JPS6287969A - light receiving member - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention relates to the use of light (here, light in a broad sense, such as ultraviolet rays, visible light,
It relates to a light-receiving member that is sensitive to electromagnetic waves such as infrared rays, X-rays, gamma rays, etc.

More specifically, the present invention relates to a light receiving member suitable for using coherent light such as laser light.

[Description of prior art]

As a method for recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is developed. Further, there are known methods of recording images that perform processes such as transfer and fixing as necessary. Among them, in the image forming method using electrophotography, a small and inexpensive He-Ne laser or a semiconductor laser ( It is common practice to perform image recording using a light emitting wavelength (usually having an emission wavelength of 650 to 820 nm).

By the way, as a light-receiving member for electrophotography suitable when using a semiconductor laser, in addition to being superior in consistency of its photosensitivity region compared to other types of light-receiving members,
Amorphous materials containing silicon atoms (hereinafter referred to as A light-receiving member made of [abbreviated as a-8iJ] is attracting attention.

However, in the light-receiving member, if the light-receiving layer is made of a single-layer a-8i layer, it is possible to maintain its high photosensitivity while ensuring a dark resistance of 1 (112Ωα or more) required for electrophotography. 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, so various conditions are required during layer formation. There are considerable limitations on the design tolerances of light-receiving members, such as the need to strictly control the Proposals have been made to improve the sensitivity by making it more effective.For example, Japanese Patent Application Laid-Open No. 54-121743, Japanese Patent Application Laid-Open No. 57-4053, and Japanese Patent Application Laid-Open No. 57-41
As seen in Japanese Patent Publication No. 72, the photoreceptive layer has a layer structure of two or more layers having different conductivity characteristics, and a depletion layer is formed inside the photoreceptive layer, or as disclosed in JP-A No. 57-52178.
No. 52179, No. 52180, No. 58159, No. 58160, and No. 58161, a barrier layer is provided between the support and the photoreceptive layer or/and on the upper surface of the photoreceptive layer. A light-receiving member has been proposed that has a multilayer structure with an increased apparent dark resistance.

However, in such a light-receiving member 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, each layer constituting the photoreceptive layer, and the layer interface between the support and the photoreceptor layer
From now on, the term "free surface" and "layer interface" will be used together.
It is called "interface". ) The reflected light beams that are reflected from each other often interfere with each other.

This interference phenomenon occurs in the visible image that is formed.
It appears as an interference fringe pattern, picture 1! This may cause defects.

Particularly in the case of forming a half-tone image with high gradation, an image with extremely poor distinguishability is produced.

Another important point is that as the wavelength range of the semiconductor laser light used becomes longer, the absorption of the laser light in the photoreceptive layer decreases, so there is a problem that the above-mentioned interference phenomenon becomes more noticeable. .

That is, for example, in a device with a structure of two or more layers (multilayer), interference effects occur in each of those layers, and each interference acts synergistically to create an interference fringe pattern. This directly affects the transfer member, and there is a problem that interference fringes corresponding to the interference fringe pattern are transferred and fixed onto the member and appear in the visible image, resulting in a defective tooth gap.

As a measure to solve these problems, (a) the surface of the support is diamond-cut to
A method of forming a light scattering surface by providing unevenness of OA (for example, see Japanese Patent Application Laid-Open No. 162975/1982), (b) black alumite treatment of the surface of the aluminum support, or,
A method of providing a light absorption layer by dispersing carbon, colored pigments, and dyes in a resin (for example, Japanese Patent Application Laid-Open No. 57-165845
(C) A method of providing a light-scattering anti-reflection layer on the surface of the support by subjecting the surface of the aluminum support to a satin-like alumite treatment or by sandblasting to provide fine roughness in the form of grains (for example, a special method). (see Japanese Patent Publication No. 16554/1983), etc. have been proposed.

Although these proposed methods provide some results, they are not sufficient to completely eliminate the interference fringe pattern that appears on images.

That is, in method (a), a large number of 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 some extent,
As for light scattering, the specularly reflected light component still remains, so 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, causing substantial This results in a significant decrease in resolution.

Regarding method (b), complete absorption is not possible with black alumite treatment, and the reflected light on the support surface remains. In addition, when providing a colored pigment dispersed resin layer,
When forming the a-8i layer, a degassing phenomenon occurs from the resin layer,
The layer quality of the formed photoreceptive layer will deteriorate significantly, and the resin layer will be damaged by the plasma during the formation of the a-8i layer, reducing its original absorption function, and the subsequent a - There are problems such as having an adverse effect on the formation of the 3i layer.

Regarding method (c), for example, if we look at the incident light, a part of it is reflected on the surface of the photoreceptive layer and becomes reflected light,
The remainder enters the inside of the light-receiving layer and becomes transmitted light. At the surface of the support, part of the transmitted light is scattered and becomes diffused light, the rest is specularly reflected and becomes reflected light, and part of it becomes emitted light and goes outside. However, since the emitted light 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, some attempts have been made to increase the diffusivity of the surface of the support so that multiple reflections do not occur within the photoreceptive layer, but such attempts instead cause light to be absorbed within the photoreceptive layer. is diffused and causes halation, which ultimately results in a decrease in resolution.

In particular, in a multilayered light-receiving member, even if the surface of the support is irregularly roughened, the light reflected from the first layer surface, the light reflected from the second layer, and the specularly reflected light from the support surface are all affected. The interference results in an interference fringe pattern depending on the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it is impossible to completely prevent interference fringes by irregularly roughening the surface of the support.

Furthermore, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies greatly between layers, and even in the same lot, the degree of roughness is uneven, making it difficult to manufacture. There are management issues. In addition, relatively large protrusions are often formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer.

Furthermore, if the surface of the support is simply roughened regularly,
Since the light-receiving layer is deposited along the uneven shape of the surface of the support, the inclined surface of the unevenness of the support and the inclined surface of the unevenness of the light-receiving layer become parallel, and in that part, the incident light is directed to the bright area. This results in a dark area, and also a striped pattern of light and dark appears in the entire photoreceptive layer due to the non-uniformity of the layer thickness of the photoreceptive layer. Therefore, simply by regularly roughening the surface of the support, it is not possible to completely prevent the occurrence of interference fringes.

Also, when a multilayered light-receiving layer is deposited on a support whose surface is regularly roughened, specular reflection light on the support surface and
In addition to the interference with the reflected light on the surface of the light-receiving layer, there is also interference due to the reflected light at the interface between each layer, so that the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member with a single-layer structure.

[Purpose of the invention]

The object of the present invention is to eliminate the above-mentioned problems and to provide a light-receiving member having a light-receiving layer mainly composed of a-3i, which satisfies various demands.

That is, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable without depending on the usage environment, have excellent light fatigue resistance, and exhibit no deterioration phenomenon even after repeated use. To provide a light-receiving member having a light-receiving layer made of a-8i, which has excellent durability and moisture resistance, has no or almost no residual potential, and is easy to manage in production. be.

Another object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-8i, which has high photosensitivity in the entire visible light range, has excellent matching properties with semiconductor lasers, and has a fast photoresponse. It is about providing.

Still another object of the present invention is to provide a light-receiving member having a light-receiving layer composed of a-3i, which has high photosensitivity, high signal-to-noise ratio characteristics, and high electrical voltage resistance.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
A-
An object of the present invention is to provide a light-receiving member having a light-receiving layer made of 3i.

Still another object of the present invention is to provide an image f using coherent monochromatic light.
Suitable for image formation, even after long-term repeated use, there is no appearance of interference fringes or spots during reversal development, and there is no image defect or blurring of the image, resulting in high density and clear halftones. The object of the present invention is to provide a light-receiving member having a light-receiving layer made of a-3i, which can obtain high-quality strokes with high resolution and high resolution.

[Structure of the invention]

The present inventors have conducted intensive research to overcome the above-mentioned problems with conventional light-receiving members and achieve the above-mentioned objectives, and as a result, have obtained the following knowledge, and have developed the present invention based on this knowledge. It was completed.

That is, the present invention provides an amorphous material containing, on a support, silicon atoms, at least one of germanium atoms or tin atoms, and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms. a first layer composed of silicon atoms, and atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms that are different from the atoms contained in the first layer. A light-receiving member comprising a light-receiving layer that is separated from a second layer made of an amorphous material, wherein the first layer contains at least one of germanium atoms and tin atoms. and,
A light having a multi-layered structure including layers containing neither germanium atoms nor tin atoms in order from the support side, and the surface of the support having an uneven shape formed by a plurality of spherical trace depressions. Relating to a receiving member.

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 structure of 1000 layers of a light-receiving member according to the present invention.
and a second layer 103.

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.

FIG. 3 is an enlarged view of a part of a conventional light-receiving member in which a multilayer light-receiving layer is deposited on a support whose surface is regularly roughened. In reading, 3 (11 is the first layer, 3 (12) is the second layer, 303 is the free surface, 304
indicate the interface between the first layer and the second layer, respectively. As shown in Fig. 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. The sloped surface of the unevenness on the body surface and the sloped surface of the unevenness on the photoreceptive layer are in a parallel relationship.

This is due to the fact that, for example, the photoreceptive layer or the m − layer 3 (
In a light-receiving member having a multilayer structure consisting of two layers, ie, the first layer 11 and the second layer 3 (12), for example, the following transitions 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 reflected light R1 at the interface 304 and the reflected light R1 at the free surface match in direction, 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. Since the light-receiving layer thereon is deposited along the uneven shape, for example, the light-receiving layer overlaps the first layer 2 (11) and the second layer 2 (
12), the interface 2 between the first layer 2 (11) and the second layer 2 (12)
04 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 on the interface 204 is it, and the curvature of the spherical trace depression formed on the free surface 203 is R2, then R1 and R2 are R+ 'i' R2
As a result, the reflected light at the interface 204 and the free surface 203
The reflected light at θ1. in FIG. 2 has different reflection angles. θ2 is θ, lol θ2, the directions are different, and using 11, 12, 13 shown in Fig. 2, l
Since the wavelength shift, expressed as ++12it3, is not constant but changes, shearing interference corresponding to the so-called Newton's ring phenomenon occurs, and the interference fringes are dispersed within the depression. As a result, even if interference fringes appear microscopically in the image appearing through such a light-receiving member, they are not visible to the naked eye.

That is, the use of a support having such a surface shape is for a light-receiving member having a multi-layered light-receiving layer formed thereon, in which light passes through the light-receiving layer and reaches the layer interface and the support. Reflection on the surface and their interference effectively prevent the formed image from becoming striped, leading to a light receiving member capable of forming an excellent image.

By the way, the curvature R and width of the uneven shape due to the spherical trace depressions on the support surface 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. This is an important factor. The present inventors have investigated the following points as a result of various experiments.

That is, if the curvature I (and the width satisfy the following formula: % formula %, there will be 0.5 or more Newton rings due to shearing interference in each trace depression.Furthermore, the following formula :% Formula % If the following formula is satisfied, one or more Newton rings due to shearing interference will exist in each trace depression.

For this reason, in order to disperse the interference fringes that occur throughout the light receiving member into each trace depression and to prevent the occurrence of interference fringes in the light receiving member, the above-mentioned T should be set to 0.03.
5, preferably 0.055 or more.

In addition, the width of the unevenness due to the trace depression is at most 500
It is desirable that the thickness be about .mu.m, preferably 200 .mu.m or less, more preferably 100 .mu.m or less.

The light-receiving layer of the light-receiving member of the present invention provided on the support having the above-mentioned specific surface shape consists of a first layer and a second layer, and the first layer contains silicon atoms, An amorphous material containing at least one of germanium atoms or tin atoms, at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and more preferably at least one of hydrogen atoms or halogen atoms
-3i (Ge, Sn) (0, C, N) (H, X)
It is written as J. ]. The second layer is a layer containing at least one of germanium atoms and tin atoms (i.e., a-3i (Ge).

a-8i (0,C,N) (H,X)) and a layer containing neither germanium atoms nor tin atoms (i.e. )
The second layer may further contain a substance that controls conductivity, and particularly preferably, a substance that controls conductivity. One of its constituent layers is a charge injection blocking layer containing a substance that inhibits the charge injection and/or a so-called barrier layer made of an electrically insulating material.

Further, the second layer includes at least one selected from silicon atoms, oxygen atoms, carbon atoms, and nitrogen atoms! An amorphous material containing one kind of atoms different from the atoms contained in the first layer [hereinafter referred to as a-3
i (0, C-N) (H.

It is written as X). ] Consists of.

Regarding the first layer and second layer configurations of the light-receiving member of the present invention, in order to efficiently achieve the above-mentioned objects of the present invention,
70 Since it is necessary to precisely control the layer thickness at an optical level, vacuum deposition methods such as glow discharge method, sputtering method, and ion blating method are usually used. A thermal CVD method or the like may also be employed.

Hereinafter, specific details of the light-receiving member of the present invention will be explained according to illustrated examples, but the light-receiving member of the present invention is not limited to these examples.

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention, in which 100 is the light-receiving member, 1 (11 is the support), and 1 (12) is the First layer, 1 (12
)' is a layer containing at least one of germanium atoms or tin atoms, 1 (12)'' is a layer containing neither germanium atoms nor tin atoms, 103 is the second layer, 1
04 indicates the free surface, respectively.

Support The support 1 (11) in the light-receiving member of the present invention has irregularities on its surface that are finer than the resolution required for the light-receiving member, and the irregularities are formed 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 by these. It's not a thing.

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 Figure 4, 4(1
1 is a support, 4 (12) 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, it is shown that the spherical trace depression 404 can be formed by letting the rigid true sphere 403 fall naturally from a position at a predetermined height from the support surface 4 (12) and colliding with the support surface 4 (12). ing. Then, by using a plurality of rigid true spheres 403 having approximately the same diameter R' and dropping them simultaneously or sequentially from the same height h, onto the support surface 4 (12),
A plurality of spherical trace depressions 404 having approximately the same curvature R and the same width 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 figure M5 (A), the surface 5 (of the support 5 (11)
12) A plurality of spheres 50 with approximately the same diameter in different parts of
3. 503. ... are regularly dropped from approximately the same height to form a plurality of trace depressions 604. having approximately the same curvature and approximately the same width. 604. . . . are formed densely so as to overlap one another to form a regularly uneven shape. In this case, the recesses 504. which overlap with each other. 5
04. .
03. 503. It goes without saying that it is necessary to allow ... to fall naturally.

Furthermore, in the example shown in FIG. 5(B), two types of spheres 503. 503'... are dropped from approximately the same height or different heights to form a plurality of depressions 5 with two types of curvature and two types of width on the surface 5 (12) of the support 5 (11).
04. 504'... are formed densely so as to overlap each other, thereby forming irregularities with irregular heights on the surface.

Furthermore, in the example shown in FIG. 5(C) (front view and cross-sectional view of the surface of the support), the surface 5 (12) of the support 5 (11) is
A plurality of spheres 503 with approximately the same diameter. 503°... are irregularly dropped from approximately the same height to form a plurality of depressions 504. 504.
... are made to overlap with each other to form irregular irregularities.

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 rigid true sphere and the surface of the support, or the amount of spheres to be dropped, a plurality of spherical trace depressions having the desired curvature and width can be created on the surface of the support.
It can be formed with a predetermined density.

That is, by selecting the above-mentioned conditions, the height of the unevenness and the pitch of the unevenness formed on the surface of the support 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, it is essential to use cutting oil, remove chips that are inevitably generated by cutting, and remove cutting oil that remains on the cutting surface. However, in the present invention, since the uneven surface shape of the support is formed by spherical trace depressions as described above, the above-mentioned problems can be completely eliminated and the support with the desired uneven surface can be obtained. It can be created efficiently and easily.

The support 1 (11) used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, Al,
Cr, Mo, Au, Nb, Ta, V, Ti
, Pt, Pb, or 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, paper, and the like. 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, the surface may have NiCr, Al, etc.
-Cr, Mo, Au, Ir, Nb, Ta,
V, Ti.

Pt, Pd, In2O3, SnO2, ITO (
Conductivity can be imparted by providing a thin film made of In2O3+5n(12), etc., or if it is a synthetic resin film such as a polyester film, NiCr, kl
, Ag, Pb, Zn, Ni,
Au-Cr, Mo, Ir,
Nb, Ta, V.

A thin film of metal such as Tl or PL is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal to impart conductivity to the surface. The shape of the support body can be any shape such as cylindrical shape, belt shape, plate shape, etc., but depending on the use and desired,
Its shape can be determined as appropriate. For example, if the light-receiving member 100 of FIG. 1 is to be used as a one-image forming member for Seiko's photograph, it is preferable that it be in the shape of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is appropriately determined so as to form a light-receiving member with the desired shape, but if flexibility is required as a light-receiving member, the thickness of the support should be determined within a range that allows the support to function adequately. can be made as thin as possible. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

Next, when the light-receiving member of the present invention is used as a light-receiving member for electrophotography, an example of an apparatus for manufacturing the surface of the support will be explained with reference to FIGS. 6(A) and 6(B). However, the present invention is not limited thereto.

As a support for a light-receiving member for electrophotography, an aluminum alloy or the like is subjected to ordinary extrusion processing to form a boathole tube or mandrel tube, and the drawn tube obtained by further drawing processing is subjected to heat treatment and conditioning as necessary. A cylindrical (cylinder-shaped) substrate that has been subjected to a quality treatment, etc. is used, and a sixth
(A).

(B) Using the manufacturing apparatus shown in the figure, an uneven shape is formed on the surface of the support.

Examples of the spheres used to form the above-mentioned uneven shape on the surface of the support include various rigid spheres made of metals such as stainless steel, aluminum, steel, nickel, and brass, ceramics, and plastics. Rigid spheres made of stainless steel and steel are preferred for reasons such as low cost and cost reduction. And the hardness of such a sphere is
The hardness may be higher or lower than that of the support, but if the sphere is to be used repeatedly, it is desirable that the hardness be higher than that of the support.

6A and 6B are schematic cross-sectional views of the entire manufacturing apparatus;
(11 is an aluminum cylinder for making a support, and the surface of the cylinder 6 (11) may be finished to an appropriate degree of smoothness in advance.

The cylinder 6 (11) is supported by a rotating shaft 6 (12), and is driven by a suitable drive means 603 such as a motor, so that it can rotate approximately around the axis. It is determined and controlled as appropriate, taking into account the density of the spherical trace depressions, the supply amount of rigid true spheres, etc.

604 is a dropping device for allowing the rigid true sphere 605 to fall naturally, and a pole feeder 606 for storing and dropping the rigid true sphere 605. A vibrator 60 that vibrates so that the rigid true sphere 605 easily falls from the feeder 606
7. A recovery tank 608 for collecting the rigid true spheres 605 that collide with the cylinder and fall, and a ball feeding device 609 for transporting the rigid true spheres 605 collected in the recovery tank 608 through a pipe to the feeder 606. A cleaning device 610 for cleaning the rigid body with liquid midway through the feeding device 609. Cleaning device 61
A liquid reservoir 611.0 for supplying cleaning liquid (solvent, etc.) to 0 through a nozzle or the like. It is composed of a collection tank 612 that collects the liquid used for cleaning.

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 opening 613, the degree of shaking by the vibrator 607, and the like.

First Layer In the light-receiving member of the present invention, the first layer 1 (12) is provided on the support 1 (11), and the -th layer is formed from the support 1 (11 side) by a -8i (Ge, Sn) (
0,C,N )(I(,X) Layer 1 (1
2)' and a layer 1 (12)'' composed of a-8i (0, C, N) (H, Furthermore, a substance for controlling conductivity can be contained as necessary.

Specific examples of the halogen atom (X) contained in the first layer include fluorine, chlorine, bromine, and iodine,
Particularly preferred are fluorine and chlorine. The amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer 1 (12), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 1.
40 atomic%, preferably 5-3Q atomic
It is desirable to set it to c%.

In addition, in the light-receiving member of the present invention, the layer thickness of the first layer is one of the important factors for efficiently achieving the object of the present invention.
In order to give the light-receiving member the desired characteristics, it is necessary to pay sufficient attention when designing the light-receiving member.
0μ, more preferably 2 to 50μ.

By the way, the purpose of containing germanium atoms and/or tin atoms in the first 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 first 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 in the entire wavelength range from relatively short wavelengths to relatively short wavelengths. This is particularly noticeable when a semiconductor laser is used as a light beam.

In the first layer of the light-receiving member of the present invention, germanium atoms and/or tin atoms are contained in the layer 1 (12)' in contact with the support 1 (11) in a uniformly distributed state, or in a non-uniformly distributed state. (Here, 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 layer 1 (12)'. Yes, layer 1 (1
2)' is uniform in the layer thickness direction, and a non-uniform distribution state means that the distribution concentration of germanium atoms and/or tin atoms is parallel to the support surface of layer 1 (12)'. It means that the layer 1 (12)' is uniform in the plane direction, but is non-uniform in the thickness direction of the layer 1 (12)'. ) and layer 1(12)' of the invention
In particular, it is desirable that germanium atoms and/or tin atoms be contained in a state where they are more distributed on the support side than on the layer 1 (12) side; in such a case, the end portion on the support side By extremely increasing the distribution concentration of germanium atoms and/or tin atoms in layer 1 (12), when a long wavelength light source such as a semiconductor laser is used, the long wavelength light that can hardly be absorbed by layer 1 (12) can be substantially completely absorbed in layer 1 (12)', and interference by reflected light from the surface of the support is prevented.

Furthermore, in the light-receiving member of the present invention, layer 1 (12)'
Since the amorphous materials constituting the layer 1 and the layer 1 (12) each 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 layer 1 (12)' in the thickness direction of layer 1 (12)' will be described below, using germanium atoms as an example. This will be explained with reference to FIGS.

7 to 15, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of layer 1 (12)', and t is the end of layer 1 (12)' on the support side. The position of the part is t
? indicates the position of the end face on the side of layer 1 (12) opposite to the support side. That is, layer 1 containing germanium atoms (
12)', the layer is formed more toward the IT side than the t side.

In addition, 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 easy understanding. This is a schematic diagram for explanation.

FIG. 7 shows a first typical example of the distribution state of germanium atoms contained in layer 1 (12)' in the layer thickness direction.

In the example shown in FIG. 7, the surface of the support on which layer 1 (12)' containing germanium atoms is formed and
)', germanium atoms are contained in layer 1 (12)', while the distribution concentration C of germanium atoms takes a constant value of concentration C1 up to the position tl from the interface position t, where is gradually and continuously decreased from the concentration C2 up to the interface position tT. At the interface position t, the distribution concentration C of germanium i atoms is substantially zero.

(Here, "substantially zero" means that the amount is less than the detection limit.) In the example shown in FIG. 8, the distribution concentration C of the contained germanium atoms is from position t to position A distribution state is formed in which the concentration gradually and continuously decreases from C3 to reach C4 at position [7].

In the case of FIG. 9, position t, position t? Up to this point, the distribution concentration of germanium atoms is assumed to be at a constant position with cue degree C6, and the positions t2 and t? The distribution concentration C is gradually and continuously decreased between the two, and the distribution concentration C is substantially zero at the position 1T.

In the case of FIG. 10, the distribution concentration C of germanium atoms gradually decreases continuously starting from the concentration C6 until reaching the position 1T from the position t, and rapidly decreases continuously from the position t. It is substantially zero at position t.

In the example shown in FIG. 11, the distribution concentration C of germanium atoms is a constant value of concentration C7 between position t and position 12, and at position t? In this case, the distribution concentration C is assumed to be zero. Between the position t4 and the position 1T, the distribution density C is linearly linearly shifted from the position t4 to the position 1. has been reduced to.

In the example shown in FIG. 12, the distribution concentration C is at the position t
, the density C8 takes a constant value up to position t, and from position t
, up to position ta, the distribution state is such that the concentration decreases linearly from the concentration C8 to the concentration CIO.

In the example shown in FIG. 13, from position tIl to position tT
Until , the distribution concentration C of germanium atoms becomes the concentration C1
, is decreased more linearly and reaches zero.

In FIG. 14, from position tIl to position t6, the distribution concentration C of germanium atoms decreases linearly from concentration C1□ to concentration CI3, and between position t and position ta, An example in which the concentration CI3 is set to a constant value is shown.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a concentration CI4 at the position t, and is slowly decreased from this concentration C14 until reaching the position t7, and near the position [7]. , is rapidly decreased to a concentration CI5 at position t.

Between position t7 and position t8, the decrease is rapid at first, and then gradually decreased to position [8].
The concentration becomes CI6, and between positions t and t,
It is gradually decreased to iic,7 at position tI. Between position t and position 1T, the concentration CI□ is reduced to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 7 to 15, some typical examples of the distribution state of germanium atoms and/or tin atoms contained in layer 1 (12)' in the layer thickness direction, the present invention In the light-receiving member, on the support side, there is a part where the distribution concentration C of germanium atoms and/or tin atoms is high, and on the interface tT side, the distribution concentration C is considerably lower than that on the support side. The distribution state of germanium atoms and/or tin atoms having
)' is preferable.

That is, layer 1 (12
)' preferably has a localized region containing germanium atoms and/or tin atoms at a relatively high concentration on the support side as described above.

In the light-receiving member of the present invention, the localized regions can be explained using the symbols shown in FIGS. 7 to 15, such as the interface position t,
It is more desirable that the distance be within 5μ.

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

Whether the localized region is a part or all of the layer 1 (12)' is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region contains germanium atoms or/
and the distribution state of tin atoms in the layer thickness direction, the maximum value Cmax of the distribution concentration of germanium atoms and/or tin atoms
is preferably 1000 ato
mic ppm or more, more preferably 5000 atoms
IC ppm or more, optimal Niha 1×104104ato
It is desirable that the layers be formed in such a way that a distribution state of at least ppm can be obtained.

That is, in the light-receiving member of the present invention, the layer 1 (12)' containing germanium atoms and/or tin atoms is
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5 μm (layer region of 5 μm layer from tm) in terms of layer thickness from the support side.

In the light-receiving member of the present invention, the content of germanium atoms and/or tin atoms contained in the layer 1 (12)' must be appropriately determined as desired so as to efficiently achieve the object of the present invention. , usually 1-6 x 1051
05ato ppm, preferably 10-3X
10' atomic ppm, more preferably I
X 1 (12) ~ 2 X 10' atomic pp
Let it be m.

Further, the purpose of containing at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in the first layer of the light-receiving member of the present invention is mainly to increase the photosensitivity and increase the dark resistance of the light-receiving member. and improve the adhesion between the support and the first layer.

In the first layer of the present invention, when at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms is contained, it is contained in a uniform distribution state in the layer thickness direction, or in a uniform distribution state in the layer thickness direction. Whether or not it should be contained in a uniformly distributed state depends on the above-mentioned objectives and expected effects, and therefore the amount to be contained will also vary.

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

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

In the light-receiving member of the present invention, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms contained in the first layer is determined by the characteristics required for the first layer as described above. In addition to consideration of organic relationships such as the characteristics at the contact interface with the support, the
ic%, preferably 0.0(12) to 40 atoms
c%, optimally 0.003 to 30 atomic%.

By the way, if it is contained in the entire layer area of the first layer, or if the proportion of the layer thickness of a part of the layer area to be contained in the layer thickness of the first layer is large, the above-mentioned amount to be contained may be The upper limit will be lowered. That is, in that case, for example, the layer thickness of the layer region to be contained is usually 3Q atomic% or less, preferably 20 atomic% of the layer thickness of the first layer.
c% or less, optimally 10 atomic% or less.

Next, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms to be contained in the first layer of the present invention is relatively large on the support side, and from the end of the support side. It is distributed so that it decreases toward the end of the second layer side, and becomes a relatively small amount or substantially close to zero near the end of the first layer on the second layer side. Some typical examples are shown in Figures 16 to 24.
This will be explained using figures. However, the present invention is not limited to these examples. Hereinafter, at least one type selected from carbon atoms and oxygen atoms will be referred to as "atoms (0, C, N
) Written as J.

In FIGS. 16 to 24, the horizontal axis represents atoms (0, C.

N) distribution concentration C, the vertical axis indicates the layer thickness of the first layer, and t
, indicates the position of the interface between the support and the first layer, and 1T indicates the position of the interface between the first layer and the second layer.

Figure 16 shows atoms (0, C,
A first typical example of the distribution state of N) in the layer thickness direction is shown. In the example, atoms (0,C.

From the interface position t between the first layer containing N) and the support, the distribution concentration C of atoms (0, C, N) takes a constant value of (11), and from position 1. Up to the interface position t with the second layer, the distribution concentration C of atoms (0, C, N) also decreases continuously, and the concentration C2 also decreases continuously, and at position IT, atoms (
0, C, N) becomes 03.

In another typical example shown in FIG. 17, the distribution concentration C of atoms (0, C, N) contained in the first layer is at the position t,
From position t? The concentration C4 also decreases continuously until reaching position 1. The density becomes C6.

In the example shown in FIG. 18, from position t11 to position t2, the distribution concentration of atoms (0, C, N) maintains a constant value of CIJ'' - mystery degree C6, and from position t2 to position IT,
The distribution concentration C of atoms (0, C, N) gradually and continuously decreases from the concentration C7, and at position t1, the distribution concentration C of atoms (0, C, N) decreases gradually and continuously from the concentration C7.
) is substantially zero.

In the example shown in FIG. 19, the distribution concentration C of atoms (0, C, N) is from position t to position t? The concentration gradually decreases from C8 until , and at the position [T, the atom (-0
, C, N) is substantially zero.

In the example shown in the d420 diagram, the concentration C of atoms (0, C, N) is the concentration C0 between position t and position t3.
The density is at a constant value between the positions [3 and IT], and decreases numerically from the density C0 to the density C1o.

In the example shown in FIG. 21, the distribution of atoms (0, C, N) C is at a constant concentration Co from position t to position t4, and from position t4 to position fifty, the concentration Co is constant. It decreases linearly from CI□ to the concentration Cps.

In the example shown in FIG. 22, the distribution concentration C of atoms (0, C, N) decreases in a linear manner from position tll to position IT, from a concentration C14 to substantially zero.

In the example shown in Figure n, the distribution concentration C of atoms (0, C, N)
decreases linearly from the concentration C1 to the concentration CI6 from position 1B to position t, and maintains a constant value of concentration CI6 from position t to position IT.

Finally, in the example shown in FIG. 24, atoms (0, C.

The distribution concentration C of N) is the concentration C1□ at position t, and the distribution concentration C at position 1. From position t to position t, the concentration initially decreases slowly from C87, rapidly decreases near position t, and reaches concentration CI8 at position t. Next, from position t6 to position t, the concentration decreases rapidly at first, and then gradually decreases, and at position t7, the concentration reaches C8°. Further, between the positions t7 and t8, the concentration gradually decreases very slowly, and reaches the concentration C20 at the position t8.

Furthermore, from position t to position ta, the concentration C
It gradually decreases from 20 to essentially zero.

As in the examples shown in FIGS. 16 to 24, the end of the first layer on the support side has a portion with a rich distribution concentration C of atoms (0, C, N), and At the end on the second layer side,
J
A localized region having a relatively high distribution concentration of atoms (0, C, N) is provided at the end of the first layer on the support side, and preferably the localized region is located between the support surface and the first layer. By providing the layer within 5μ from the interface position 1B with the pigeon, it is possible to improve the adhesion between the support and the first layer even more efficiently.

The localized region may be all or a part of the layer region at the end of the first layer on the support side that contains atoms (0, C, N); Whether to do so or not is determined as appropriate depending on the characteristics required of the first layer to be formed.

The amount of atoms (0, C, N) contained in the localized region is such that the maximum value of the distribution concentration C of atoms (0, C, N) is 5QQ at
omic ppm or more, preferably 3QQatomic
ppm or more, optimally 1000 atomic ppm
It is desirable to have a distribution state as described above.

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

Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, which are atoms belonging to group Ⅰ of the periodic table (hereinafter simply referred to as ``group Ⅰ'') that give P-type conductivity.
"group atoms". ), or atoms belonging to Group Ⅰ of the periodic table (hereinafter simply referred to as ``Group Ⅰ atoms'') that provide n-type conductivity are used. Specifically, as group Ⅰ atoms,
Examples include B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), etc., and particularly preferred are B and Ga. Group III atoms include P (phosphorus), As (arsenic),
Examples include Sb (antimony) and BI (bismane), but particularly preferred are r' and sb.

When the first layer of the present invention contains group (III) atoms or group (III) atoms, which are substances that control conductivity, it is determined whether they are 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 first layer, it is contained in the entire layer region of the photoreceptive layer. The content of atoms may be relatively small, usually I
0 ” ~ I X 103ato103ato,
Preferably 5×10−2 to 5×1(12)1(
12) ato ppm, optimally l Xl0-1-2
X 1 (12) 1 (12)ato ppm.

In addition, the group (I) atoms or group (V) atoms may be contained in a uniform distribution state in a part of the layer region in contact with the support, or the distribution humidity of the group (I) or group V atoms in the layer thickness direction may be When the content is high in concentration on the side in contact with the support, the layer region containing Group Ⅰ atoms or constituent layers containing Group Ⅰ atoms or layer regions containing Group 1N atoms in high concentration is It functions as a blocking layer.

In other words, when the group 1 atoms are contained, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the movement of electrons injected from the support side into the photoreceptor layer becomes more efficient. In addition, when the group (III) atoms are contained, when the free surface of the photoreceptive layer is charged to e-polarity, it is injected into the photoreceptor layer from the support side. The movement of holes can be more efficiently prevented.

In such cases, the content is relatively large,
Specifically, 30-5 X 10'atomic pp
m, preferably 50 to I x 10' atomic
ppm, optimally I x 10” to 5 x 1031
03ato ppm. Furthermore, in order to efficiently exhibit the effect as the charge injection blocking layer, the layer thickness of the layer or layer region provided at the end portion on the side of the support containing group (I) atoms is t, and the layer thickness of the photoreceptive layer is t. When the thickness is T, t/
It is desirable that the relationship T≦0.4 holds true, and more preferably that the value of the relational expression is 0.35 or less, most preferably 0.3 or less. Further, the layer thickness t of the layer or layer ridge region is generally 3X10-3 to 10μ, preferably 4X10-3 to 8μ, and optimally 5X1
It is desirable to set it to 0-3~5μ.

The amount of group (III) atoms or group (III) atoms contained in the second layer is relatively large on the support side, and decreases from the support side toward the second layer side, and A typical example of distributing Group II atoms or Group V atoms so that the amount is relatively small or substantially close to zero near the side end face is as follows: oxygen atom,
At least one of a carbon atom or a nitrogen atom
The present invention can be explained using examples similar to those shown in FIGS. 16 to 24, which illustrate the case of containing one or more of the following, but the present invention is not limited to these examples.

As shown in the examples shown in FIGS. 16 to 24, the first layer has a portion with a high distribution concentration C of group (III) atoms or group (III) atoms on the side closer to the support, and If, on the side of the layer closer to the second layer, the distribution concentration C has a portion of fairly low concentration or a portion of concentration close to substantially zero, the group Alternatively, by providing a localized region where the distribution concentration of group (III) atoms is relatively high, preferably by providing the localized region within 5μ from the interface position in contact with the support surface, the group (iii) atoms or The above-mentioned effect that the layer region in which the distribution concentration of group (I) atoms is high forms the charge injection blocking layer is more effectively achieved.

As mentioned above, regarding the distribution state of Group ■ atoms or Group ■ atoms,
Although the effects of each have been described individually, in order to obtain a light-receiving member having characteristics that can achieve the desired purpose, the distribution state of these Group 1 II atoms or Group Ⅰ atoms and the content in the first layer are important. It goes without saying that the amounts of group (I) atoms or group (I) atoms to be used may be appropriately combined as necessary. For example, when a charge injection blocking layer is provided at the end of the first layer on the support side, a substance that controls conductivity contained in the charge injection blocking layer is added to the first layer other than the charge injection blocking layer. It may contain a substance that controls conductivity of a polarity different from the polarity, or it may contain a substance that controls conductivity of the same polarity in an amount much smaller than that contained in the charge injection blocking layer. You can force it.

Furthermore, in the light-receiving member of the present invention, as a constituent layer provided at the end on the support side, instead of the charge injection blocking layer,
A so-called barrier layer made of an electrically insulating material can also be provided, or both the barrier layer and the charge injection blocking layer can be constituent layers. Examples of materials constituting such a barrier layer include inorganic electrically insulating materials such as Al2O3, SiO□, and Si3N4, and organic electrically insulating materials such as polycarbonate.

Second layer The second layer 103 of the light-receiving member of the present invention is a layer provided on the above-mentioned first layer 1 (12) and has a free surface 104, that is, a surface layer. Amorphous silicon containing at least one of atoms or nitrogen atoms in a uniform distribution [hereinafter referred to as "a-3i"
(0,C,N) (H.

X) Written as J. ].

The purpose of providing the second layer 103 in the light receiving member of the present invention is to
The purpose is to improve moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability, etc. The purpose of these is to add oxygen atoms, carbon atoms, or This is achieved by containing at least one nitrogen atom.

Further, in the light receiving member of the present invention, the first layer 1 (12
) and the amorphous material constituting the second layer 103 each have a common constituent atom, silicon atoms, so that chemical formation occurs at the interface between the first layer 1 (12) and the second layer 103. Stability can be ensured.

The second layer 103 contains oxygen atoms, carbon atoms, and nitrogen atoms in a uniformly distributed state, and as the amount of these atoms contained increases, the above-mentioned properties improve. However, too much will reduce the layer quality and the electrical and mechanical properties. For this reason, the content of these atoms is usually 0.0 (11 to 90 atoms).
mic%, preferably l −9Qatomic%, optimally 10 to 80 atomic%.

It is desirable that the second layer also contain at least one of hydrogen atoms or halogen atoms, and the amount of hydrogen atoms (H) contained in the second layer, or the amount of halogen atoms (X), or hydrogen The sum of the amounts of atoms and halogen atoms (H+X) is usually 1 to 40 atomic%, preferably 5 to 3Q atomic%, optimally 5 to 25 atomic%.
Let it be mic%.

The second layer 103 must be carefully formed to obtain the desired properties. In other words, a substance whose constituent atoms are silicon atoms, at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, or in addition, hydrogen atoms and/or halogen atoms, is determined by the content of each constituent atom and other preparations. Depending on the conditions, the morphology can range from crystalline to amorphous, the electrical properties can range from conductivity to semiconductivity to insulating properties, and the photoelectric properties can range from photoconductive to non-photoconductive properties. , it is important to select the content of each constituent atom, production conditions, etc. so that the second layer 103 having desired characteristics depending on the purpose can be formed.

For example, when the second layer 103 is provided with the main purpose of improving electrical voltage resistance, the amorphous material constituting the second layer 103 has a remarkable electrically insulating behavior under the usage conditions. Form. In addition, when the second layer 103 is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the amorphous material constituting the second layer 103 has the above-mentioned degree of electrical insulation. Although it alleviates it to some extent,
It is formed to have a certain degree of sensitivity to the irradiating light.

Further, in the present invention, the layer thickness of the second layer is also one of the important factors for efficiently achieving the purpose of the present invention, and is determined as appropriate depending on the intended purpose. However, the amount of oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms to be contained in the layer, or the characteristics required for the second layer, must be determined based on mutual and organic relationships. There is. Furthermore, it is also necessary to consider economic efficiency, which also takes into account productivity and mass production. For this reason, the layer thickness of the second layer is usually 3 x 10" to 30 µm, more preferably 4 x 10" to 20 µm, particularly preferably 5 x 10" to 20 µm.
x10-3 to 10μ.

By having the above-described layer structure, the light-receiving member of the present invention can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when laser light, which is light, is used as a light source, it is possible to significantly prevent the appearance of interference fringe patterns in formed images due to interference phenomena, and to form extremely high-quality visible images.

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 is fast, and also exhibits extremely excellent electrical, optical, photoelectric properties, electrical voltage resistance, and use environment characteristics.

In particular, when applied as a light-receiving member for electrophotography, it has no influence of residual potential on image formation, has stable electrical characteristics, has high sensitivity, and has a high signal-to-noise ratio. It has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

Next, a method for forming the photoreceptive layer of the present invention will be explained.

The amorphous material constituting the photoreceptive layer of the present invention is deposited by a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blasting method. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the light-receiving member to be manufactured. The glow emission method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the receiving member and it is easy to introduce carbon atoms and hydrogen atoms together with silicon atoms. is suitable.

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

In order to form a photoreceptive layer composed of a-3iGe (H,X) by the glow discharge method, silicon atoms (S
i) a raw material gas for supplying Si that can supply a raw material gas for supplying Si that can supply germanium atoms (Ge);
A hydrogen atom (■]) or/and a halogen atom (X) capable of supplying a hydrogen atom (I1) or/and a halogen atom (X)
A raw material gas for supply is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber to cause the gas to flow onto the surface of a predetermined support that has been placed at a predetermined position. , a-3iGe (H,X).

The substance that can serve as the raw material gas for supplying Si is S.
Gaseous or gasifiable silicon hydride (silanes) such as iH,,5i2H,,5i3H6,5I4I-Ilo, etc.
Of these, SiH and 5i2H are particularly preferred from the viewpoint of ease of handling during layer formation work and good Si supply efficiency.

In addition, the substances that can be the raw material gas for supplying Ge include GeH4, Ge2H6, Ge3H8, Ge4H, o
,Qe,H1□,Ge6H,,,Ge7H,6,Ge,
Germanium hydride in a gaseous state or gasified state such as H, 8, Ge, H2O, etc. can be used. In particular, GeH4, Ge2H, and Ge3H are preferred from the viewpoint of ease of handling during layer formation work and good Ge supply efficiency.

Furthermore, there are many halogen compounds as substances that can serve as the raw material gas for supplying halogen atoms, such as halogen gas, halogen compounds, interhalogen compounds, halogen-substituted silane derivatives, etc. A gasifying compound can be used. Specifically, halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF3, BrF3,
BrF, , IF, , IF7, I (J, IBr etc. 7
・Interlogen compounds, and S i F4.5i2F",
, S 1C44, S 1Br4, etc.) and silicon rogens.

When forming a silicon compound containing a halogen atom as described above in a gaseous state or that can be gasified by a glow discharge method as a raw material gas, use silicon hydride gas as a raw material gas for supplying Si atoms. This is particularly effective since it is possible to form a layer composed of a-3i containing no-rogen atoms on a predetermined support without any modification.

When forming a photoreceptive layer using the glow discharge method, basically silicon halide is used as a raw material gas for supplying Si, germanium hydride is used as a raw material for supplying Ge, and Ar
, 1-I2, 1-1e, etc. are introduced into the deposition chamber at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. A photoreceptive layer is formed on a support,
In order to make it easier to control the content of hydrogen atoms (1-1), which is extremely effective in controlling electrical or photoelectric properties, it has been necessary to Raw material gases can also be mixed. As the gas for supplying hydrogen atoms, hydrogen gas or 8iI-I4
．． Si□l-16, S i , H,,5i4f-t,
A silicon hydride gas such as O is used. In addition, as a gas for supplying hydrogen atoms, HF, f(Cd, HBr, HI
Halides such as SiH2F2, SiH, I2, S
1H2c12.5iHCd3.5iH2Br2.5iH
When a gaseous or gasifiable substance such as halogen-substituted silicon hydride such as Br is used, it is effective because hydrogen atoms (H) are introduced simultaneously with the introduction of halogen atoms (X).

a-8iGe (H,X) by sputtering method
To form a photoreceptive 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. Do by doing.

When forming a photoreceptive layer using the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in a deposition boat as evaporation sources, respectively, and the evaporation sources are This can be done by heating and evaporating by a resistance heating method or an electron beam method (E, 13. method), and passing the flying evaporated material through a desired gas plasma atmosphere.

In both the sputtering method and the ion blasting 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 Hz or the above-mentioned gases such as hydrogenated silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. What is necessary is to form a plasma atmosphere of the following gases. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are effective, but in addition, HF, HCd, HB
r, HI etc. (I Hydrogen Genide, S t N2 F2,
S mountain 2I2.5iH2C12, SiHCg5.5iH2
Halogen-substituted silicon hydrides such as Br2.5iHEr3, and GeHF3, GeH2F2, Ge1 (3F, Ge
H(J3, GeH2C12, QeI-1, C71!, G
eI-IBr,, GeN2Br2, GeH3Br,
Hydrogenated germanium halides such as GeHI, GeN2I2, GeH,I, GeF4. GeCl4. Ge
Br4%GeI4. GeF2, GeC12, GeBr2
Gaseous or gasifiable substances such as kermanium halides, GeI2, etc., can also be used as effective starting materials.

In a preferred example of the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms contained in the first layer constituting the photoreceptive layer to be formed. (H+X) is preferably 0. (11-40 a
tomic%, more preferably 0.05 to 30 a to
It is desirable that the amount is mic%, most preferably 0.1 to 25 atomic%.

To form a photoreceptive layer composed of amorphous silicon containing tin atoms (hereinafter referred to as ra-8iSn(H,X)J) using a glow discharge method, a sputtering method, or an ion blating method. is the above a
-3iGe (H,
n) By using it in place of the starting material for supply and incorporating it in the layer to be formed in a controlled amount.

Substances that can serve as raw material gas for supplying tin atoms (Sn) include tin hydride (5nH4) and SnF2.5nF.
4,5nC12,5nC14, SnBr2, SnBr
4. A gaseous or gasifiable substance such as tin halide such as SnI2.8nI can be used,
When tin halide is used, it is particularly effective because a layer composed of a-3i containing halogen atoms can be formed on a predetermined support.

Among them, 5nC114 is preferable from the viewpoint of ease of handling during layer construction work and good Sn supply efficiency.

When 5nC14 is used as a starting material for supplying tin atoms (Sn), in order to gasify it, solid 5nC14 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.

Using a glow discharge method, a-3iGe (H,X), a-8ig containing oxygen atoms, carbon atoms, or nitrogen atoms
n (H,X) or a-S 1GeSn (H,X
) or a part of the layer region, the above-mentioned a-8iGe (H,X) or/and a-8iSn
(H.

During the formation of a layer consisting of atoms (0, C.

N) The starting material for introduction is a-8iGe (I(,X)
or/and a-8iSn (H,

As a starting material for such introduction of atoms (0, C, N), most gaseous substances or substances that can be gasified have at least atoms (0, C, N) as constituent atoms. can be used.

Specifically, as starting materials for introducing oxygen atoms (0), for example, oxygen ((12)), ozone C05), -nitrogen oxide (NO), nitrogen dioxide (NO,), -nitrogen dioxide (N2
0), nitrogen sesquioxide < N, 0. ), nitrogen tetroxide (
N20. ), nitrogen sesquioxide (N20.), nitrogen trioxide (No3), silicon atom (Sl) and oxygen atom (0
) and a hydrogen atom (H) as constituent atoms, for example, disiloxane (H3Si08iH3), trisiloxane (1
Examples of starting materials for introducing carbon atoms (C) include methane (CH,), ethane (C2H
6), propane (C3H8), n-buta7 (n-C4
Saturated hydrocarbons having 1 to 5 carbon atoms such as H, o8 < methane (C, H1□), ethylene (C2H4), propylene (C8
H,), butene-1 (C,H,), butene-2 (C,H
8), Isojchin (C4Ha), Henfon (Ca
Ethylene hydrocarbons having 2 to 5 carbon atoms such as Hlo), acetylene (C2H2), methylacetylene (C3H,),
Examples include acetylenic hydrocarbons having 2 to 4 carbon atoms such as butyne (C4H,), and examples of starting materials for introducing nitrogen atoms (N) include nitrogen (N2), ammonia (Nl-
H3), hydrazine (H2NNH2), hydrogen azide (H
Ns ), ammonium azide (NH4N, ), nitrogen trifluoride (F,N), nitrogen tetrafluoride (14N), and the like.

In addition, atoms (0, C) can be prepared by sputtering.

a-8iGe(H,X) containing N), a-3iS
n (H.

X) or a-S 1GeSn (H, In addition to starting materials that can be solidified, examples of starting materials that can be solidified include Sin, Si3N, carbon black, and the like. These can be used in the form of targets such as Si.

A -5iGe (H,X) or/and a5iGe (H,
isn (H,X) or a part of the layer region, the above a-8iGe(H,X) or/
and a-8ign (H,X) When forming a layer consisting of a-8iGe (H, 8ign
This is done by using them together with the starting materials for (H,

Specifically, starting materials for introducing group (III) atoms include B2H,, B, H, o, B, H,, B
,H,,,B,I-I,. , B , H, □, B6
Examples include boron hydrides such as H14, boron halides such as BF3, BCI, and BBr. In addition, klc13
, GaCl3, Ga (CB3) 2, InC11s,
TlC133 and the like can also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, hydrogen ratios such as PH3, P2H, etc., PI-
(,I, PI!”8, PF3, Pc1s, PCl,
, PBr, , PBr, , PI3, and other halogen north neighbors are mentioned. In addition, AsH3, AsF, , AsCl3
．． AsBr, , AsF5.5bH1, SbF3,
SbF, , 5bC63, 5bCl, , BiH3,
B1Cd5, B113r, etc. may also be mentioned as effective starting materials for the introduction of Group V atoms.

Amorphous silicon containing at least one of an oxygen atom, a carbon atom, or a nitrogen atom is produced using a glow discharge method, a sputtering method, or an ion blating method.

To form the second layer 103 composed of a-8i (0,C,N) (H,X), a-3i (0,C,N
)(H,X) to form a-8iGe (H,X) or/
and a-8iSn (H,X) layer structure first
+7) Proceed in the same manner as when forming layers.

For example, in order to form a layer or a layer region containing oxygen atoms by a glow discharge method, a raw material gas containing silicon atoms (Si) and a raw material gas containing oxygen atoms (0) are used as necessary. Depending on the situation, a raw material gas containing hydrogen atoms (H) or halogen atoms (X) may be mixed at a desired mixing ratio, or silicon atoms (Sl) may be used.
A raw material gas having constituent atoms and a raw material gas having oxygen atoms (0) and hydrogen atoms (H) are mixed at a desired mixing ratio.
) and silicon atoms (Si).
, an oxygen atom (0), and a hydrogen atom (H) as constituent atoms can be mixed and used.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (0) as constituent atoms.

The starting material for introducing oxygen atoms may be any gaseous material containing oxygen atoms as a constituent atom or a gasified material that can be gasified.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (0□), ozone (03), -nitrogen oxide (NO),
Nitrogen dioxide (No2), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide < N204)
, nitrogen sesquioxide (N20.), nitrogen trioxide (NOl),
For example, disiloxane (H) whose constituent atoms are silicon atoms (Si), oxygen atoms (0), and hydrogen atoms (H)
lS i O81I-I3), trisiloxane (H3S
Examples include lower siloxanes such as iO81H20S 1H8).

To form a layer containing oxygen atoms by sputtering, a single crystal or polycrystalline Si wafer or a Si
This can be carried out by sputtering a wafer containing O2 waenourethane or a mixture of Si and 5in2 in various gas atmospheres.

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

Alternatively, by using Si and SiO□ as separate targets, or by using a single mixed target of Si and SiO2, at least hydrogen atoms (H )
Or/and by sputtering in a gas atmosphere containing halogen atoms (X) as constituent atoms.

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

Further, for example, in order to form a second layer containing carbon atoms by the glow release method, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing carbon atoms (C) as constituent atoms, If necessary, a raw material gas containing hydrogen atoms (1-i) and/or halogen atoms (X) may be mixed at a desired mixing ratio, or silicon atoms (
A raw material gas whose constituent atoms are Si) and a raw material gas whose constituent atoms are carbon atoms (C) and hydrogen atoms (H) are mixed at a desired mixing ratio.
A raw material gas whose constituent atoms are silicon atoms (Si) and silicon atoms (S
i), a raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms is mixed;
A raw material gas containing Si) and hydrogen atoms (■ () as constituent atoms and a raw material gas containing carbon atoms (C) as constituent atoms are mixed and used.

Si is effectively used as such raw material gas.
SiH4, S1□I-I, whose constituent atoms are and
S i3H,,,Si,H,. etc.: y (5il
silicon hydride gas such as ane), saturated hydrocarbons having 1 to 4 carbon atoms, containing C and H as constituent atoms, 2 carbon atoms, etc.
-4 ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, the saturated hydrocarbon is methane (CH,)
, ethane (C2H6), propane (C3H8), rope tough (n -Cd(,o), penta7 (C,H,□
), :I-ethylene hydrocarbons include ethylene (
C2H,), propylene < C3H6), butene-1 (
C,H,), butene-2 (C4H,), isobutylene (
C4I (,), pentene (C5H+o), and acetylenic hydrocarbons.

Acetylene (C2H2), Methylacetylene (C3H
, ), butyne (C4H6), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, 5
Examples include alkyl silicides such as i(CHs)<, Si (C2H,)4. In addition to these raw material gases, H
Of course, H2 can also be used as a source gas for four people.

To form the second layer composed of a-8iC(H,X) by sputtering, single-crystal or polycrystalline S
i wafer or C (graphite) wafer or Si
Sputtering is performed using a wafer containing a mixture of C and C as a target and sputtering them in a desired gas atmosphere.

For example, when using a Si wafer as a target, the source gas for introducing carbon atoms, hydrogen atoms, and/or halogen atoms may be Ar,
The gas may be diluted with a diluent gas such as He, introduced into a deposition chamber for sputtering, and a gas plasma of this gas may be formed to sputter a Si wafer.

In addition, although Si and C are used as separate targets, or when used as a mixed target of Si and C, hydrogen atoms or /
The raw material gas for introducing halogen atoms may be diluted with a diluent gas if necessary, and introduced into a deposition chamber for sputtering to form gas plasma and perform sputtering. As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method described above can be used as is.

Furthermore, in order to form a second layer made of amorphous silicon containing nitrogen atoms by the glow discharge method, for example, a raw material gas containing silicon atoms (Si) and a nitrogen atom (N) as constituent atoms are used. A raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms is used by mixing them at a desired mixing ratio. ) and a raw material gas containing nitrogen atoms (N) and hydrogen atoms (H) at a desired mixing ratio can be used.

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

The starting material for introducing nitrogen atoms may be any gaseous substance containing at least nitrogen atoms or a gasified substance that can be gasified.

Specifically, starting materials for introducing nitrogen atoms include nitrogen (N2) and ammonia (NH3), which have a nitrogen atom as a constituent atom or a nitrogen atom and a hydrogen atom as constituent atoms.
, hydrazine (H2NNH2), hydrogen azide (HN3)
, nitrogen such as ammonium azide (NH4N3), and nitrogen compounds such as nitrides and azides. In addition, nitrogen trifluoride (F, N), nitrogen tetrafluoride < F4
Examples include halogenated nitrogen compounds such as N2),
When using these halogenated nitrogen compounds, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced.

To form a layer region containing nitrogen atoms by the sputtering method, a monocrystalline or polycrystalline Si wafer, a Si, N4 wafer, or a wafer containing a mixture of Si and Si3N is used as a target. etc., by sputtering in a gas atmosphere.

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

Alternatively, Si, Si, and N4 may be used as separate targets, or by using a single mixed target of Si, Si, and N4, in an atmosphere of dilution gas as a sputtering gas, or at least Hydrogen atom (
This is accomplished by sputtering in a gas atmosphere containing H) or/and halogen atoms (X) as constituent atoms.

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

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. Alternatively, the content of Group V atoms, oxygen atoms, carbon atoms or nitrogen atoms, or hydrogen atoms and/or halogen atoms can be controlled by controlling the gas flow lid or This is done by controlling the gas flow rate ratio between each starting material for supplying atoms.

In addition, conditions such as the support temperature, gas pressure in the deposition chamber, and discharge power during the formation of the first layer and the second layer are important factors in order to obtain a light-receiving member with desired characteristics. It is selected as appropriate, taking into consideration 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 contained in the first layer and the second layer, consideration must be given to the type and amount of the atoms to be contained. It is also necessary to consider and make a decision.

Specifically, when forming the second layer consisting of a-3i (H, ,
Particularly preferably, it is 50 to 250C. The gas pressure inside the deposition chamber is normally 0. (11 to I Torr, particularly preferably 0.1 to 0.5 Torr.Also, the discharge power is usually 0.005 to 50 W, but
More preferably 0. (11 to 30 w7.H, particularly preferably 0.(11 to 20 W/d).

When forming a first layer consisting of a-8iGe (H,X), or forming a first layer consisting of a-8iGe (H, In this case, the support temperature is usually 50 to 350C.
However, it is more preferably 100 to 300C, and more preferably 100 to 300C.

The gas pressure inside the deposition chamber is usually 0. (11~5To
rr, preferably 0.0 (11 to 3 Tor
r, particularly preferably 0.1 to 1 Torr. Further, the discharge power is usually 0.005 to 50 W/7, but preferably 0.005 to 50 W/7. (11 to 30 W/i, particularly preferably 0.(11 to 20 W/cy).

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, germanium atoms and/or tin atoms, atoms (0, C', N) contained in the photoreceptive layer of the present invention
, Group ■ atom or Group ■ atom, or hydrogen atom or /
In order to make the distribution state of the halogen atoms uniform, it is necessary to keep the above-mentioned conditions constant when forming the photoreceptive layer.

In addition, in the present invention, when forming the photoreceptive layer, germanium atoms, tin atoms, atoms (
In order to form a photoreceptive layer having a desired distribution state in the layer thickness direction by changing the distribution concentration of group (0, C, N) or group (III) atoms or group (III) atoms in the layer thickness direction, a glow discharge method is used. If used, the gas flow rate when introducing into the deposition chamber the gas of the starting material for introducing germanium atoms and/or tin atoms, atoms (0, C, N), or group II atoms or group V atoms. is formed by appropriately changing the rate of change according to a desired rate of change while keeping other conditions constant. Specifically, in order to change the gas flow rate, the opening of a predetermined needle valve provided in the middle of the gas flow path system is gradually opened by some commonly used method, such as manually or by an externally driven motor. All you have to do is perform an operation to change it. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

In addition, when forming the photoreceptive layer using a sputtering method, germanium atoms or tin atoms, atoms (0, C, N
), or to form a desired distribution state in the layer thickness direction by changing the distribution concentration in the layer thickness direction of group m atoms or group , germanium atom or tin atom, atom (0, C, N)
Alternatively, a group (I) atom or a starting material for introducing a group (I) 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 a desired rate of change.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 13, but the present invention is not limited thereto.

In each example, the photoreceptive layer was formed using a glow discharge method. FIG. 5 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

25 (12) in the figure. 2503.2504.2505.
The gas cylinder No. 2506 is sealed with raw material gas for forming each layer of the present invention, and as an example,
For example, 25(12) is SiF4 gas (purity 99.9
99%) cylinder, 2503 contains B, H, diluted with H2.
Gas (purity 99,999%, hereinafter referred to as B2 He/H2
It is abbreviated as ) cylinder, 2504 is CH4 gas (purity 99.
999%) cylinder, 2505 is Ge F4 gas (purity 9
9.999%) cylinder, 2506 is an inert gas (H
e) It is a cylinder.

And 2506' is a sealed container containing 5nCd.

In order to flow these gases into the reaction chamber 25 (11), the valves 2522 to 25 of the gas cylinders 25 (12) to 2506 are used.
26. Check that the leak valve 2535 is closed, and also check the inflow valves 2512 to 2516 and the outflow valve 2.
517 to 2521, confirm that the auxiliary valves 2532 and 2533 are open, and first open the main valve 253.
4 is opened and the interior of the reaction chamber 25 (11) is vented. Next, an example of forming the first layer and the second layer on the vacuum Al cylinder 2537 will be described below.

First, 5IF4 gas from gas cylinder 25 (12), B2H0/Hz gas from gas cylinder 2503, gas cylinder 2
CH4 gas from 504, GeF from gas cylinder 2505
.

Valve 2522.2523.2524.2 for each gas
Open 525 and outlet pressure gauge 2527.2528.25
29.2530 to I Kf/crl, gradually opening the inlet valves 2512.2513.2514.2515 and mass 70 controllers 2507.2508.
2509.2510. Subsequently, the outflow valves 2517.2518.2519.2520 and the auxiliary valves 2532 are gradually opened to supply the gas to the reaction chamber 25 (11).
flow into the world.

At this time, SiF4 gas flow rate, Ge F, gas flow rate, C
Outflow valve 2517.2518.2519 so that the H4 gas flow rate, 82H6/H2 gas flow rate ratio is the desired value.
．． 2520, and also adjust the opening of the main valve 2534 while checking the reading of the vacuum gauge 2536 so that the pressure inside the reaction chamber 25 (11) reaches the desired value. After confirming that the temperature is set in the range of 50 to 400 C, the power source 2540 is set to the desired power to generate a glow discharge in the reaction chamber 25 (11).
S i F, gas, GeF according to a flow rate change rate line designed in advance using a microcomputer (not shown).

First, a layer 1 (12)' containing silicon atoms, germanium atoms, carbon atoms, and boron atoms is formed on the base cylinder 2537 while controlling the gas flow rates of gas, CH, gas, and B2H, /H2 gas.

At the stage when layer 1 (12)' has been formed to the desired layer thickness, the outflow valves 2518 and 2520 are completely closed and the glow discharge is continued in the same manner, except for changing the discharge conditions as necessary. A layer 1 (12)'' that does not substantially contain germanium atoms can be formed on (12)'.

In this way, after forming the first layer 1 (12) having layer 1 (12)' and layer 1 (12)'' in order from the support side, the second layer 103 is formed on the first layer 1 (12). To form,
By the same operation as above, for example, SiF4 gas and C
H, gas, He, Ar, H2 as necessary.
The reaction chamber 25 is diluted with a diluent gas such as
11 and generates a glow discharge according to desired conditions.

Needless to say, all the outflow valves other than the outflow valves for the gases required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer flows into the reaction chamber 25 ( 11, from the outflow pulps 2517 to 2521 to the reaction chamber 25 (in order to avoid remaining in the gas piping leading to the inside of 11, the outflow pulps 2517 to 2521 are closed, the auxiliary pulps 2532 and 2533 are opened, and the main pulp 253 is
4 is fully opened and the system is once evacuated to a high vacuum, as necessary.

In addition, when containing tin atoms in the first layer and using a gas containing 5nC14 as a starting material, solid 5nC contained in 2506'
14 is heated using a heating means (not shown), and an inert gas cylinder 2 such as Ar or He is placed in the 5nC14.
Inert gas such as Ar, He, etc. is blown in from 506 and bubbled. The generated 5nC14 gas is
F4 gas, GeF, gas, CH4 gas, B2H6,"I
(Flow into the reaction chamber using the same procedure as for 2 gases, etc.)

Test Example Using a SUS stainless steel rigid true 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 Figure 6 above. Ta.

When we investigated the relationship between the diameter R' of a true sphere, the fall height h, and the curvature and width of the trace depression, we found that the curvature R and width of the trace depression are as follows.
It was confirmed that it is determined by conditions such as the diameter R' of the true sphere and the falling height h. In addition, the pitch of the dents (the density of the dents and the pitch of the unevenness) is determined by the rotational speed of the cylinder,
It has been confirmed that it is possible to adjust the pitch to a desired pitch by controlling the number of rotations, the amount of fall of the rigid true sphere, etc.

Example 1 The surface of an aluminum alloy cylinder was treated in the same manner as in the test example, and a cylindrical Al support (cylinder holder 1) having D and - shown in the upper column of Table 1A was prepared.
(11-106) was obtained.

Next, a light-receiving layer was formed on the AI support (Cylinder 1 (11-106)) using the manufacturing apparatus shown in FIG. 5 under the conditions shown in Table 1B below.

These light-receiving members were subjected to image exposure by irradiating laser light with a wavelength of 7 gQmm and a spot diameter of 80 μm using the image exposure apparatus shown in the figure, followed by development and transfer to obtain images. The occurrence of interference fringes in the obtained image was as shown in the lower column of Table 1A.

Note that FIG. 26(A) is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 26(B) is a schematic side view schematically showing the entire exposure apparatus. In the figure, 26 (11 is a light receiving member, 26 (12) is a semiconductor laser, 2603
(c) fθ lens; 2604 indicates a polygon mirror.

Next, as a comparison, we will show an aluminum alloy cylinder (YA 107) whose surface was treated with a conventional diamond tool.
) (Diameter 6Qmm, length 298mm.

Using an uneven pitch of 100 μm and an uneven depth of 3 μm,
A light receiving member was produced in the same manner as described above.

When the obtained light-receiving member was observed under an electron microscope, it was found that the support surface, the layer interface of the light-receiving layer, and the surface of the light-receiving layer were parallel to each other. Using this light-receiving member, images were formed in the same manner as described above, and the obtained images were evaluated in the same manner as described above. The results were as shown in the lower column of Table 1A.

Example 2 All procedures were carried out in the same manner as in Example 1 except that the photoreceptive layer was formed according to the layer forming conditions shown in Table 2B.

A light-receiving layer was formed on an Al support (cylinder A1 (11 to 107).
The gas flow rates of GeF4 gas and GeF4 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 f was as shown in the lower column of Table 2A.

Examples 3-11 Al support of Example 1 (cylinder & 103-106)
A light-receiving member was produced in the same manner as in Example 1 except that a light-receiving layer was formed thereon according to the layer formation conditions shown in Tables 3 to 11. In addition, in Examples 3 to 11, the flow rate of the gas used during the first layer formation 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, the boron atoms contained in the first layer were introduced into the gradation layer as much as about 200 ppm.

Image formation was performed on the obtained light-receiving member in the same manner as in Example 1.

No interference fringes were observed in any of the images obtained.
And it was of extremely good quality.

[Summary of effects of the invention]

By having the above-described layer structure, the light-receiving member of the present invention can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. Even when laser light, which is light, is used as a light source, it is possible to significantly prevent the appearance of interference fringe patterns in formed images due to interference phenomena, and to form extremely high-quality visible images.

In addition, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers, and has a high photoresponsiveness. It exhibits excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment properties.

In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing an example of the light-receiving member of the present invention, and FIGS. 2 and 3 are diagrams for explaining the principle of preventing the generation of interference fringes in the light-receiving member of the present invention. FIG. 2 is a partially enlarged view showing that interference fringes are prevented from occurring in a light-receiving member in which unevenness is formed by spherical trace depressions on the surface of the support, and FIG. 3 is a diagram showing a conventional surface. FIG. 3 is a diagram showing that interference fringes occur in a light-receiving member in which a light-receiving layer is deposited on a regularly roughened support. FIGS. 4 and 5 are schematic diagrams for explaining the uneven shape of the support surface of the light-receiving member of the present invention and the method for producing the uneven shape. FIG. 6 is a diagram schematically showing 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, and FIG. 6(A) is a front view. , 6th
(B) is a longitudinal sectional view. Figures 7 to 15 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the first layer of the present invention, and Figures 16 to 24 are diagrams showing the distribution of oxygen atoms in the first layer of the present invention. , is a diagram showing the distribution state of carbon atoms or nitrogen atoms, or group (III) atoms or group (III) atoms in the layer thickness direction,
In each figure, the vertical axis represents the layer thickness of the first layer, and the horizontal axis represents the distribution concentration of each atom. FIG. 5 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. Second
FIG. 6 is a diagram illustrating an image exposure device using laser light. The nth to audience diagrams are diagrams showing changes in the gas flow rate in the first layer formation of the present invention, where the vertical axis shows the layer thickness of the first layer, and the horizontal axis shows the gas flow rate of the used gas. . Regarding FIGS. 1 to 3, 100... Light-receiving member 1 (11... Support 1 (
12), 2(11.3(11...first layer 1(12)
'...Layer 1 (12) containing at least one of germanium atoms or tin atoms'...Layers 103 and 2 (12) containing neither germanium atoms nor tin atoms
). 3(12)...second layer 104, 203.303
...Free surfaces 204, 304... Regarding the interface between the first layer and the second layer in Figure 4.5, 4(11, 5(11・I・Support 4(12).5(
12)...Support surface 403, 503.5o3<...
Rigid true spheres 404, 504...Regarding the spherical depressions in FIG.
5... Rigid true sphere 606... Ball feeder 607... Vibrator 608... Collection tank 609
...Ball feeding device 610...Cleaning device 611.
...Cleaning liquid reservoir 612...Cleaning liquid collection tank 613.
...Regarding the drop opening in Figure 5, 25 (11... Reaction chambers 25 (12) to 2506...
Gas cylinder 2506'-5nC14 airtight container 2507-2511... Mass flow controller 2512-2516... Inflow pulp 2517-2521... Outflow pulp 2522-2526... Pulp 2527-2
531...Pressure regulator 2532, 2533...Auxiliary pulp 2534...Main pulp 2535...Leak pulp 2536...Vacuum gauge 2537...
Base cylinder 2538...Heating heater 2539
...Motor 2540...About high frequency power supply Figure A,

Claims (12)

[Claims] (1) An amorphous material containing, on a support, silicon atoms, at least one of germanium atoms or tin atoms, and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms. an amorphous layer containing silicon atoms and atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms that are different from the atoms contained in the first layer; A light-receiving member comprising a light-receiving layer having a second layer made of a material, wherein the first layer contains at least one of germanium atoms or tin atoms, and a layer containing germanium atoms. and a layer containing no tin atoms in order from the support side, and the surface of the support has an uneven shape formed by a plurality of spherical trace depressions. . (2) The light-receiving member according to claim (1), wherein the second layer contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniformly distributed state. (3) The light-receiving member according to claim (1), wherein the first layer contains a substance that controls conductivity. (4) The light-receiving member according to claim (1), wherein the first layer has as one of the constituent layers a charge injection blocking layer containing a substance that controls conductivity. (5) The light-receiving member according to claim (1), wherein the first layer has a barrier layer as one of the constituent layers. (6) The light-receiving member according to claim (1), wherein the plurality of uneven shapes provided on the surface of the support are uneven shapes formed by spherical trace depressions having the same curvature. (7) The light-receiving member according to claim (1), wherein the plurality of uneven shapes provided on the surface of the support are uneven shapes formed by spherical trace depressions having the same curvature and the same width. (8) Claim No. 1, wherein the uneven shape on the surface of the support is an uneven shape due to trace depressions of the rigid true spheres obtained by naturally falling a plurality of rigid true spheres onto the surface of the support body. The light-receiving member described in 2. (9) Claim No. 1, wherein the uneven shape on the surface of the support is an uneven shape due to the vestigial depressions of the rigid true spheres obtained by dropping rigid true spheres of approximately the same diameter from approximately the same height. The light-receiving member described in 2. (10) The curvature R and width D of the spherical trace depression are expressed by the following formula: 0.
The light-receiving member according to claim 1, which has a value satisfying 035≦D/R. (11) The light-receiving member according to claim (10), wherein the width of the spherical trace depression is 500 μm or less. (12) Claim No. 1, wherein the support is a metal body.
) The light-receiving member according to item 1.