, and Pb, and alloys thereof. Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, and paper. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side. For example, if it is glass, NiCr,
A, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Conductivity can be imparted by providing a thin film made of Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr ,A,Ag,Pb,Zn,
Ni, Au, Cr, Mo, Ir, Nb, Ta, V, T, Pt
Conductivity is imparted to the surface by providing a thin film of a metal such as the above by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support body can be any shape such as cylindrical shape, belt shape, plate shape, etc.
Its shape can be determined as appropriate depending on the purpose and desire. For example, if the light-receiving member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferable to use an endless belt or a cylindrical shape for continuous high-speed copying. The thickness of the support is appropriately determined so as to form a desired light-receiving member, but if flexibility is required as a light-receiving member, the thickness should be determined within a range that allows the support to fully perform its function. can be made as thin as possible. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more. Next, when the light-receiving member of the present invention is used as a light-receiving member for electrophotography, an example of an apparatus for manufacturing the surface of the support will be explained with reference to FIGS. 6A and 6B. It is not limited to this. As a support for a light-receiving member for electrophotography, an aluminum alloy or the like is subjected to ordinary extrusion processing to form a boathole tube or a mandrel tube, and the drawn tube obtained by further drawing processing is subjected to heat treatment and conditioning as necessary. Cylindrical shape with quality treatment etc.
A substrate is used, and the manufacturing apparatus shown in FIGS. 6A and 6B is used on the cylindrical substrate to form an uneven shape on the surface of the support. Examples of the spheres used to form the above-mentioned uneven shape on the surface of the support include various rigid spheres made of metals such as stainless steel, aluminum, steel, nickel, and brass, ceramics, and plastics. Rigid spheres made of stainless steel and steel are preferred for reasons such as flexibility and cost reduction. The hardness of such spheres may be higher or lower than the hardness of the support, but if the sphere is to be used repeatedly, it is desirable that the hardness be higher than the hardness of the support. 6A and 6B are schematic cross-sectional views of the entire manufacturing apparatus, and 601 is an aluminum cylinder for producing a support, and the surface of the cylinder 601 may be previously finished to an appropriate degree of smoothness. The cylinder 601 is supported by a rotating shaft 602, and is driven by a suitable driving means 603 such as a motor, so as to be able to rotate approximately around the axis. The rotation speed is appropriately determined and controlled in consideration of the density of the spherical trace depressions to be formed, the amount of rigid spheres supplied, and the like. 604 is a dropping device for naturally falling the rigid true sphere 605, which stores the rigid true sphere 605,
A ball feeder 606 for dropping the ball, a vibrator 607 for shaking the rigid true sphere 605 so that it can easily fall from the feeder 606, a collection tank 608 for collecting the rigid true sphere 605 that collides with the cylinder and falls, and collection. A ball feeding device 609 for transporting the rigid true spheres 605 collected in the tank 608 through a pipe to the feeder 606; a cleaning device 610 for cleaning the rigid true spheres with liquid midway through the feeding device 609;
It is comprised of a liquid reservoir 611 that supplies cleaning liquid (solvent, etc.) to the cleaning device 610 through a nozzle or the like, a recovery tank 612 that collects the liquid used for cleaning, and the like. The amount of rigid true spheres that naturally fall from the feeder 606 is adjusted as appropriate depending on the degree of opening and closing of the drop port 613, the degree of shaking by the vibrator 607, and the like. Light-receiving layer In the light-receiving member of the present invention, the light-receiving layer 10
2 is provided on the above-mentioned support 101, and the photoreceptive layer includes germanium atoms from the support 101 side.
At least one of Ge or a tin atom Sn,
Preferably, a-Si further contains at least one of a hydrogen atom and a halogen atom [hereinafter referred to as
It is written as "a-Si(Ge,Sn)(H,X)". ] and a-Si [hereinafter referred to as "a-Si(H,X)"] containing at least one of hydrogen atoms and halogen atoms as necessary. ] The photoreceptive layer 102 has a multilayer structure in which layers 102'' are laminated in order.The photoreceptive layer 102 can further contain a substance for controlling conductivity, if necessary.In the photoreceptor layer Specific examples of the halogen atom Amount of atom H or halogen atom 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 %. In addition, in the light-receiving member of the present invention, the layer thickness of the light-receiving layer is one of the important factors for efficiently achieving the object of the present invention, and is one of the important factors for imparting desired characteristics to the light-receiving member. Therefore, it is necessary to pay sufficient attention when designing the light-receiving member.
The thickness is preferably 100μ, preferably 1 to 80μ, more preferably 2 to 50μ. Incidentally, the purpose of containing germanium atoms and/or tin atoms in the light-receiving layer of the light-receiving member of the present invention is mainly to improve the absorption spectrum characteristics of the light-receiving member on the long wavelength side. That is, by containing germanium atoms and/or tin atoms in the light-receiving layer, the light-receiving member of the present invention exhibits various excellent properties, especially in the visible light region. It has excellent photosensitivity and fast photoresponsiveness to light of all wavelengths from relatively short wavelengths to relatively long wavelengths. This is particularly noticeable when a semiconductor laser is used as a light beam. In the light-receiving layer of the light-receiving member of the present invention, germanium atoms and/or tin atoms are contained in the layer 102' in contact with the support 101 in a uniform distribution state or in a non-uniform distribution state. It is something. (Here, a uniform distribution state means that the distribution concentration of germanium atoms and/or tin atoms is uniform in the plane direction parallel to the support surface of the layer 102', and is also uniform in the layer thickness direction of the layer 102'. Also, the non-uniform distribution state means that the distribution concentration of germanium atoms and/or tin atoms is uniform in the plane direction parallel to the support surface of the layer 102'; In the layer 102' of the present invention, in particular,
Germanium atoms and/or tin atoms are present in layer 10
It is desirable to contain the germanium atoms and/or tin atoms so that they are more distributed on the support side than on the 2″ side. When a long wavelength light source such as a semiconductor laser is used, the layer 102' can substantially completely absorb the long wavelength light, which is almost completely absorbed by the layer 102''. Interference due to reflected light from the surface is prevented. Further, in the light receiving member of the present invention, the layer 10
2' and layer 102'', respectively,
Since they have a common constituent element of silicon atoms, sufficient chemical stability is ensured at the laminated interface. Hereinafter, some typical examples of the distribution state of germanium atoms and/or tin atoms contained in the layer 102' in the thickness direction of the layer 102' will be explained using FIGS. 7 to 15 using germanium atoms as an example. . 7 to 15, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the layer 102', t _B is the position of the end of the layer 102' on the support side, t _T indicates the position of the end surface of the layer 102'' side opposite to the support side. That is, the layer 102' containing germanium atoms is formed toward the _tT side rather than the _tB side. , In each figure, the layer thickness and concentration are shown in an extreme form because if the values are shown as they are, the differences between each figure will not be clear, and these figures are only for ease of understanding. FIG. 7 shows a first typical example of the distribution state of germanium atoms contained in the layer 102' in the layer thickness direction. In the example shown, the distribution concentration C of germanium atoms is equal to the concentration C ₁ from the interface position t _B where the layer 102 ′ contacts the support surface where the layer ₁₀₂ ′ containing germanium atoms is formed.
germanium atoms in layer 1 while taking a constant value
02', and the concentration is gradually and continuously decreased from the position t ₁ to the interface position t _T from the concentration C ₂ . At the interface position _tT , the distribution concentration C of germanium atoms is substantially zero. (Here, "substantially zero" means that the amount is less than the detection limit.) In the example shown in _{FIG .}
A distribution state is formed in which the concentration gradually and continuously decreases from C ₃ until reaching C ₄ at position t _T . In the case of Fig. 9, from position t _B to position t _T ,
The distribution concentration C of germanium atoms is assumed to be a constant concentration _C5 , and between position _t2 and position _tT ,
The distribution concentration C is gradually and continuously decreased, and at the position _tT , the distribution concentration C is substantially zero. In the case of Fig. 10, the distribution concentration C of germanium atoms gradually decreases continuously from position _tB to position _tT , starting from the concentration _C6 , and decreases rapidly and continuously from position _t3. and is substantially zero at position _tT . In the example shown in FIG. 11, the distribution concentration C of germanium atoms between position t _B and position t ₄ is as follows:
The concentration _C7 is a constant value, and the distribution concentration C is zero at the position _tT . Between the position t ₄ and the position t _T , the distribution concentration C is linearly decreased from the position t ₄ to the position t _T . In the example shown in FIG. 12, the distribution concentration C
takes a constant value of concentration C ₈ from position t _B to position t ₅ , and from position t ₅ to position t _T it takes a constant value of concentration C ₉ to concentration C ₁₀
It is said that the distribution state decreases in a linear function until . In the example shown in Fig. 13, the position t _B is
Up to t _T , the distribution concentration C of germanium atoms decreases linearly from the concentration C ₁₁ and reaches zero. In FIG. 14, the distribution concentration C of germanium atoms from position t _B to position t ₆ is
The concentration is linearly decreased from C ₁₂ to C ₁₃ , and the position
An example is shown in which the concentration C ₁₃ is kept at a constant value between t ₆ and position t _T. In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a concentration C ₁₄ at a position t _B , and is gradually decreased from this concentration C ₁₄ until reaching a position t _{7 .} Near the position, the concentration decreases rapidly to a concentration _C15 at position _t7 . Between position t ₇ and position t ₈ , the concentration decreases rapidly at first, and then gradually decreases to reach C ₁₆ at position t ₈ , and between position t ₈ and position t ₉ , , the concentration at position t ₉ is gradually decreased
C ₁₇ . Between position _t9 and position _tT , the concentration is
C ₁₇ is reduced to substantially zero according to a curve shaped as shown in the figure. As described above, as shown in FIGS. 7 to 15, the layer 102'
As described above, some typical examples of the distribution state of germanium atoms and/or tin atoms contained therein in the layer thickness direction, in the light-receiving member of the present invention, germanium atoms and/or tin atoms are contained on the support side. The constituent layer 102 has a distribution state of germanium atoms and/or tin atoms which has a portion where the distribution concentration C of atoms is high and has a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. ′
It is desirable that the That is, the layer 102' constituting the light-receiving member in the present invention preferably has a localized region containing germanium atoms and/or tin atoms at a relatively high concentration on the support side, as described above. is desirable. In the light-receiving member of the present invention, the localized region is desirably provided within 5 μm from the interface position _tB , as explained using the symbols shown in FIGS. 7 to 15. The localized region may be the entire layer region up to 5 μm thick from the interface position _tB , or may be a part of the layer region. Whether the localized region is a part or all of the layer 102' is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. The localized region has a distribution state of germanium atoms and/or tin atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration of germanium atoms and/or tin atoms is preferably 1000 atomic ppm relative to silicon atoms. Above, more preferably
5000 atomic ppm or more, optimally 1×10 ⁴ atomic
It is desirable that the layer be formed in such a way that it can have a distribution state of ppm or more. That is, in the light receiving member of the present invention, the layer 10 containing germanium atoms and/or tin atoms
2' is the layer thickness from the support side within 5μ (5μ from t _B)
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists in the layer region). In the light-receiving member of the present invention, the content of germanium atoms and/or tin atoms contained in the layer 102' needs to be appropriately determined as desired so as to efficiently achieve the object of the present invention. 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 light-receiving layer may contain a substance that controls conductivity in the entire layer region or in a part of the layer region in a uniform or non-uniform distribution state. Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, such as atoms belonging to group of the periodic table that provide P-type conductivity (hereinafter simply referred to as "group atoms"), or ,
Atoms belonging to group of the periodic table (hereinafter simply referred to as "group atoms") that provide n-type conductivity are used. Specifically, the group atoms include B (boron), A (aluminum), Ga (gallium), In
(indium), T (thallium), etc., but particularly preferred are B and Ga. Group atoms include P (phosphorus), As (arsenic),
Examples include Sb (antimony) and Bi (bismane), but particularly preferred are P and Sb. When the photoreceptive layer of the photoreceptive member of the present invention contains a group atom or a group atom that is a substance that controls conductivity, it is determined whether the group atom or group atom is contained in the entire layer region or in a part of the layer region. As will be described later, the amount to be included will vary depending on the intended purpose or expected effect. That is, when the main purpose is to control the conductivity type and/or conductivity of the photoreceptive layer, it is contained in the entire layer area of the photoreceptive layer. The amount may be relatively small, typically 1 x 10 ^-3 to 1 x 10 ³ atomic ppm, preferably 5 x 10 ^-2 to 5 x 10 ² atomic ppm.
ppm, optimally between 1×10 ⁻¹ and 2×10 ² atomic ppm. In addition, it is possible to contain group atoms or group atoms in a uniform distribution state in some layer regions in contact with the support, or the group atoms or distribution concentration of group atoms in the layer thickness direction is such that the group atoms or group atoms are in contact with the support. When it is contained in a high concentration on the side,
Such a group atom or a constituent layer containing a group atom, or a layer region containing a group atom or a high concentration of a group atom functions as a charge injection blocking layer. In other words, when the group atom is contained, the movement of electrons injected from the support side into the photoreceptive layer is more efficiently blocked when the free surface of the photoreceptive layer is subjected to polar charging treatment. In addition, when group atoms are contained, the movement of holes injected from the support side into the photoreceptive layer when the free surface of the photoreceptive layer is subjected to polar charging treatment. can be prevented more efficiently. In such a case, the content is relatively large, specifically, 30 to 5×10 ⁴ atomic
ppm, preferably 50 to 1×10 ⁴ atomic ppm, optimally 1×10 ² to 5×10 ³ atomic ppm. Furthermore, in order to efficiently exhibit the effect of the charge injection blocking layer, the layer thickness of the layer or layer region provided at the end of the support side containing group atoms or group atoms should be t, and When the thickness of the layer is T, it is desirable that the relationship t/T≦0.4 holds true, and more preferably the value of this relational expression is 0.35 or less, most preferably 0.3 or less.
Further, the layer thickness t of the layer or layer region is generally 3
×10 ^-3 to 10μ, preferably 4×10 ^-3 to 8μ,
The optimum value is 5×10 ⁻³ to 5 μ. Next, the amount of group atoms or group atoms contained in the photoreceptive layer is relatively large on the support side and decreases from the support side toward the free surface side, and the amount of group atoms contained in the photoreceptive layer is relatively large on the support side and decreases from the support side toward the free surface side. Figures 16 to 24 show some typical examples where group atoms or group atoms are distributed in relatively small amounts or substantially close to zero near the edges. However, the present invention is not limited to these examples. In each figure, the horizontal axis represents group atoms or the distribution concentration C of group atoms, the vertical axis represents the layer thickness of the photoreceptive layer, t _B represents the interface position between the support and the photoreceptive layer, and t _T represents The position of the free surface of the photoreceptive layer is shown. FIG. 16 shows a first typical example of the distribution state of group atoms or group atoms contained in the photoreceptive layer in the layer thickness direction. In this example, from the interface position _tB where the group atom or the photoreceptive layer containing the group atom and the support surface are in contact with _each other, the distribution concentration C of the group atom or group atom becomes _C1. From the position _t1 to the free surface position _tT , the distribution concentration C of group atoms or group atoms decreases continuously from the concentration C2, and at position _tT , the group atom or group atom distribution concentration C decreases continuously from the concentration _C2 . The distribution concentration C of atoms becomes _C3 . FIG. 17 shows one other typical example.
In this example, the distribution concentration C of group atoms or group atoms contained in the photoreceptive layer is from position t _B to position t _T
The concentration decreases continuously from C ₄ until reaching , and reaches a concentration of ₅ at position t _T . In the example shown in FIG. 18, from position t _B to position t ₂ , the group atom or the distribution concentration C of the group atom is the concentration
C ₆ is maintained at a constant value, and from position t ₂ to position t _T , the distribution concentration of group atoms or group atoms C
gradually and continuously decreases from the concentration _C7 , and at the position _tT , the group atom or the distribution concentration C of the group atom becomes substantially zero. However, here, "substantially zero" refers to a case where the amount is less than the detection limit amount. In the example shown in FIG. 19, the distribution concentration C of group atoms or group atoms gradually decreases from the concentration C ₈ from position t _B to position t _T , and at position t _T Distribution concentration C of atoms or group atoms
is effectively zero. In the example shown in FIG. 20, the group atom or the distribution concentration C of the group atom is at a constant concentration C ₉ from position t _B to position t ₃ , and from position t ₃ to position t _T
Between, from concentration C ₉ to concentration C ₁₀ ,
Decrease linearly. In the example shown in FIG. 21, the group atom or the distribution concentration C of the group atom is at a constant concentration C ₁₁ from position t _B to position t ₄ , and from position t ₄ to position t _T
The concentration decreases linearly from C ₁₂ to C ₁₃ . In the example shown in FIG. 22, the group atom or the distribution concentration C of the group atom decreases linearly from position t _B to position t _T from the concentration C ₁₄ to substantially zero. . In the example shown in FIG. 23, the distribution concentration C of group atoms or group atoms decreases linearly from position _tB to position _t5 , from concentration _C15 to concentration _C16 , and at position t ₅ to position t _T, the concentration C ₁₆ remains constant. Finally, in the example shown in FIG. 24, the group atom or the distribution concentration C of the group atom is a concentration C ₁₇ at position t _B , and from position t _B to position t ₆ , the concentration C ₁₇ is initially constant. The concentration decreases rapidly near position t ₆ , and reaches a concentration of C ₁₈ at position t ₆ . next,
From position t ₆ to position t ₇ , the concentration decreases rapidly at first, and then gradually decreases, reaching the concentration C ₁₉ at position t ₇ . Further, it gradually decreases very slowly between position t ₇ and position t ₈ , and reaches the concentration C ₂₀ at position t ₈ . Furthermore, from position _t8 to position _tT , the concentration gradually decreases from _C20 to substantially zero. As in the examples shown in FIGS. 16 to 24, the photoreceptive layer has a portion with a high distribution concentration C of group atoms or group atoms on the side closer to the support, and is closer to the free surface of the photoreceptor layer. On the side, if the distribution concentration C has a portion with a considerably low concentration or a portion with a concentration substantially close to zero, the distribution concentration of group atoms or group atoms in the portion close to the support side is comparatively small. providing a localized area with high concentration of
Preferably, by providing the localized region within 5 μm from the interface position in contact with the support surface, the layer region having a high distribution concentration of group atoms or group atoms forms a charge injection blocking layer. The effects of the above can be achieved even more efficiently. The effects of each of the group atoms or the distribution state of the group atoms have been described individually above, but in order to obtain a light-receiving member having characteristics that can achieve the desired purpose, these group atoms or the distribution state of the group atoms It goes without saying that the distribution state of group atoms and the amount of group atoms or group atoms contained in the photoreceptive layer may be appropriately combined as necessary. For example, when a charge injection blocking layer is provided at the end of the photoreceptive layer on the support side, the polarity of the conductivity controlling substance contained in the charge injection blocking layer in the photoreceptive layer other than the charge injection blocking layer A substance that controls conductivity of a polarity different from that may be contained,
Alternatively, a substance controlling conductivity of the same polarity may be contained in an amount much smaller than that contained in the charge injection blocking layer. Furthermore, in the light-receiving member of the present invention, a so-called barrier layer made of an electrically insulating material may be provided as a constituent layer provided at the end on the support side, instead of the charge injection blocking layer, or the barrier layer may be made of an electrically insulating material. It is also possible to use both the charge injection blocking layer and the charge injection blocking layer as constituent layers. Examples of materials constituting such a 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. The light-receiving member of the present invention has the above-described layer structure, thereby solving all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when monochromatic laser light is used as a light source, it is possible to significantly prevent the appearance of interference fringes in the formed image due to interference phenomena, and to form an extremely high-quality visible image. In addition, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers, and has a high photoresponsiveness. It exhibits excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment properties. In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it has high sensitivity.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution. Next, a method for forming the photoreceptive layer of the present invention will be explained. The amorphous material constituting the photoreceptive layer of the present invention is deposited by a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. The manufacturing method for these is
Manufacturing conditions, level of equipment capital investment, manufacturing scale,
They are selected and adopted as appropriate depending on factors such as the desired characteristics of the light-receiving member to be produced, but it is relatively easy to control the conditions for producing a light-receiving member having the desired characteristics. The glow discharge method or the sputtering method is preferable because carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. Further, the glow discharge method and the sputtering method may be used together in the same apparatus system. For example, a-Si(H,
In order to form a layer composed of X), basically a raw material gas for introducing hydrogen atoms H and/or for introducing halogen atoms , is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, thereby forming a layer consisting of a-Si (H, . As the raw material gas for supplying Si, SiH ₄ , Si ₂
Examples include gaseous or gasifiable silicon hydrides (silanes) such as H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , and in particular,
SiH ₄ and Hi ₂ H ₆ are preferred in terms of ease of layer formation work and good Si supply efficiency. Further, the raw material gas for introducing halogen atoms includes many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen compounds in a gaseous state such as halogen-substituted silane derivatives, or halogen compounds that can be gasified. is preferred. Specifically, halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CF, CF ₃ , BrF ₅ ,
Interhalogen compounds such as BrF ₃ , IF ₇ , IC, IBr, etc.
and silicon halides such as SiF ₄ , Si ₂ F ₆ , SiC ₄ , and SiBr ₄ . This is particularly effective because a layer composed of a-Si containing halogen atoms can be formed without using gaseous or gasifiable silicon halides as described above. In addition, the raw material gas for supplying hydrogen atoms includes hydrogen gas, halides such as HF, HC, HBr, and Hi, and silicon hydrides such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ . , or SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ C
₂ , SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ and other halogen-substituted silicon hydrides can be used in a gaseous state or can be gasified. When these raw material gases are used, electric or photoelectric This is effective because the content of hydrogen atoms H, which is extremely effective in controlling physical characteristics, can be easily controlled. When the hydrogen halide or the halogen-substituted silicon hydride is used, the hydrogen atom H is also introduced at the same time as the halogen atom, which is particularly effective. In order to form a layer consisting of a-Si(H, A silicon compound gas containing halogen atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Bye. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. A layer made of a-Si(H,X) is formed on the support. To form a layer composed of a-SiGe (H, and a raw material gas for supplying hydrogen atoms H and/or halogen atoms X, which can supply hydrogen atoms H and/or halogen atoms , a glow discharge is generated in the deposition chamber to form a layer composed of a-SiGe (H, Substances that can be used as raw material gas for supplying Si, raw material gas for supplying halogen atoms, and raw material gas for supplying hydrogen atoms are used when forming the layer composed of a-Si(H,X) mentioned above. What you have is used as is. In addition, the substances that can be the raw material gas for supplying Ge include GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ,
Germanium hydride in a gaseous _state or capable of being gasified can be used, such _{as Ge5H12 , Ge6H14} , _{Ge7H16 , Ge8H18 , Ge9H20 .} In particular, from the viewpoint of ease of handling during layer creation work and good Ge supply efficiency,
GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferred. a-SiGe(H,X) by sputtering method
In order to form a layer composed of , a target made of silicon and a target made of germanium are used, or a target made of silicon and germanium is used, and these are sputtered in a desired gas atmosphere. It is done by a-SiGe using ion plating method
When forming a layer composed of (H,X),
For example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated and evaporated using a resistance heating method or an electron beam method (EB method). This can be done by allowing the flying vapor to pass through the desired gas plasma atmosphere. In both the sputtering method and the ion plating method, in order to contain halogen atoms in the layer to be formed, a gas of the above-mentioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber, and the gas is It is sufficient to form a plasma atmosphere of In addition, when introducing hydrogen atoms, a raw material gas for supplying hydrogen atoms, such as H ₂ or the above-mentioned gases such as hydrogenated silanes and/or hydrogenated germanium, is introduced into the deposition chamber for sputtering. A plasma atmosphere of gases such as the like may be formed. Further, as the raw material gas for supplying atoms for halogen, the above-mentioned halides or silicon compounds containing halogen are effective, but hydrogen halides such as HF, HC, HBr, and HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ C ₂ ,
Halogen-substituted silicon hydrides such as SiHC ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F,
GeHC ₃ , GeH ₂ C ₂ , GeH ₃ C, GeHBr ₃ ,
GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I
Hydrogenated germanium halides etc., GeF ₄ , etc.
GeC ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeC ₂ ,
Gaseous or gasifiable substances such as germanium halides such as GeBr ₂ , GeI ₂ and the like can also be used as effective starting materials. Amorphous silicon containing tin atoms (hereinafter referred to as "a-SiSn (H,
X)”. ) To form a photoreceptive layer composed of a-SiGe (H, This is done by using it in place of the starting material and controlling its amount in the layer to be formed. Substances that can serve as raw material gas for supplying the tin atoms include tin hydride SnH ₄ , SnF ₂ , SnF ₄ ,
Gaseous or gasifiable tin halides such as SnC ₂ , SnC ₄ , SnBr ₂ , SnBr ₄ , SnI ₂ , SnI ₄ etc. can be used, and when tin halides are used, they can be This method is particularly effective because a layer composed of a-Si containing halogen atoms can be formed on the body. Among them, SnC ₄ is preferred from the viewpoint of ease of handling during layer creation work, good Sn supply efficiency, and the like. When SnC ₄ is used as a starting material for supplying tin atoms, Sn, in order to gasify it, solid SnC ₄ is heated and an inert gas such as Ar or He is blown into the inert gas. It is preferable to perform bubbling using a gas, and the gas thus generated is introduced at a desired gas pressure into a deposition chamber whose interior is kept under reduced pressure. a-Si(H,X) using glow discharge method, sputtering method, or ion plating method
Alternatively, to form a layer composed of an amorphous material in which a-Si(Ge,Sn)(H,X) further contains group atoms or group atoms, a-Si(H,X)
Or, when forming a layer of a-Si (Ge, Sn) (H, (Ge,
Sn)(H, Specifically, starting materials for introducing boron atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅
Examples include boron hydride such as H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ and boron halides such as BF ₃ , BC ₃ and BBr ₃ . In addition, AC ₃ , GaC ₃ ,
Ga(CH ₃ ) ₂ , InC ₃ , TC ₃ and the like may also be mentioned. As a starting material for introducing a group atom, specifically for introducing a phosphorus atom, hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC ₃ , PC ₅ ,
Examples include phosphorus halides such as PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsC ₃ , AsBr ₃ ,
AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbC ₃ , SbC ₅ ,
BiH ₃ , BiC ₃ , BiBr ₅ and the like can also be mentioned as effective starting materials for introducing group atoms. As described above, the light-receiving layer of the light-receiving member of the present invention is formed using a glow discharge method, a sputtering method, etc., and germanium atoms and/or tin atoms, group atoms or The content of group atoms, hydrogen atoms, and/or halogen atoms can be controlled by controlling the gas flow rate of each starting material for supplying atoms flowing into the deposition chamber or the gas flow rate ratio between each starting material for supplying atoms. This is done by controlling the Further, the temperature of the support during formation of the photoreceptive layer of the present invention,
Conditions such as the gas pressure in the deposition chamber and the discharge power are important factors for obtaining a light-receiving member having desired characteristics, and are appropriately selected with consideration to the function of the layer to be formed. Furthermore, since these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be included in the photoreceptive layer, they should be determined by taking into consideration the type and amount of atoms to be included. There is also a need to do so. Specifically, a layer consisting of a-Si(H,X), or a layer containing group atoms or group atoms
When forming a photoreceptive layer made of -Si(H,X), 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 0.5 Torr. Also, the discharge power is
It is usually 0.005 to 50 W/cm ² , more preferably 0.01 to 30 W/cm ² , particularly preferably 0.01
~20W/ ^cm2 . When forming a layer consisting of a-SiGe (H,X), or when forming a layer consisting of group atoms or a-SiGe (H, , usually 50~350℃
However, the temperature is more preferably 50 to 300°C, 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 0.1 to 3 Torr.
Set to 1 Torr. In addition, the discharge power is 0.005 ~
It is usually 50W/ ^cm2 , but preferably
0.01~30W/ ^cm2 , particularly preferably 0.01~
20W/ ^cm2 . However, the specific conditions for layer formation, such as support temperature, discharge power, and gas pressure in the deposition chamber, are usually difficult to determine individually. Therefore, in order to form an amorphous material layer with desired characteristics, it is desirable to determine optimal conditions for layer formation based on mutual and organic relationships. By the way, in order to make the distribution state of germanium atoms and/or tin atoms, group atoms or group atoms, or hydrogen atoms and/or halogen atoms contained in the photoreceptive layer of the present invention uniform, it is necessary to form a photosensitive layer. In doing so, it is necessary to keep the above conditions constant. Further, in the present invention, when forming the photoreceptive layer, the distribution concentration of germanium atoms and/or tin atoms, group atoms, or group atoms contained in the layer is changed in the layer thickness direction to obtain a desired value. To form a layer having a distribution state in the layer thickness direction,
When using the glow discharge method, the gas flow rate when introducing into the deposition chamber the gas of germanium atoms and/or tin atoms, group atoms, or the starting material for introducing group atoms is adjusted according to the desired rate of change. It is formed by changing the conditions as appropriate and keeping other conditions constant. And to change the gas flow rate,
Specifically, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method, such as manually or using an externally driven motor. At this time, the rate of change in flow rate does not need to be linear;
For example, a desired content rate curve can be obtained by controlling the flow rate using a microcomputer or the like according to a predesigned change rate curve. In addition, when forming the photoreceptive layer using a sputtering method, the distribution concentration of germanium atoms, tin atoms, group atoms, or group group atoms in the layer thickness direction is changed in the layer thickness direction to obtain a desired layer thickness direction. To form the distribution state, germanium atoms or tin atoms,
Alternatively, a group atom or a starting material for introducing a group atom is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is varied in accordance with the desired rate of change. [Example] The present invention will be explained in more detail below according to Examples 1 to 11, but the present invention is not limited thereto. In each example, the photoreceptive layer was formed using a glow discharge method. FIG. 25 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method. 2502, 2503, 2504, 250 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the gas cylinder No. 5,2506,
As an example, 2502 is a SiF ₄ gas (purity 99.999%) cylinder, and 2503 is a B ₂ H ₄ gas diluted with H ₂ (purity 99.999%, hereinafter abbreviated as B ₂ H ₄ /H ₂ ) cylinder. , 2504 is SiH ₄ gas (purity
99.999%) cylinder, 2505 is GeF ₄ gas (purity
99.999%) cylinder, 2506 is an inert gas He cylinder. And 2506' is a closed container containing SnC ₄ . In order to flow these gases into the reaction chamber 2501, valves 252 of gas cylinders 2502 to 2506 are used.
2-2526, confirm that the leak valve 2535 is closed, and also check that the inflow valve 2512-2
516, confirm that the outflow valves 2517 to 2521 and the auxiliary valves 2532 and 3533 are open, and first open the main valve 2534 to exhaust the reaction chamber 2501 and gas piping. Next, vacuum A
An example of forming a light-receiving layer on the cylinder 2537 will be described 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 supplied to the valve 2522, respectively.
Open 2523, 2525 and check the outlet pressure gauge 252
Adjust the pressure of 7, 2528, 2530 to 1Kg/cm ² and gradually open the inflow valves 2512, 2513, 2515,
7,2508,2510. Subsequently, the outflow valves 2517, 2518, 2520 and the auxiliary valve 2532 are gradually opened to supply the gas to the reaction chamber 2.
501. At this time, the outflow valves 2517 and 251 are adjusted so that the ratio of SiF ₄ gas flow rate, GeF ₄ gas flow rate, and B ₂ H ₆ /H ₂ gas flow rate becomes the desired value.
8, 2520, and the opening of the main valve 2534 while checking the reading on the vacuum gauge 2536 so that the pressure inside the reaction chamber 2501 reaches the desired value. After confirming that the temperature of the base cylinder 2537 is set to a temperature in the range of 50 to 400°C by the heating heater 2538, the power supply 2537
540 to a desired power to generate a glow discharge in the reaction chamber 2501, and using a microcomputer (not shown), SiF ₄ gas,
First, a layer 102' containing silicon atoms, germanium atoms, and boron atoms is formed on the base cylinder 2537 while controlling the gas flow rates of GeF ₄ gas and B ₂ H ₆ /H ₂ gas. Layer 10 to desired layer thickness
2' is formed, the outflow valve 25
18, 2520 and continue glow discharge according to the same procedure except for changing the discharge conditions as necessary to form a layer 102'' that does not substantially contain germanium atoms on the layer 102'. It goes without saying that all outflow valves other than the outflow valves for gases required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer may react. Inside chamber 2501, outflow valve 2
In order to avoid gas remaining in the gas piping leading from 517 to 2521 into the reaction chamber 2501, the outflow valves 2517 to 2521 are closed and the auxiliary valve 253
2, 2533 is opened, the main valve 2534 is fully opened, and the system is temporarily evacuated to a high vacuum, as necessary. In addition, in the case of containing tin atoms in the photoreceptive layer, when using SnC ₄ as a starting material gas, solid SnC ₄ placed in 2506' is heated by heating means (not shown). ), and Ar, He, _etc.
Inert gas such as Ar, He, etc. is blown in from an inert gas cylinder 2506, and bubbled. The generated SnC ₄ gas is caused to flow into the reaction chamber using the same procedure as for the SiF ₄ gas, GeF ₄ gas, B ₂ H ₆ /H ₂ gas, etc. described above. Test example: Using a SUS stainless steel rigid sphere with a diameter of 2 mm,
The surface of an aluminum alloy cylinder (diameter 60 mm, length 298 mm) was treated to form irregularities using the apparatus shown in FIG. 6 described above. The diameter R′ of the true sphere, the falling height h and the curvature R of the trace depression,
When we investigated the relationship with the width D, we found that the curvature R of the trace depression
It was confirmed that the width D and the width D are determined by conditions such as the diameter R' of the true sphere and the falling height h. In addition, it was confirmed that the pitch of the dents (the density of the dents, and the pitch of the unevenness) can be adjusted to the desired pitch by controlling the rotational speed and number of cylinders, or the amount of fall of the rigid sphere. It was done. Example 1 The surface of an aluminum alloy cylinder was treated in the same manner as in the test example, and a cylindrical A support (cylinder No.
101-106) were obtained. Next, a light-receiving layer was formed on the A support (cylinder Nos. 101 to 106) using the manufacturing apparatus shown in FIG. 25 under the conditions shown in Table 1B below. These light-receiving members were exposed to light at a wavelength of 780 nm and a spot diameter using the image exposure device shown in Fig. 26.
Image exposure is performed by irradiating 80 μm laser light,
An image was obtained by performing the phenomenon and transfer. The occurrence of interference fringes in the obtained image was as shown in the lower column of Table 1A. Note that FIG. 26A is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 26B is a schematic side view schematically showing the entire exposure apparatus. In the figure, 260
1 is a light receiving member, 2602 is a semiconductor laser, 2
603 is an fθ lens, and 2604 is a polygon mirror. Next, as a comparison, an aluminum alloy cylinder (diameter 60 mm, length 298 mm, uneven pitch 100 μm,
A light-receiving member was produced in the same manner as described above using the unevenness (depth of 3 μm). When the obtained light-receiving member was observed under an electron microscope, it was found that the support surface, the layer interface of the light-receiving layer, and the surface of the light-receiving layer were parallel to each other. Using this light-receiving member, images were formed in the same manner as described above, and the obtained images were evaluated in the same manner as described above. The results were as shown in the lower column of Table 1A.

[Table] ×…Unpractical ○…Good practicality
△…Practically acceptable ◎…Particularly good practicality

[Table] Example 2 A
A photoreceptive layer was formed on the support (cylinder Nos. 101 to 107). In addition, when forming the photoreceptive layer, SiF ₄
The gas flow rates of the gas and GeF ₄ gas were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG. When an image was formed on the obtained light-receiving member in the same manner as in Example 1, the occurrence of interference fringes in the obtained image was as shown in the lower column of Table 2A.

[Table] ×…Unpractical ○…Good practicality
△…Practically acceptable ◎…Particularly good practicality

[Table] Examples 3 to 11 Everything was the same as in Example 1 except that the photoreceptive layer was formed according to the layer formation conditions shown in Tables 3 to 11.
A light-receiving layer was formed on Support A (Samples Nos. 103 to 106). At this time, in each example, the gas flow rate of the gas used when forming the photoreceptive layer was 28th to 3rd, respectively.
The flow rate was automatically adjusted by microcomputer control according to the flow rate change line shown in Figure 6. Further, in Examples 5 to 11, boron atoms contained in the photoreceptive layer were introduced as much as possible to about 200 ppm throughout the layer. When images were formed on these light-receiving members in the same manner as in Example 1, the images obtained were of extremely good quality with no interference fringes observed.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Summary of effects of the invention]

The light-receiving member of the present invention has the above-described layer structure, thereby solving all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when monochromatic laser light is used as a light source, it is possible to significantly prevent the appearance of interference fringes in the formed image due to interference phenomena, and to form an extremely high-quality visible image. In addition, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers, and has a high photoresponsiveness. It exhibits excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment properties. In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it has high sensitivity.
It has a high signal-to-noise ratio, has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing an example of the light-receiving member of the present invention, and FIGS. 2 and 3 are diagrams for explaining the principle of preventing the generation of interference fringes in the light-receiving member of the present invention. FIG. 2 is a partially enlarged view showing that the generation of interference fringes can be prevented in a light-receiving member in which irregularities formed by spherical trace depressions are formed on the surface of the support, and FIG. 3 is a diagram showing a conventional surface. FIG. 3 is a diagram showing that interference fringes occur in a light-receiving member in which a light-receiving layer is deposited on a regularly roughened support.
FIGS. 4 and 5 are schematic diagrams for explaining the uneven shape of the support surface of the light-receiving member of the present invention and the method for producing the uneven shape. FIG. 6 is a diagram schematically showing a configuration example of an apparatus suitable for forming the uneven shape provided on the support of the light-receiving member of the present invention, in which FIG. 6A is a front view and FIG. 6B is a front view. The figure is a longitudinal sectional view. 7 to 15 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the photoreceptive layer of the present invention, and FIGS. FIG. 3 is a diagram showing the distribution state of group atoms in the layer thickness direction; in each diagram, the vertical axis represents the layer thickness of the photoreceptive layer, and the horizontal axis represents the distribution concentration of each atom. FIG. 25 is an example of an apparatus for manufacturing the light-receiving layer of the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. FIG. 26 is a diagram illustrating an image exposure apparatus using laser light. 27 to 36 are diagrams showing changes in the gas flow rate ratio in forming the photoreceptive layer of the present invention, where the vertical axis represents the layer thickness of the photoreceptive layer, and the horizontal axis represents the gas flow rate of the gas used. Regarding FIGS. 1 to 3, 100...light-receiving member, 101...support, 102...light-receiving layer, 1
02′...layer containing at least one of germanium atoms or tin atoms, 102″...
Layer containing neither germanium atoms nor tin atoms, 201, 301...first layer, 202,
302... second layer, 103, 203, 303...
...free surface, 204,304...interface between the first layer and the second layer. Regarding FIGS. 4 and 5, 401,501...Support, 402,502...Support surface, 403,5
03,503'...Rigid true sphere, 404,504...
...Spherical depression. Regarding Figure 6, 601...Cylinder, 60
2...Rotating shaft, 603...Driving means, 604...
Dropping device, 605... Rigid true sphere, 606... Ball feeder, 607... Vibrator, 608... Collection tank, 609... Ball feeding device, 610... Cleaning device, 611... Cleaning liquid reservoir, 612... ...Washing liquid recovery tank, 613...Drop port. Regarding FIG. 25, 2501...reaction chamber, 25
02~2506...Gas cylinder, 2506'...
Sealed container for SnC ₄ , 2507-2511...mass flow controller, 2512-2516...inflow valve, 2517-2521...outflow valve,
2522-2526... Valve, 2527-25
31...Pressure regulator, 2532, 2533...Auxiliary valve, 2534...Main valve, 2535
...Leak valve, 2536 ...Vacuum gauge, 253
7... Base cylinder, 2538... Heater, 2539... Motor, 2540... High frequency power supply. Regarding FIG. 26, 2601...light receiving member;
2602...Semiconductor laser, 2603...Fθ lens, 2604...Polygon mirror.

Claims (1)

[Scope of Claims] 1. On a support, a layer (a) made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms; A light-receiving member comprising a light-receiving layer having a multi-layered structure including layers made of an amorphous material containing no tin atoms in order from the support side, wherein the surface of the support has a width of a recess. 1. A light-receiving member characterized by having unevenness formed by a plurality of spherical trace depressions in which D is 500 μm or less and the radius of curvature R and the width D of the depressions are 0.035≦D/R. 2. The light-receiving member according to claim 1, wherein the light-receiving layer contains atoms belonging to Group 1 or Group 3 of the periodic table. 3. The light-receiving member according to claim 1, wherein the light-receiving layer has, as one of its constituent layers, a charge injection prevention layer containing atoms belonging to Group 1 or Group 3 of the periodic table. 4. The light-receiving member according to claim 1, wherein the light-receiving layer has a barrier layer as one of the constituent layers. 5. The light-receiving member according to claim 1, wherein the irregularities formed by the spherical trace depressions have the same radius of curvature. 6. The light-receiving member according to claim 1, wherein the unevenness caused by the spherical trace depressions is formed by depressions having substantially the same radius of curvature and width. 7. The light-receiving member according to claim 1, wherein the support is a metal body. 8. The distribution concentration of atoms belonging to Group 3 or Group 3 of the periodic table contained in the photoreceptive layer is relatively high on the support side, and is considerably low or substantially close to zero on the surface side. The light-receiving member according to claim 2, wherein the light-receiving member is non-uniformly distributed in the thickness direction. 9 The distribution concentration of germanium atoms or tin atoms contained in the layer A is relatively high on the support side, and the concentration on the layer B side, which does not contain either germanium atoms or tin atoms, is considerably lower than that on the support side. The light-receiving member according to claim 1, wherein the light-receiving member is non-uniformly distributed in the layer thickness direction.