JPS62115454A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To obtain a photoreceptive member matchable well with semiconductor laser by providing a proper structure to a photoreceptive layer contg. a-Si as the principal component. CONSTITUTION:A photoreceptive layer having a photosensitive layer 102 of an amorphous material contg. Si and at least one between Ge and Sn and a surface layer 103 is formed on a support 101. The surface layer 103 has a multilayered structure consisting essentially of a wear resistant layer as the top layer and an inner antireflection layer. The surface of the support 101 has a finely uneven cross-sectional shape formed by the superposition of secondary peaks on primary peaks. The photoreceptive layer on the surface of the support 101 has at least one pair of nonparallel interfaces within a short range and may nonparallel interfaces are arranged in at least one direction is a plane perpendicular to the thickness direction of the layer.

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,
The present invention relates to a light-receiving member sensitive to electromagnetic waves such as infrared rays, X-rays, R-rays, etc.

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

[Description of prior art]

A method for recording digital image information as an image.

As a method, 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 or, if necessary, transferred. Methods of recording images that perform processes such as fixing are known, and in particular, in image forming methods using electrophotography, small and inexpensive Hθ-No lasers or semiconductor lasers (usually 650 to 820 nm) are used as lasers.
Generally, image recording is performed using a light emitting device having an emission wavelength of .

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 ra-8iJ (abbreviated as ra-8iJ) has been attracting attention.

However, in the light-receiving member, if the light-receiving layer is a single-layer a-8i layer, in order to maintain its high photosensitivity and ensure a dark resistance of 10120 m or more required for electrophotography, It is necessary to structurally contain hydrogen atoms, halogen atoms, or boron atoms in addition to these in a specific amount range in a controlled manner in the layer, so various conditions must be strictly controlled during layer formation. There are considerable limitations on the design tolerances of the light-receiving member, such as the need to control the Proposals have been made to improve such design tolerance problems by making it possible to effectively utilize the high light sensitivity even if the dark resistance is low to some extent. That is, for example, JP-A-54-121743, JP-A-57-4 (153), JP-A-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 apparent increase in 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 cause interference.

This interference phenomenon causes the so-called,
This appears as an interference fringe pattern and causes image defects. Particularly when forming a half-tone image with high gradation, a positive 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. .

This point will be explained below with reference to the drawings.

FIG. 6 shows the light weight o incident on a certain layer constituting the light-receiving layer of the light-receiving member, the reflected light R1 reflected at the upper interface 602,
Reflected light R2 reflected at the lower interface 601 is shown.

There, the average layer thickness of a layer is d, the refractive index is n, and the wavelength of light is λ, and the layer thickness of a certain layer is 2.
na=mλ (m is an integer, reflected light strengthens each other) and 2na
=(m+)λ (m is an integer, reflected light weakens each other) The amount of absorbed light and transmitted light of a certain layer changes depending on which of the following conditions is met. That is, in the case where the light-receiving member has a two or more layer (multilayer) structure as shown in FIG.
The interference effect shown in the figure occurs, resulting in the state shown in Figure 7, and as a result, each interference acts synergistically to create an interference fringe pattern, which is transferred as it is. There is a problem in that interference fringes corresponding to the interference fringe pattern appear on the visible image transferred and fixed on the member, resulting in a defective image.

As a measure to solve this problem, (a) the surface of the support is diamond-cut to provide unevenness of ±500A to ±10,000A to form a light scattering surface (for example, JP-A-58
(Refer to Japanese Patent Application Laid-Open No. 162975), (method of providing a light absorption layer by subjecting the surface of the BL aluminum support to black alumite treatment, or dispersing carbon, coloring pigments, and dyes in a resin (for example, Japanese Patent Laid-Open No. 16297- 165845), (C) A method of providing a light-scattering anti-reflection layer on the surface of the support by applying a satin-like alumite treatment to the surface of the aluminum support or providing fine grain-like irregularities by sandblasting (for example, (see Japanese Patent Laid-Open No. 57-16554), 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 the method (a), a large number of irregularities of a specific size 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. This results in a substantial decrease in resolution.

Regarding method (1)), in black alumite treatment,
Complete absorption is impossible, and the light reflected on the support surface remains. In addition, when a colored pigment dispersed resin layer is provided, when forming the a-8i layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed light-receiving layer is significantly deteriorated. There are problems such as damage caused by plasma during the formation of the -8i layer, which reduces the original absorption function and adversely affects the subsequent formation of the a-8i layer due to deterioration of the surface condition.

Regarding the method (C), as shown in FIG. It enters the interior and becomes transmitted light with a weight of l. The transmitted light weight 1 is the support 8
On the surface of 01, part of it is scattered and becomes diffused light Kl, 2, K3, etc., and the remaining part is specularly reflected and becomes reflected light R2, and part of it becomes emitted light R3. However, the emitted light R3 is a component that interferes with the reflected light R1 and remains in any case, so the interference fringe pattern still does not disappear completely.

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 801 so that multiple reflections do not occur inside the light-receiving layer, but in such a case, on the contrary, the light-receiving layer The light diffuses and causes halation, which ultimately reduces resolution.

In particular, in a multilayered light-receiving member, even if the surface of the support 901 is irregularly roughened, as shown in FIG.
Reflected light R2 on the surface of layer 902, reflected light R on the second layer
1. The specularly reflected lights R3 on the surface of the support 901 interfere with each other, resulting in an interference fringe pattern according to the thickness of each layer of the light-receiving member. Therefore, in a light-receiving member having a multilayer structure, the support 9
It is impossible to completely prevent interference fringes by irregularly roughening the 01 surface.

Furthermore, when the surface of the support is irregularly roughened by methods such as sandblasting, the degree of roughness varies greatly between lots, and even within 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, when the surface of the support is simply roughened regularly, as shown in FIG.
0 (along 13, the photoreceptive layer 1002 is deposited,
The sloped surface of the unevenness of the support 1001 and the sloped surface of the unevenness of the light-receiving layer 1002 are parallel to each other as shown by 10 (13', 1004').

Therefore, the relationship 2ndl=mλ or 2na1-(m+-)λ is established for the incident light in that part, which becomes a bright part or a dark part, respectively. In addition, in the entire photoreceptive layer, the thickness of each of the layer thicknesses d1, d2, d3, and d4 of the photoreceptive layer is uneven, so that the maximum of the differences is 1 or more. appears.

Therefore, simply by regularly roughening the surface of the support 1001, it is not possible to completely prevent the occurrence of interference fringes.

Furthermore, even when a multilayered light-receiving layer is deposited on a support whose surface is regularly roughened, regular reflection on the surface of the support as explained in connection with the single-layered light-receiving member shown in FIG. In addition to the interference between the light and the reflected light on the surface of the light-receiving layer, interference due to the reflected light at the interface between each layer is added, so that the degree of interference fringe pattern development becomes more complicated than that of a single-layered light-receiving member.

Furthermore, the problem of interference caused by reflected light in such a multilayered light-receiving member also relates to its surface layer. That is, as is clear from the above, if the thickness of the surface layer is not uniform, an interference phenomenon will occur due to reflected light at the interface between the surface layer and the photosensitive layer in contact with it, causing damage to the light receiving member. It impairs function.

By the way, the state in which the layer thickness of the surface layer is non-uniform is not only suppressed during the formation of the surface layer, but also caused by abrasion, particularly partial abrasion, during use of the light-receiving member. Particularly in the latter case, as described above, not only will an interference pattern appear, but also sensitivity changes and sensitivity unevenness will occur in the entire light-receiving member.

Attempts have been made to make the surface layer as thick as possible in order to eliminate these surface layer-related problems, but in this case, in addition to creating a factor that increases the residual potential, On the contrary, the layer thickness unevenness increases, and a light-receiving member having such a surface layer has factors that cause problems such as changes in sensitivity and unevenness in reading when it is formed. In other words, the initial image may not be worth adopting.

[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-8i, 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 made of a-8i, 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 8i.

Still another object of the present invention is to be suitable for image formation using coherent monochromatic light, to be free of interference fringes and spots during reversal development even after repeated use over a long period of time, and to be free from image defects and image formation. To provide a light-receiving member having a light-receiving layer made of a-8i, capable of obtaining a high-quality image with no blur, high density, clear halftones, and high resolution. It is in.

[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 includes a photoreceptive layer having a photosensitive layer made of an amorphous material containing K, silicon atoms, and at least one of germanium atoms and tin atoms on a support, and a surface layer. The surface layer has a multilayer structure having at least an abrasion resistant layer on the outermost shell and an antireflection layer inside, and the surface of the support has a main peak and a subpeak superimposed on the surface layer. The light-receiving layer on the surface of the support has at least one pair of non-parallel interfaces within a short range, and the non-parallel The present invention relates to a light-receiving member in which a large number of such interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction.

By the way, the findings obtained by the present inventors as a result of extensive research are summarized below.

That is, in a light-receiving member equipped with a light-receiving layer having a photosensitive layer and a surface layer on a support, the surface layer has at least an abrasion-resistant layer on the outermost layer and an anti-reflection layer on the inside. In the case of a multilayer structure having a multilayer structure, reflection of incident light at the interface between the surface layer and the photosensitive layer is prevented, and interference caused by layer thickness unevenness during formation of the surface layer and/or layer thickness unevenness due to abrasion of the surface layer is prevented. This solves the problem of uneven patterns and sensitivity.

Further, while forming an uneven shape on the surface of the support that is smaller than the resolution required for the light receiving member, in a minute part (hereinafter referred to as "short range") within one period of the uneven shape, If at least one pair of non-parallel interfaces is provided and a large number of non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction, the problem of interference fringes appearing during image formation can be solved. , and in that case, the vertical cross-sectional shape of the convex portion of the unevenness provided on the support surface is
controlled non-uniformity of the layer thickness of each layer formed within a short range, good adhesion between the support and the layer provided directly on the support, or even desired electrical contact. In order to ensure this, it is desirable to have a shape in which a sub-peak is superimposed on a main peak.

Incidentally, the latter finding 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 an example of the layer structure of the light-receiving member according to the present invention. In this example, the surface of the support 1010 is
It has a cross-sectional shape in which a main peak and a sub-peak are superimposed to form a plurality of minute irregularities. layer 1
(It is equipped with a light-receiving layer formed from 13.

FIGS. 2 to 4 are diagrams for explaining how the problem of interference fringes is solved in the light-receiving member of the present invention.

FIG. 2(A) shows the photosensitive layer of the light-receiving member shown in FIG.
This is an enlarged view of a part of the surface layer, and Figure 2 (B) is a diagram showing the brightness in the same part.In the figure, 202
is a photosensitive layer, 2 (13 is a surface layer, 204 is a free surface, 2 (
15 indicates the interface between the photosensitive layer and the surface layer. Second (A
) As shown in the figure, the layer thickness of the surface layer 2 (13) changes continuously from d21 to d22 within the short range, so the free surface 204 and the interface 2 (15) have different slopes. Therefore, coherent light such as a laser beam incident within this short range L causes interference in the short range t, producing a minute interference fringe pattern.However, the interference occurring in the short range t The stripes are formed because the size of the short range t is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit.
It never appears in the image. Although it is unlikely, even if a situation were to appear in the image, it would be below the resolution of the naked eye, so there would be virtually no problem.

On the other hand, as shown in FIG. 3 (in the figure, 302 is a photosensitive layer, 3 (13 is a surface layer, 304 is a free surface, and 3 (15 is an interface between the photosensitive layer 302 and the surface layer 3 (13)). When the interface 3 (15) between the photosensitive layer 302 and the surface layer 3 (13) and the free surface 304 are non-parallel (see Figure 3(A)), the reflected light R for the incident light amount o, Since the traveling direction is different from that of the emitted light R3, the interface 3 (15 and the free surface 30
4 are parallel (see Figure 3(B)),
The degree of interference is reduced. That is, even if interference occurs, the third (
C) As shown in the figure, the degree of interference is smaller when a pair of interfaces are in a non-parallel relationship than when the pair of interfaces are parallel, so the difference in brightness of the interference fringe pattern is It becomes negligibly small, and as a result, the amount of incident light is averaged out.

This means that the surface layer 2 (1
3 is macroscopically non-uniform, that is, the layer thickness a23, R24 of the surface layer at any two different positions.
The same is true even when dz34 R2, and the amount of light incident on the entire layer region is uniform as shown in FIG. 2(D).

The case where the photosensitive layer and the surface layer are laminated on the support has been described above, but when the photosensitive layer of the light receiving member of the present invention has a multilayer structure, for example, as shown in FIG. [Even in the case where the photosensitive layer 402 consisting of two constituent layers 402' and 402'' and the surface layer 4 (13) are laminated on the support, the reflected light R is
1, R2, R3, Hiki and R5 are present, but 402'
, 402'' and 4(13), a phenomenon occurs in which the amount of incident light is averaged as explained with reference to FIG.

Moreover, the interface of each layer within the short range acts as a kind of slit, where a diffraction phenomenon occurs.

Therefore, interference in each layer appears as a cumulative effect of interference due to the difference in layer thickness and interference due to diffraction at the layer interface.

Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer, so in the photoreceptive member of the present invention, as the number of layers constituting the photosensitive layer increases, the influence of interference becomes more It can be prevented.

The support for the light-receiving member of the present invention having the above-described configuration based on the above experimentally confirmed facts has a surface having minute irregularities smaller than the resolving power required for the light-receiving member, and The cross-sectional shape of is such that a sub-peak is superimposed on a main peak. - When using a support having such a surface shape, the light that has passed through the photoreceptive layer interferes with the photoreceptive member on which the photoreceptive layer is formed by being reflected on the surface of the support. This effectively prevents the image from becoming striped, leading to the formation of an excellent image.

Regarding the surface of the support of the light-receiving member of the present invention, the size t of one cycle of the suitable uneven shape is the spot diameter of the irradiated light L.
If so, it is necessary that the relationship t≦L holds.

Further, the light-receiving layer of the light-receiving member of the present invention includes a photosensitive layer and a surface layer, and the photosensitive layer is made of an amorphous material containing silicon atoms and at least one of germanium atoms and tin atoms. and particularly preferably contains a silicon atom (Sl), at least one of a germanium atom (Ge) or a tin atom (Sn), and a hydrogen atom (H) containing at least one of a halogen atom (X). Amorphous material [hereinafter referred to as “a-8i
It is written as (Ge, 5n)(H,X)J. ], or oxygen atom (0), carbon atom (C) and nitrogen atom (
a-8 containing at least one selected from N)
i(Ge, 5n)(H,X) [Hereafter, [a-8i(G
e, 5n) (0, C, N) (JX) Written as J. ]
Further, a substance for controlling conductivity can be contained as necessary. The layer may have a multilayer structure, and particularly preferably has a charge injection blocking layer containing a substance that controls conductivity as one of the constituent layers, and/or constitutes a barrier layer. It has as one of the layers.

Further, the surface layer includes silicon atoms, at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms,
Preferably, an amorphous material further containing at least one of a hydrogen atom or a halogen atom [hereinafter referred to as
[Denoted as a-8i (0, C, N) (H, X) J.

] or at least one selected from inorganic fluorides, inorganic oxides, and inorganic sulfides, and the surface layer has a wear-resistant layer on the outermost shell and an anti-reflection layer on the inside. It has a multilayer structure including at least one layer.

In the light-receiving member of the present invention, the support having the above-described surface shape and the light-receiving layer formed on the support are closely related. That is, the light-receiving member of the present invention has a photosensitive layer and a surface layer laminated on a support, and the photosensitive layer has a layer that prevents interference, as will be described in detail later. For the purpose of forming a localized region (i.e., a charge blocking layer) containing a relatively large amount of a substance controlling the property;
Or/and it is desirable to form a barrier layer at the end of the photosensitive layer on the support side, and in the light-receiving member of the present invention having such a structure, a plurality of interfaces formed by a plurality of layers are formed on the support. In the light-receiving member of the present invention, at least one pair of non-parallel interfaces exists within the short range.

In order to achieve the object of the present invention more effectively, the difference in layer thickness in the short range t, for example, the difference between d21 and "22 in FIG. When the wavelength is λ, it is desirable to satisfy the following formula: The upper limit of the difference in layer thickness is preferably 0.1 μm to 2 μm.
m, more preferably 0.1 μm-1.5ttm1, optimally 0.2am to lttm.

As mentioned above, in the light-receiving member of the present invention, the layer thickness of each layer is controlled so that at least any two interfaces are in a non-parallel relationship within a short range, but as long as this condition is satisfied. , there may be interfaces in a parallel relationship. However, in that case, take any two positions of the parallel interfaces, let the difference in layer thickness at those positions be Δt, and let the wavelength of the irradiated light be λ,
When the refractive index of the layer is n, it is desirable to form the layer or layer region so as to satisfy the following formula:

Regarding the preparation of the photosensitive layer and surface layer of the present invention, in order to efficiently achieve the above-mentioned object of the present invention, it is necessary to accurately control the layer thickness at an optical level, so the glow discharge method, Vacuum deposition methods such as sputtering and ion blasting are commonly used, but in addition to these, optical CV
D method, thermal CVD method, etc. can also be adopted.

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

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention, in which 100 is the light-receiving member, 101 is the support, 102 is the photosensitive layer, 1 (13 indicates the surface layer, and 104 indicates the free surface.

Support The support 101 in the light-receiving member of the present invention has surface irregularities smaller than the resolving power required for the light-receiving member, and the cross-sectional shape of the irregularities is such that a sub-peak is superimposed on a main peak. It is something that has a shape.

The uneven shape provided on the surface of the support can be formed by chemical methods such as chemical etching and electroplating, physical methods such as vapor deposition and sputtering, and mechanical methods such as lathe processing. To make it easier,
Mechanical processing methods such as lathes are preferred.

For example, when machining the surface of a support with a lathe, a tool with a 7-shaped cutting edge is fixed at a predetermined position on a cutting machine such as a milling machine or a lathe, and the cylindrical support is designed in advance according to the desired results. By regularly moving in a predetermined direction while rotating according to a specified program, the surface of the support can be accurately cut to create the desired uneven shape.
Formed by pitch and depth. The linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The helical structure of the protrusion may be a double or triple helical structure, or a crossed helical structure.

Alternatively, a linear structure along the central axis may be introduced in addition to the spiral structure.

Moreover, in order to efficiently achieve the object of the present invention, the uneven shape is preferably arranged regularly or periodically. Furthermore, in addition to this, in order to efficiently scatter incident light in one direction, the uneven shape is either symmetrical (FIG. 5(A)) or asymmetrical (FIG. 5(A)) about its main peak.
It is preferable that they be unified as shown in Figure (B)). but,
In order to increase the degree of freedom in controlling the processing of the support, it is preferable for both to be present together.

In the present invention, the dimensions of the irregularities provided on the surface of the support in a controlled manner are set in such a way that the object of the present invention can be achieved as a result, taking into account the following points.

That is, firstly, the a-8i layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the layer quality changes greatly depending on the surface condition.

Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the a-8i layer.

Second, if the free surface of the photoreceptive layer has extreme irregularities,
Cleaning cannot be completed completely after image formation.

Further, when performing blade criminage/gu, there is a problem that the blade becomes damaged quickly.

After considering the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, we found that:
The pitch of the recesses on the surface of the support is usually 0.3 μm to 50 μm.
It is desirable that the thickness is 0 μm, preferably 1 μm to 200 μm, more preferably 5 μm to 50 μm.

Further, the maximum depth of the recess is preferably 061 μm to 5 μm.
1 more preferably 0.3 μm to 3 μm 1 optimally 0.6
It is preferable that the thickness is from μm to 2 μm. When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the recesses (or linear protrusions) is preferably 1 degree to 15 degrees, more preferably 3 degrees to 15 degrees. , optimally between 4 degrees and 10
It is desirable to set it as a degree.

The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, At,
Cr%Mo, Au, Nb5Ta, V.

Examples include metals such as T1, pt, pb, and alloys thereof.

As an electrically insulating support: 1. l? Examples include films or sheets of synthetic resins such as IJ ester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramics, and paper. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is provided on the conductively treated surface side.

For example, if it is glass, the surface may contain Cr, At,
Cr, MO, Au1, Nb, Ta, V, Ti, pt
lpa, In2O3, 5n02, Engineering To (Engineering n2 (13
Conductivity is imparted by providing a thin film consisting of NiCr, At, Ag1, etc. in the case of a synthetic resin film such as a polyester film.
Pb, Zn, Ni, Au, Cr, Mo, Cr, Nb
A thin film of metal such as , Ta, V1Tt%Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, S/Q tuttering, etc.
Alternatively, the surface is laminated with the metal to impart conductivity to the surface. The shape of the support can be any shape such as cylindrical, belt-like, plate-like, etc., but depending on the purpose,
The shape can be determined as desired. For example, if the light-receiving member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferable to use an endless belt or a cylindrical shape for continuous high-speed copying. The thickness of the support is appropriately determined so as to form a desired light-receiving member, but if flexibility is required as a light-receiving member, the thickness should be determined within a range that allows the support to fully perform its function. can be made as thin as possible. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

Photosensitive layer In the light-receiving member of the present invention, a photosensitive layer 102 is provided on the above-mentioned support 101, and the photosensitive layer has a-
8i(Ge, 5n)(H,X) or a-8i(Ge, 5
n) (0, C, N) (H, X), and preferably can further contain a substance that controls conductivity.

The halogen atom (X) contained in the photosensitive layer is as follows:
Specific examples include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. Hydrogen atoms (H) contained in the photosensitive layer 102
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 40 a
atomic %, preferably 5-3Q atomic %
It is desirable that this is done.

Furthermore, in the light-receiving member of the present invention, the layer thickness of the photosensitive layer is
One of the important factors for efficiently achieving the object of the present invention is the need to pay sufficient attention when designing the light-receiving member so that the desired characteristics are imparted to the light-receiving member. It is usually 1 to 100μ, preferably 1 to 80μ.
μ, more preferably 2 to 50 μ.

Incidentally, the purpose of containing germanium atoms and/or tin atoms in the photosensitive layer of the light-receiving member of the present invention is mainly to improve the absorption decay characteristics of the light-receiving member on the long wavelength side.

That is, by containing germanium atoms and/or tin atoms in the photosensitive layer, the light-receiving member of the present invention exhibits various excellent properties, especially those in the visible light region. It has excellent photosensitivity and fast photoresponsiveness to light in the entire range of wavelengths from short wavelengths to relatively short wavelengths. This is particularly noticeable when a semiconductor laser is used as a light beam.

In the photosensitive layer of the present invention, even if germanium atoms and/or tin atoms are contained in the entire layer region,
Alternatively, it may be contained in a part of the layer region in contact with the support. In the latter case, the photosensitive layer has a layer structure in which a constituent layer containing germanium atoms and/or tin atoms and a constituent layer containing neither germanium atoms or/and tin atoms are laminated in this order from the end on the support side. It will have the following. In both cases where germanium atoms and/or tin atoms are contained in the entire layer region or only in a part of the layer region, germanium atoms and/or tin atoms are contained in the layer or layer region. , may be contained in a uniformly distributed state, or may be contained in a non-uniformly distributed state.

(Here, the uniform distribution state refers to germanium atoms or/
This means that the distribution concentration of tin atoms and tin atoms is uniform in the plane direction parallel to the support surface of the photosensitive layer, and is also uniform in the layer thickness direction of the photosensitive layer. This means that the distribution concentration of atoms and/or tin atoms is uniform in the plane direction of the photosensitive layer parallel to the support surface, but is non-uniform in the layer thickness direction of the photosensitive layer. ) In the photosensitive layer of the present invention, a layer containing relatively large amounts of germanium atoms and/or tin atoms in a uniform distribution is provided particularly at the end on the support side, or a layer containing a relatively large amount of germanium atoms and/or tin atoms in a uniformly distributed state is provided, or the free surface side is also supported. It is desirable to contain germanium atoms and/or tin atoms so that they are more distributed toward the body side, and in this case, the distribution concentration of germanium atoms and/or tin atoms is extremely increased at the end on the support side. As a result, when a long wavelength light source such as a semiconductor laser is used, the long wavelength light is almost completely absorbed by the constituent layers or layer regions near the free surface of the photoreceptive layer.
Since the light is absorbed substantially completely in the constituent layers or layer regions of the light-receiving layer that are in contact with the support, interference due to reflected light from the support surface is prevented.

As mentioned above, in the photosensitive layer of the present invention, germanium atoms and/or tin atoms can be uniformly distributed in the entire layer or some of the constituent layers, or the germanium atoms and/or tin atoms can be distributed uniformly in the whole layer or some of the constituent layers. It is also possible to distribute the atoms continuously and non-uniformly in the layer thickness direction. Below, we will introduce some typical examples of continuous and non-uniform distribution states in the layer thickness direction, using germanium atoms as an example. This will be explained with reference to FIGS. 11 to 19.

11 to 19, the horizontal axis shows the distribution concentration C of germanium atoms, the vertical axis shows the layer thickness of the entire photosensitive layer or a part of the constituent layer in contact with the support, and tB shows the photosensitive layer on the support side. The position of the end face of the layer, tT, indicates the end face on the surface layer side opposite to the support side, or the position of the interface between the constituent layer containing germanium atoms and the constituent layer not containing germanium.

That is, the photosensitive layer containing germanium atoms is formed from the tB side toward the tT 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 explaining the process.

FIG. 11 shows a first typical example of the distribution state of germanium atoms contained in the photosensitive layer in the layer thickness direction.

In the example shown in FIG. 11, from the interface position tB where the photosensitive layer containing germanium i atoms is formed and the layer contacts the interface position tB to the position tl, the distribution concentration C of germanium atoms is the concentration C1. Germanium atoms are contained in the photosensitive layer while taking a certain value, and from the position t1, the concentration C
2 to the interface position tT.

At the interface position tT, the distribution concentration C of germanium atoms is
is essentially zero. (Here, substantially zero means that the amount is less than the detection limit.) In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms is from the concentration C3 to the position tT from position 1B. A distribution state is formed in which the concentration gradually and continuously decreases to a concentration C4 at the position tT.

In the case of FIG. 13, from position tB to position t2, the distribution concentration C of germanium atoms is constant at the concentration C5, and gradually and continuously decreases between position t2 and position 1. At position tT, the distribution concentration C is substantially zero.

In the case of FIG. 14, the distribution concentration C of germanium atoms is gradually and continuously reduced from the position tB to the position t3, starting from the concentration C6, and from the position t3, it is rapidly and continuously reduced to the position tT. is essentially zero.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a constant value of concentration C7 between the positions tB and t4, and the distribution concentration C is zero at the position tT. . Between the position t4 and the position 1T, the distribution concentration C is linearly decreased from the position t4 to the position tT.

In the example shown in FIG. 16, the distribution concentration C is at the position t
From B to position t5, the concentration C8 takes a constant value, and at position t
From position 5 to position tT, the distribution state decreases linearly from the concentration C9 to the concentration C10.

In the example shown in FIG. 17, from position tB to multiple positions 1T, the distribution concentration C of germanium atoms is the concentration C1l.
It is reduced more linearly and reaches zero.

In FIG. 18, from position tB to position t6, the distribution concentration C of germanium atoms decreases linearly from concentration C12 to concentration C13, and from position t6 to position 1.
An example is shown in which the concentration C13 is kept at a constant value between C13 and T.

In the example shown in FIG. 19, the distribution concentration C of germanium atoms is a concentration C14 at a position tB, and is slowly decreased from this concentration C14 until reaching a position twa, and near a position t7, It is rapidly decreased to position 1. In this case, the concentration is assumed to be CX5.

Between position t7 and position t8, the decrease is rapid at first, and then slowly and gradually decreased until position t8.
The density becomes C16, and between position t8 and position t9,
The concentration is gradually decreased to reach the concentration C17 at position t9. Between position t9 and position tT, the concentration is reduced from C17 to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 11 to 19, some typical examples of the distribution state of germanium atoms and/or tin atoms contained in the photosensitive layer in the layer thickness direction, the light receiving member of the present invention In this case, 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, there is a part where the distribution concentration C is significantly lower than that on the support side. It is desirable that the photosensitive layer has a distribution state of atoms and/or tin atoms.

That is, the photosensitive layer constituting the light receiving member in the present invention is
Preferably, as described above, it is desirable to have a localized region containing germanium atoms and/or tin atoms at a relatively high concentration on the support side.

In the light-receiving member of the present invention, the localized region can be explained using the symbols shown in FIGS.
It is desirable to provide it within 5μ from B.

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

Whether the localized area is a part or all of the layer area is determined by
It is determined as appropriate according to the characteristics required of the photoreceptive layer to be formed.

The localized region contains germanium atoms or/
And as 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 IQQQ atom with respect to silicon atoms.
ic I) l) m or more, more preferably 5QQQ ato
mic ppm or more, optimally lXl0'atomic
It is desirable that the layers be formed so as to achieve a distribution state of ppm or more.

That is, in the light-receiving member of the present invention, the photosensitive layer containing germanium atoms and/or tin atoms has a layer thickness of 5 μm or less from the support side (layer region of the layer 5 μm from tIl).
It is preferable that the distribution density be formed such that the maximum value c max of the distribution concentration exists at .

In the light-receiving member of the present invention, the content of germanium atoms and/or tin atoms contained in the photosensitive layer must be determined as desired so as to efficiently achieve the object of the present invention, and usually is 1~6 X 10' atoms
ic ppm, preferably 10-3X10X
1 (15atOp:Pm, j rihot LahaI
X 102~2 X 10' atomic ppm.

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

In the photosensitive 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 non-uniform distribution state in the layer thickness direction. The state in which it is contained depends on the above-mentioned objectives and expected effects, and therefore the amount to be contained also differs.

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

In addition, when the purpose is to improve the adhesion between the support and the photosensitive layer, it may be contained uniformly in a part of the layer area at the support side end of the photosensitive layer, or it may be added to the support side end of the photosensitive layer. In this case, at least one selected from carbon atoms, oxygen atoms, and nitrogen atoms is contained in a distribution state such that the distribution concentration thereof is high; in this case, among the oxygen atoms, carbon atoms, and nitrogen atoms contained in the photosensitive layer. The amount of at least one selected from the following is set to a relatively large amount 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 to be contained in the photosensitive layer is determined, however, in addition to consideration of the properties required for the photosensitive layer as described above. It is determined by taking into account organic relationships such as the characteristics at the contact interface with the support, and usually 0.001 to 50 atomic
%, preferably 0.002-40 atomie%,
The optimum value is 0.0 (13 to 30 atomic %).

By the way, if it is contained in the entire layer area of the photosensitive layer, or if the ratio of the layer thickness of a part of the layer area to which it is contained is large in the layer thickness of the photosensitive layer, the above-mentioned upper limit of the amount to be included is less. be made into That is, in that case, for example, when the layer thickness of the layer region to be contained is τ of the layer thickness of the photosensitive layer, the amount to be contained is usually 3Q ato
mic% or less, preferably 20atOmiC or less,
Optimally, it is set to below IQ atomic %.

Next, the amount of at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms to be contained in the photosensitive layer of the present invention is relatively large on the support side, and from the end on the support side to the surface layer side. Some typical examples are cases where the distribution decreases toward the edge and becomes a relatively small amount or substantially close to zero near the edge on the surface layer side of the photosensitive layer. , and will be explained with reference to FIGS. However, the present invention is not limited to these examples. Hereinafter, at least one selected from carbon atoms, oxygen atoms, and nitrogen atoms will be referred to as "atoms (0, C,
N) Written as J.

In the fourth to fourth additions, the horizontal axis shows the distribution concentration C of atoms (0, C, N), the vertical axis shows the layer thickness of the photosensitive layer, tB shows the interface position between the support and the photosensitive layer, and tT The position of the interface between the photosensitive layer and the surface layer is shown.

The second figure shows atoms (0, C, N) contained in the photosensitive layer.
The first typical example of the distribution state in the layer thickness direction is shown. On the chain side, from the interface position tB between the support and the photosensitive layer containing atoms (0,C,N) to position 11, atoms (0,C,N)
, N) takes a constant value C□, and the position t
From 1 to the interface position tT with the surface layer, atoms (0, C, N
) decreases continuously from concentration C2, and at position tT, the distribution concentration of atoms (0, C, N) becomes (1
It becomes 3.

In another typical example shown in FIG. 21, the distribution concentration C of atoms (0, C, N) contained in the photosensitive layer is at the position t
The concentration decreases continuously from C4 to position tTK, and reaches C5 at position tT.

In the example shown in FIG.
, C, N) gradually and continuously decreases from the concentration C7, and at position tT, the distributed concentration C of atoms (0, C, N) becomes substantially zero.

In the example shown in FIG.
The distribution concentration C of C, N) becomes substantially zero.

In the example shown in FIG. U, the distribution concentration C of atoms (0, C, N) is at a constant concentration C9 between position tB and position t3, and between position t3 and position 1T,
The concentration decreases in a negative order function from the concentration C9 to the concentration C1o.

In the example shown in FIG. 5, the distribution concentration C of atoms (0, C, N) is the concentration C1l from position tB to position t4.
It is at a constant value from position t4 to position 1T [from the density C12 to the density C13, which decreases in a -dimensional function.

In the example shown in FIG. A, the distribution concentration C of atoms (0, C, N) decreases linearly from the concentration C14 to substantially zero from the position tB to the position tT.

In the example shown in Figure n, the distribution concentration C of atoms (0, C9N)
decreases from the position tB to the position t5VC in a -order function from the concentration C15 to the concentration C16, and at the position t5VC.
The concentration C16 is maintained at a constant value from to position tT.

Finally, in the example shown in FIG. 4, the distribution concentration C of atoms (0, C, N) is the concentration C1'7 at the position tB, and from the position tB to the position t6, the concentration C1'F starts from the concentration C1'F. It decreases slowly, then sharply decreases near position t6, and reaches the concentration C18 at position t6. Next, from position t6 to position t7, the concentration decreases rapidly at first, and then gradually decreases, and at position 1°, the concentration reaches C19. 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 t8 to position tT, the concentration C
It gradually decreases from 20 to essentially zero.

As shown in the examples shown in Figs. If the stone has a portion where the distribution concentration C is quite low or has a concentration substantially close to zero, atoms (0, C, N) are present at the end of the photosensitive layer on the support side. ) is provided, preferably a localized region having a relatively high distribution concentration of
By providing within μ, the adhesion between the support and the photosensitive layer can be improved even more efficiently.

The localized region may be all or a part of the layer region at the support side end of the photosensitive layer containing atoms (0, C, N 2 ); is determined as appropriate according to the characteristics required of the photosensitive layer to be formed.

The amount of atoms (0, C, N) contained in the localized region is:
The maximum value of the distribution concentration C of atoms (0, C, N) is 5QQ
Atomic ppm or more, preferably 800 ato
mic ppm or more, optimally 1QQQ atomic
It is desirable to have a distribution state in which the amount is ppm or more.

In the light-receiving member of the present invention, a substance for controlling photosensitive jK conductivity can be contained in the entire layer region or a part of the layer region in a uniformly or non-uniformly distributed state.

Examples of the substance that controls the conductivity include so-called impurities in the semiconductor field, and atoms belonging to group Ⅰ of the periodic table (hereinafter simply referred to as ``group Ⅰ'') that give P conductivity.
"group atoms". ), or atoms belonging to Group V of the periodic table (hereinafter simply referred to as "Group V atoms") that provide n-type conductivity are used. Specifically, as group Ⅰ atoms,
B (boron), At (aluminum), Ga (gallium)
, Indium (Indium), and Thallium (Tt), among which B and Ga are particularly preferred.

Group V atoms include P (phosphorus), AS (arsenic), and sb.
(antimony), B1 (bismane), etc., but particularly preferred are p and sb.

When the photosensitive layer of the present invention contains group (III) atoms or group (III) atoms, which are substances that control conductivity, whether to contain them in the entire layer region or in some layer regions will be described later. Thus, the amount to be included will vary depending on the purpose or expected effect.

That is, when the main purpose is to control the conductivity type and/or conductivity of the photosensitive layer, it is contained in the entire layer area of the photosensitive layer. The amount may be relatively small, usually I x 10-3
˜I×IQ” atomic ppm, preferably 5
ppm.

Optimally, I X IF1~'l X IQ" atom
ic 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 concentration of the group (II) or group V atoms in the layer thickness direction may be When it is contained at a high concentration on the side in contact with the support, a constituent layer containing such group (III) atoms or group V atoms or a layer containing a high concentration of group (III) atoms or group V atoms. The region is where it will function as a charge injection blocking layer. In other words, when the group Ⅰ 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 is made more efficient. In addition, when Group V atoms are contained, when the free surface of the photoreceptive layer is charged with polarity, it is injected into the photoreceptor layer from the support side. The movement of holes can be more efficiently blocked. In such a case, the content is relatively large, specifically, 30 to 5 X IQ' atomic
ppm, preferably u 50 to 1 x to'a
tomic ppm, optimally □IX 102~5
X 10" atomic ppm.Furthermore, in order to efficiently exhibit the effect of the charge injection and blocking layer, a layer or When the layer thickness of the layer region is t and the layer thickness of the photoreceptive layer is T, it is desirable that the relationship t/T≦0.4 holds true, and it is more preferable that the value of the relational expression be 0.4. It is desirable that the value be 35 or less, most preferably 0.3 or less.

Further, the layer thickness t of the layer or layer region is generally 3
10-3 to lOμ, preferably 4X to-
”~8μ, optimally 5×10−3~5μ.

Next, the amount of Group Ⅰ atoms or Group V atoms contained in the photosensitive layer is relatively large on the support side, decreases from the support side toward the surface layer, and near the interface with the surface layer. A typical example of distributing Group II atoms or Group V atoms such that the amount is relatively small or substantially close to zero is that oxygen atoms, carbon atoms, and nitrogen atoms are distributed in the photosensitive layer. This can be explained using an example similar to the rural example shown in FIG. 20, in which at least one selected from the following is included. However, the present invention
These examples are not intended to be limiting.

As shown in the examples shown in FIG. 20 to FIG.
If the distribution concentration C has a part with a high concentration C on the interface side with the surface layer, or a part with a concentration substantially close to zero, the part close to the support side has a part with a high concentration C. By providing a localized region where the distribution concentration of group (III) atoms or 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 above-mentioned effect that the layer region in which the distribution concentration of Group (1) atoms or Group V atoms is high forms a charge injection blocking layer can be achieved even more efficiently.

As mentioned above, regarding the distribution state of Group Ⅰ atoms or Group V 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 II atoms or group V atoms and the number of groups to be contained in the photosensitive layer are important. It goes without saying that the amounts of Group (2) atoms or Group V atoms may be used in appropriate combinations as necessary. For example, when a charge injection blocking layer is provided at the end of the photosensitive layer on the support side, the polarity of the substance that controls conductivity contained in the charge injection blocking layer is different from the polarity of the substance contained in the charge injection blocking layer in the photosensitive layer other than the charge injection blocking layer. The material may contain a substance that controls conductivity of the same polarity, or may contain a substance that controls conductivity of the same polarity in an amount that is much smaller than that contained in the charge injection blocking layer. .

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. Materials constituting such a barrier layer include At2(13, 5i02, Si, 3
Examples include inorganic electrical insulating materials such as N4 and organic electrical insulating materials such as polycarbonate.

Surface Layer The surface layer 1 (13) of the light-receiving member of the present invention is provided on the above-mentioned photosensitive layer 102 and has a free surface 104.

The surface layer 1 (13) reduces the reflection of incident light on the free surface 104 of the light-receiving member, increases transmittance, and improves the moisture resistance, continuous repeated use characteristics, electrical pressure resistance, and use environment characteristics of the light-receiving member. It is formed on the photosensitive layer 102 for the purpose of improving various properties such as durability and durability.The second layer is formed on the photosensitive layer 102 so that the layer formed with it has an excellent antireflection function. In addition to the requirement that the photoconductivity of the light-receiving member be not adversely affected, that the electrophotographic property, for example, the resistance be above a certain level, and that the liquid developable When using this method, conditions such as excellent solvent resistance and not deteriorating the various properties of the photosensitive layer that has already been formed are required. Examples that can be used include silicon atoms (Sl), at least one selected from oxygen atoms (0), carbon atoms (C), and nitrogen atoms (N), and preferably further hydrogen atoms (H) or halogens. Amorphous material containing at least one of atoms (X) [hereinafter referred to as [a-8i(0,C,N)(H,X
) Written as J. ] Or MgF2, AtaO
s, Zn8. TiO2, ZrO2, CeO2, CeF
3. At least one selected from inorganic fluorides, inorganic oxides, and inorganic sulfides such as AlF2 and NaF2 can be mentioned.

In the light-receiving member of the present invention, in order to solve the problem of interference patterns and sensitivity unevenness caused by uneven layer thickness of the surface layer, the structure of the surface layer is such that the outermost layer has a wear-resistant layer and the inner layer has a wear-resistant layer. It has a multilayer structure including at least an antireflection layer. That is, in the light-receiving member of the present invention in which the surface layer has a multilayer structure, a plurality of interfaces are generated within the surface layer, and reflections at each interface cancel each other out, so that the interface between the surface layer and the photosensitive layer is Since the reflection at the surface layer can be reduced, the conventional problem of changes in reflectance due to uneven thickness of the surface layer can be solved.

The wear-resistant layer (outermost layer) and the anti-reflection layer (inner layer) constituting the surface layer of the present invention each have a single-layer structure, as long as they are formed to satisfy the characteristics required for them. Needless to say, a multilayer structure of two or more layers may also be used.

In order to form the surface layer into such a multilayer structure, the layers constituting the wear-resistant layer (outermost layer) and the antireflection layer (inner layer) are formed to have different optical band gaps (101)t'). Specifically, the refractive index of the wear-resistant layer (outermost layer), the refractive index of the antireflection layer (inner layer), and the refractive index of the photosensitive layer on which the surface layer is directly provided are made to be different from each other.

The refractive index of the photosensitive layer is nl, the refractive index of the wear-resistant layer constituting the surface layer is nz, the refractive index of the antireflection layer is ns, the thickness of the antireflection layer is d, and the wavelength of the incident light is λ. By satisfying the following formula: % formula %) 2n3d=(-+m)λ (m represents an integer), the reflection at the interface between the photosensitive layer and the surface layer can be reduced to zero. can do.

In the above example, nl < ns < nz, but the layer is just one example and does not need to be limited to this, for example,
When the surface layer is composed of an amorphous material containing silicon atoms and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, the amount of oxygen atoms, carbon atoms, or nitrogen atoms contained in the surface layer is By making the abrasion layer and the antireflection layer different, the refractive index is made different. Specifically, if the photosensitive layer is made of a-8iH and the surface layer is made of a-8iCH, the amount of carbon atoms contained in the antireflection layer is equal to the amount of carbon atoms contained in the antireflection layer. By increasing the amount of atoms and increasing the refractive index nl of the photosensitive layer,
The refractive index n3 of the antireflection layer, the refractive index n2 of the wear-resistant layer, and the layer thickness d of the wear-resistant layer are each nx = 2.0 and ng = 3.5.
, n3=2.65, and d4755A. In addition, oxygen atoms, carbon atoms, or nitrogen atoms contained in the surface layer,
By making the wear-resistant layer and the anti-reflection layer different, each wear layer is formed of a-8iC(H,X), and the anti-reflection layer is formed of a-8iN(JX) or a-8iO(H). ,X)
It can be formed by

The wear-resistant layer and antireflection layer constituting the surface layer contain at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform distribution state;
As the amount of these atoms contained increases, the above-mentioned properties improve. However, if it is too large, the layer quality will deteriorate and the electrical and mechanical properties will also deteriorate. For this reason, the amount of these atoms contained in the surface layer is usually Q
, QQI ~9Q atomic $, preferably 1
~9Q atomic %, optimally lQ ~80 a
tomic%. Furthermore, it is desirable that the surface layer also contain at least either a hydrogen atom or a halogen atom.
), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is - usually 1 to 4
0 atomic %, preferably 5-30 atomic
c%, optimally 5-25 atomic%.

Furthermore, when the surface layer is composed of at least one selected from inorganic fluorides, inorganic oxides, and inorganic sulfides, the refractive index of each of the inorganic compounds and mixtures thereof exemplified below should be considered. , the photosensitive layer, the abrasion-resistant layer, and the antireflection layer each have a different refractive index, and are selected and used so as to satisfy the above-mentioned conditions. The refractive index of inorganic compounds and mixtures thereof is shown in parentheses. ZrO2(2,00), T102(
2,26), ZrO2/TiO2=6/1 (2,
(17)>, TlO2/zrO2= 3/1 (2,2
0), GeO2 (2,23), ZnS (2,24),
Atz (13 (1,63), CeF3 (1,60),
Al2O5/ Z r02 = 1/1 (1,68),
MgF2 (1°38). It goes without saying that these refractive indexes vary somewhat depending on the type of layer to be created, conditions, etc.

However, in the present invention, the layer thickness of the surface 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. It is necessary to determine the amount of oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms to be included in the layer, or the characteristics required for the surface layer, based on mutual and organic relationships. Furthermore, it is also necessary to consider economic efficiency, which also takes into account productivity and mass production.

For this reason, the thickness of the surface layer is usually 3XIO-3
~30μ, preferably 4 x 10-”~
The addition μ is particularly preferably 5×10 −3 to 10 μ.

The light-receiving member of the present invention has the above-described layer structure, so that it can solve all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon, and in particular, it 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 monochromatic light, is used as a light source, the appearance of interference fringes in the formed image due to interference phenomena can be significantly prevented, and a visible image of extremely high quality can be formed.

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. As a result, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear no-ft tones, 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 star/q scattering method, or an ion blating 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 discharge method is preferred because it is relatively easy to control the conditions for producing a light-receiving member with desired characteristics, and carbon atoms and hydrogen atoms can be easily introduced together with silicon atoms. Alternatively, a suture method is suitable.

Further, the glow discharge method and the star/Q stumbling method may be used together in the same apparatus system.

For example, in order to form a layer composed of a-81(H,X) by the glow discharge method, basically hydrogen atoms ( H) A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber. a-8i(H,X) on the support surface
form a layer consisting of

The raw material gas for supplying Si is Sin, 5i2
Examples include silicon hydride (silanes) in a gaseous state such as H,,513H8, Si, and Hl (1, etc.), which can be gasified.Especially, in terms of ease of layer formation work and good Si supply efficiency,
SiH4 and Si2H6 are preferred.

Furthermore, as the raw material gas for introducing the above-mentioned rhodan atoms, there are many rhodan compounds, such as evaporative halogen gas, rhodanide, inter-rhodan compounds, and halogen-substituted compounds. Gaseous or gasifiable rhodane compounds such as silane derivatives are preferred. Specifically, halogen gases such as fluorine, chlorine, bromine, and iodine, BrF
, C4F, C4F6, BrF5, BrF3, engineering Fwa, engineering CL, IBr, etc., and inter-rhodan compounds, and Si
Examples include silicon halides such as F4, Si□F, SiC, and 81Br4. When using the above-mentioned silicon rodanide in a gaseous state or which can be gasified, a layer composed of a-8i containing halogen atoms can be formed without using a separate raw material gas for S1 supply. It is particularly effective because it can form

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, HF, halides such as HC41HBr, Hl, SiH, 512H6, Si3H8, 514H1o, etc.
silicon hydride such as, or S 1H2F2, SiH2
Engineering 2, SiH2CLz, simc4. ．． 5iH2Br
It is possible to use gaseous or gasifiable materials such as halogen-substituted silicon hydride such as 2.5iHBrs,
When these raw material gases are used, it is possible to easily control the content of hydrogen atoms (I()), which is extremely effective in controlling electrical or photoelectric properties. , is effective.And when the above-mentioned No. Roge/hydrogen hydride or the above-mentioned ... Rodan-substituted silicon hydride is used.
- Hydrogen atoms (H) are introduced simultaneously with the introduction of Rodan atoms, which is particularly effective.

To form a layer consisting of a-8i(H,X) by reactive sputtering or ion blating,
For example, in the case of a sputtering method, in order to introduce halogen atoms, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as F2 or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. good.

For example, in the case of the reactive sputtering method, an S1 target is used, and gas for introducing halogen atoms and F2 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to create a plasma atmosphere. A layer of a-8i (JX) is formed on the support by forming and snogging the S1 target.

In order to form a layer composed of a-EtiGe (H,
A source gas for supplying Ge that can supply Ge) and a source gas for supplying hydrogen atoms (H) or/and halogen atoms (X) that can supply hydrogen atoms (H) or/and halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be depressurized, and a glow discharge is generated within the deposition chamber,
On the surface of a predetermined support that has been placed in a predetermined position in advance, a
A layer composed of -8iGe(H,X) is formed.

Substances that can be used as a raw material gas for supplying Si, a raw material gas for supplying halogen atoms, and a raw material gas for supplying hydrogen atoms include those used when forming the layer composed of the above-mentioned a-8i (H, X). What you have is used as is.

In addition, as substances that can be the raw material gas for supplying Ge, GeH, Ge2H6, Ge3H8, Ge4H1 (
,,Ge5H12,Ge6H1,,G%H16,Ge8
Germanium hydride in a gaseous state or in a gasified state such as H18, Ge9H20, etc. can be used. In particular, GeH, Ge2H6, and Ge3H8 are preferred from the viewpoint of ease of handling during single-layer production work, good Ge supply efficiency, and the like.

To form a layer composed of a-8iGe (H, etc., by sputtering in a desired gas atmosphere.

a-8iGe(H,
In the case of forming a layer composed of Heating method or electron beam method (E, B.

This can be carried out by heating and evaporating the evaporated material using a method such as the above 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 F2 or the above 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, HCz.

Hydrogen halides such as HBr1H, SiH2F2, S
iH, H engineering. , 5iH2C42, 5iHCLS, 5i
Halogen-substituted silicon hydrides such as H2Br2.5iHBr3, and GeHF3, G eH2F2, GeH3F, G
eHCt3, GeH2C1:2, GeH3C4SGeH
Br3, GeF2Br2, GeH3Br, GeH 3
, GIEIH2 Engineering. , (Hydrogenated germanium halide etc. of MIH3 engineering etc., GeF, GeC, GeBr, etc.)
Gaseous or gasifiable materials such as germanium halides such as Ge, GeF2, GaCl2, GeBr2, Ge2, etc. can also be used as effective starting materials.

A photoreceptive layer composed of amorphous silicon containing tin atoms (hereinafter referred to as [a-9ign (I(,X)j)) is formed using a glow discharge method, a sputtering method, or an ion silating method. In order to do this, when forming the layer composed of a-5iGe (H, This is carried out by controlling the amount of the compound in the layer to be formed.

Substances that can serve as raw material gas for supplying the tin atoms (Sn) include tin hydride (SnH,) and SnF2.5n.
F4.5nCz2, SnCmu, 5nEr2.5nBr,
, Sn Engineering 2, Sn Engineering.

When using tin halides, a-8i containing halogen atoms on a predetermined support can be used.
This is particularly effective since it is possible to form a layer consisting of: Among these, SnC is preferred from the viewpoint of ease of handling during layer formation work and good Sn supply efficiency.

When SnC is used as a starting material for supplying tin atoms (Sn), in order to gasify it, solid SnC is heated and Ar is added.

It is preferable to blow in an inert gas such as He or the like and perform pulling using the inert gas, and the gas thus generated is introduced at a desired gas pressure into a deposition chamber whose interior is kept at a reduced pressure.

a-8i (H,
To form a layer composed of an amorphous material in which i(Ge, 5n) (H, ,
a-9i(H,X) or a-8i(Ge, sn)
When forming a layer of (H+ Substances can be expressed as a-8i(H,X) or a-8i(
This is done by using them in conjunction with the starting materials for the formation of Ge,5n)(H,X) to control their inclusion in the layer being formed.

For example, using the glow discharge method, a layer composed of a-8i (H, X) containing atoms (0, C, N) or atoms (
a-8i (Ge, 5n) (H
, X), the above-mentioned a-8i
A layer composed of (H,X) or a-8i (Ge, 5n)
When forming a layer composed of (H,
C,N) into the layer formed using the starting materials for the formation of a-8i (H, This is done by including them in controlled amounts.

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

Specifically, as a starting material for introducing oxygen atom (0),
For example, oxygen (02), oxygen ((13), -nitrogen oxide (No2), -nitrogen dioxide (N20), nitrogen sesquioxide (N2 (13), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N2O5) ), nitrogen trioxide (N(13), silicon atom (Sl), oxygen atom (0), and hydrogen atom (H) as constituent atoms, for example, disiloxane (H38i0SiH
3), Trisiloxane (H3SiO8iH2O8 positive,)
Examples of starting materials for introducing carbon atoms (C) include methane (CH,), ethane (02H,), propane (CsHe), n-buta7 (n-C4HIO), etc. , G saturated hydrocarbons having 1 to 5 carbon atoms such as methane (C3H12), ethylene (C2H,),
Ethylene hydrocarbons with 2 to 5 carbon atoms, such as propylene (C3H6), butene-1 (C, H8), butene-2 (C4H8), inbutylene (C, H8), and thiene (Cl5HIO), acetylene (C2H2 ), methylacetylene (C3H4), butyne (C,H6), and other acetylenic hydrocarbons having 2 to 4 carbon atoms, and examples of the starting material for introducing nitrogen atoms (N) include nitrogen (N2). , ammonia (NH3), hydrazine (H2NNH2), hydrogen azide (HN3), ammonium azide (NH4N3)
), nitrogen trifluoride (F'3N), nitrogen tetrafluoride (F,N)
etc.

For example, a-8i (H, X) or a-8i (Go,
a-8i(H,X) or a-81(Ge
, 5n) (H,
(H,X) or a-Si (Go, 5n)(H,X
) by their use in conjunction with the forming starting materials to control their inclusion in the layer being formed.

Specifically, starting materials for introducing group (III) atoms include B2H6, B4HIO1BaH9, B2H6, B4HIO1BaH9,
Examples include boron hydride such as 6H□l, B6''IQ, and 6HIQs B6H14, and boron hydride such as BF3, PCL3, and BBr3.

Other examples include ALCLsSGaC&, Ga(CH3)2, ncAs, and TLCLs.

As a starting material for introducing a group V atom, specifically for introducing a phosphorus atom, hydrogen ratios such as PH3, P2I (, etc.), PH
, Engineering, PF3, PF5, PCLs, PCL, , PBr
3, PBr3, PI3, and other halogen ratios.

In addition, ASH3, AsF3, AsCl2, AsB
r3, ALP5, 81) H3, S'bF3, S 1)
F,,5bCL3.5bcz6,Bi)I3,EiCz
, , B1Br3 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

When a glow discharge method is used to form a layer or layer region containing oxygen atoms, a starting material for introducing oxygen atoms is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. .

is added. As such a starting material for introducing oxygen atoms, almost any gaseous substance or substance that can be gasified can be used as long as it has at least an oxygen atom as a constituent atom.

For example, a raw material gas containing silicon atoms (Sl), a raw material gas containing oxygen atoms (0), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
or a raw material gas containing silicon atoms (Sl) and oxygen atoms (0) and hydrogen atoms (H) at a desired mixing ratio. A raw material gas containing atoms is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Sl) and oxygen atoms (
0) and a raw material gas whose constituent atoms are three hydrogen atoms (H) can be used in combination.

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

Specifically, for example, oxygen (02), oxygen ((13),
-Nitrogen oxide (No), nitrogen dioxide (NO2), -nitrogen dioxide (N20), nitrogen sesquioxide (N2 (13), trinitrogen tetroxide (N204), nitrogen sesquioxide (N2o5), nitrogen trioxide (No3) Examples include lower siloxanes such as disiloxane (E(3Si08iH3), trisiloxane (H3SiO8iH20SiH3), etc., which have silicon atoms (Sl), oxygen atoms (0), and hydrogen atoms ()1) as constituent atoms. can.

To form a layer or layer region containing oxygen atoms by a sputtering method, monocrystalline or polycrystalline 81 Ueno-- or 5i02 Ueno-1 or Si and 5in2
This can be carried out by using a wafer containing a mixture of as a target and tumbling them in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is diluted with a diluent gas as necessary to create a deposition chamber for sputtering. A gas plasma of these gases is formed to form the Si waeno-
can be sputtered.

Alternatively, by using Si and 8102 as separate targets or a single mixed target of Sl and 8102, hydrogen atoms ( 1) or/and by sputtering in a gas atmosphere containing a rhodan atom (X) as a constituent atom.

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.

For example, in order to form a layer composed of amorphous silicon containing carbon atoms by the glow discharge method, a raw material gas containing silicon atoms (Sl) and a raw material containing carbon atoms (C) are required. The gas and, if necessary, a raw material gas containing hydrogen atoms (H) and/or rhodan atoms (X) at a desired mixing ratio, or silicon atoms (Sl) are used. A raw material gas containing constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (H) are also mixed at a desired mixing ratio, or silicon atoms (81) are mixed as constituent atoms. Mixing a raw material gas containing a silicon atom (Si), a carbon atom (C), and a hydrogen atom (H) as constituent atoms, or
Furthermore, a raw material gas whose constituent atoms are silicon atoms (Sl) and hydrogen atoms (H) and a raw material gas whose constituent atoms are carbon atoms (C) are mixed and used.

Si is effectively used as such raw material gas.
SiH4, Si2H6, Si3 whose constituent atoms are and H
H8, S i, H,. etc. (5ilane)
Silicon hydride gases such as the following, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylenic hydrocarbons having 2 to 3 carbon atoms, which have C and H as their constituent atoms. etc.

Specifically, as a saturated hydrocarbon, methane (CHt)
, ethane (C2H6), propane (C3H8), n-butane (n -C4H40), methane (C5H12),
Ethylene hydrocarbons include ethylene (C2) (4)
, propylene (C3H6), butene-1 (C4H8),
Butene-2 (C4He), inbutylene (C4H8)
, pentene (C5H1o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (
C3H4), butyne (C, H6), etc.

As a raw material gas containing 8i, C, and H as constituent atoms, S
Examples include alkyl silicides such as i(CH3)4.5i(C2H5). In addition to these raw material gases, H2 can of course also be used as the raw material gas for H introduction.

To form a layer composed of a-SiC()t,X) by sputtering, single-crystal or polycrystalline Si
Wafer or C (graphite) wafer or S
This is carried out by sputtering a wafer containing a mixture of L and C in a desired gas atmosphere.

For example, when using an S1 wafer as a target, the raw material gas for introducing carbon atoms, hydrogen atoms and/or halogen atoms may be Ar, H
The diluted gas is diluted with a diluent gas such as E, and introduced into a deposition chamber for sputtering to form a gas plasma of these gases.
All you have to do is swipe 1 ueno.

In addition, when using Si and C as separate targets, or when using a mixed target of Sl and C, hydrogen atoms or /
The raw material gas for introducing Rodan atoms may be diluted with a diluting gas as 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.

When a glow discharge method is used to form a layer or layer region containing nitrogen atoms, a starting material for introducing nitrogen atoms is added to a starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. Add. As the starting material for introducing nitrogen atoms, almost any gaseous substance or gasifiable substance having at least nitrogen atoms as a constituent atom can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (Sl), a raw material gas whose constituent atoms are nitrogen atoms (N), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
A raw material gas having constituent atoms is mixed at a desired mixing ratio, or a raw material gas having silicon atoms (Sl) and nitrogen atoms (N) and hydrogen atoms (H) having constituent atoms is used. The atomic raw material gas can also be used by mixing it in a desired mixing ratio.

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).

A starting material that is effectively used as a raw material gas for introducing nitrogen atoms (N) used when forming a layer or layer region containing nitrogen atoms is one that has N as a constituent atom or a mixture of N and H.
For example, nitrogen (N2), ammonia (
NH3), hydrazine (H2NNH2), hydrogen azide (
Gaseous or gasifiable nitrogen such as HN3), ammonium azide (NH,N3), nitrogen compounds such as nitrides and azides may be mentioned. In addition to this, nitrogen atoms (
Nitrogen halides such as nitrogen trifluoride (F'31'J) and nitrogen tetrafluoride (F,N) can be used because in addition to the introduction of nitrogen (N), it is also possible to introduce a rodan atom (X). can be mentioned.

To form layers or layer regions containing nitrogen atoms by sputtering methods, monocrystalline or polycrystalline Si wafers or Si3N wafers, or Sl and Si3N
This can be carried out by using a wafer containing a mixture of these as a target and sputtering them in various gas atmospheres.

For example, if an S1 wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the source gas is used in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing the Si wafer into the Si wafer and forming a gas plasma of these gases.

Alternatively, by using Sl and Si3N as separate targets, or by using a mixed target of Si and Si3N, it is possible to use at least hydrogen atoms in an atmosphere of dilution gas as a sputtering gas. (H)
Alternatively, it can be formed by sputtering in a gas atmosphere containing 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 also be used as an effective gas 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., and germanium atoms and/or tin atoms, group The content of Group III atoms, oxygen atoms, carbon atoms, nitrogen atoms, hydrogen atoms and/or halogen atoms can be controlled by controlling the gas flow rate of each starting material for supplying atoms flowing into the deposition chamber or by controlling the respective contents of each atom supplying starting material flowing into the deposition chamber. This is done by controlling the gas flow ratio between the starting materials for supplying atoms.

In addition, conditions such as support temperature, gas pressure in the deposition chamber, and discharge power during formation of the photosensitive layer and surface layer are important factors in order to obtain a light-receiving member with desired characteristics. It is selected appropriately taking into consideration the function.

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 photosensitive layer and surface layer, they are determined by taking into consideration the type and amount of the atoms to be contained. There is also a need to do so.

Specifically, when forming a photoreceptive layer made of a-8i (HIX) containing nitrogen atoms, oxygen atoms, carbon atoms, etc., the support temperature is usually 50 to 350 ° C. Particularly preferably, the temperature is 50 to 250°C. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, particularly preferably 0.1 to 5 Torr. In addition, the discharge power is usually 0.0 (15 to 50 W 7cm2, but more preferably 0.01 to 30 W/c
rn2, particularly preferably from 0.01 to 20 W/cm2.

When forming a photosensitive layer consisting of a-8iGe (H,
When forming a photosensitive layer consisting of -5iGe (H, do. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, and particularly preferably 0.1 to 1'rorr. Further, the electric discharge and e-warping are normally set to 0 (15 to 50 W 7 cm2), preferably 0.01 to 30 W 7 cm, and particularly preferably 0.01 to 20 W 7 cm2.

However, the specific conditions for layer formation such as support temperature, discharge 7e 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.

In the light-receiving member of the present invention, the light-receiving layer thereof must be formed to have at least one pair of non-parallel interfaces within a short range, as described above, and in order to The layer is formed so that the surface of the layer is non-parallel to the support surface, but in order to do this, the discharge, Q-war, and gas pressure are kept relatively high during the film-forming operation. It is done by keeping.

The discharge power and gas pressure vary depending on the type of gas used, the material of the support, the shape of the surface of the support, the temperature of the support, etc., and are determined in consideration of these various conditions.

By the way, the distribution state of germanium atoms and/or tin atoms, oxygen atoms, carbon atoms or nitrogen atoms, Group II atoms or Group V atoms, or hydrogen atoms and/or Rodan atoms contained in the photosensitive layer of the present invention In order to make the photosensitive layer uniform, it is necessary to keep the above-mentioned conditions constant when forming the photosensitive layer.

Further, in the present invention, when forming the photoreceptive layer, germanium atoms and/or tin atoms contained in the layer,
In order to form a layer having a desired distribution state in the layer thickness direction by changing the distribution concentration of oxygen atoms, carbon atoms, nitrogen atoms, or group II atoms or group V atoms in the layer thickness direction, a glow discharge method is used. When using germanium atoms and/or tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, or gases of starting materials for introducing Group I atoms or Group V atoms into the deposition chamber. The flow rate is changed as appropriate according to a desired rate of change, and other conditions are kept constant. In order to change the gas flow rate, the opening of a predetermined needle pulp 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.

However, when forming the photoreceptive layer using the sfumitter ring method, the distribution concentration in the layer thickness direction of germanium atoms, tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, group III atoms, or group III atoms must be adjusted. In order to form a desired distribution state in the thickness direction by changing the distribution state in the thickness direction, germanium atoms, tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, or Group Ⅰ atoms can be used, as in the case of using the glow discharge method. or Chapter V
The starting material for introducing group atoms is used in a gaseous state, and the gas flow rate at which the gas is introduced into the deposition chamber is varied according to the desired rate of change.

Furthermore, when the surface layer of the present invention is composed of at least one selected from inorganic fluorides, inorganic oxides, and inorganic sulfides, the thickness of the surface layer can also be controlled at an optical level. Since it is necessary to do so, vapor deposition method,
Examples of methods used include the S/E stumbling method, the plasma vapor phase method, the photo-CVD method, and the thermal CVD method. It goes without saying that these forming methods are appropriately selected and used in consideration of factors such as the type of material forming the surface layer, manufacturing conditions, the level of equipment capital investment, and the manufacturing scale.

Incidentally, from the viewpoint of ease of operation, ease of setting conditions, etc., when the above-mentioned inorganic compound is used to form the surface layer, it is preferable to employ the stumbling method. That is, an inorganic compound for forming a surface layer is used as a target, Ar gas is used as a SuQ sputtering gas, and the inorganic compound is sputtered to deposit a surface layer.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 26, but the present invention is not limited thereto.

In each example, the photosensitive layer was formed using a glow discharge method, and the surface layer was formed using a glow discharge method or a sputtering method. FIG. 4 shows a molding device for the light receiving member of the present invention using a glow discharge method.

2902.29 (13.2904.29 (15.
The gas chamber of 2906 is sealed with raw material gas for forming each layer of the present invention.
99%) Bo/Pe, 29 (13 diluted with B2 82
H6 gas (purity 99.999%, hereinafter abbreviated as B2H6/H2).

) cylinder, 2904 is CH4 gas (purity 99.999) cylinder, 29 (15 is GeF, gas (purity 99.99)
9%) cylinder, 2906 is He gas (purity 99.999
%) It is a cylinder. And 2906' is a closed container containing SnC.

In order to flow these gases into the reaction chamber 2901, valves 2922 to 2926 of gas cylinders 2902 to 2906,
Confirm that the leak valve 2935 is closed, and also check the inflow valves 2912 to 2916 and the outflow valve 2917.
~2921, confirm that the auxiliary valves 2932 and 2933 are open, and first open the main valve 2934 to exhaust the reaction chamber 2901 and gas piping. Next, vacuum A
An example of forming the first layer and the second layer on the cylinder 2937 will be described below.

First, from the gas cylinder 2902, SiF, gas, gas cylinder 29 (from 13 B2H6/B2 gas, gas cylinder 29 (from 15) GeF4 gas, respectively) are connected to the valve 2922.
．． Open 2923, 2925 and check the outlet pressure:) 292
Adjust the pressure of 7.2928.2930 to 1 to 9/crn2, gradually open the inlet valve 2912.2913.2915, and mass 70 controller 2907.2908,
2910. Subsequently, the outflow valve 291
7.2918.2920, the auxiliary valve 2932 is gradually opened to allow gas to flow into the reaction chamber 2901. At this time, f9iF, gas flow rate, GeF, gas flow rate, B2H67
Outlet valve 2 so that the ratio of B2 gas flow rate is the desired value.
917, 2918, 2920, and reaction chamber 2.
Vacuum gauge 2936 so that the pressure inside 901 reaches the desired value
Adjust the opening of the main valve 2934 while checking the reading. After confirming that the temperature of the base cylinder 2937 is set to a temperature in the range of 50 to 400°C by the heating heater 2938, the power source 2940 is set to the desired power to generate glow discharge in the reaction chamber 2901. and a microcomputer (not shown)
SiF, gas, GeF, gas and B2 H6/B2 according to the pre-designed flow rate change line using
While controlling the gas flow rate of the gas, the base cylinder 29
First, a first layer containing silicon atoms, germanium atoms, and boron atoms is formed on the substrate 37.

To form the second layer on the first layer by the same operation as above, for example, each of SiF, gas, and CH4 gas is diluted with a diluent gas such as He or Ar% as necessary. This is accomplished by flowing the gas into the reaction chamber 2901 at a desired flow rate and generating a glow discharge according to desired conditions.

Needless to say, all the outflow valves other than those required for forming each layer are closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into or out of the reaction chamber 2901. In order to avoid gas remaining in the gas piping leading from the valves 2917 to 2921 into the reaction chamber 2901, the outflow valves 2917 to 2921 are closed, the auxiliary valves 2932 and 2933 are opened, and the main valve 2934 is fully opened to temporarily raise the temperature in the system. Perform the operation to evacuate to vacuum as necessary.

In addition, when containing tin atoms in the first layer and using a gas starting from SnC as a raw material gas, the solid SnC placed in 2906' is heated by means of heating means (Fig. (not shown) and inert gas cylinder 2906 such as Ar or He in the SnC film.
Bubble an inert gas such as Ar or He into the solution. The generated SnC gas is caused to flow into the reaction chamber by the same procedure as the above-mentioned SiF, gas, GeF, gas, B2H6/B2 gas, etc.

In addition, when forming the photosensitive layer by the glow discharge method and then forming the surface layer by the flash tuttering method, close the leak valve for each raw material gas and dilution gas used to form the photosensitive layer. 2935 is gradually opened to return the inside of the deposition apparatus to atmospheric pressure, and then the inside of the deposition chamber is cleaned using argon gas.

Next, a target made of an inorganic compound for forming a surface layer is spread over the cathode electrode (not shown), the support on which the photosensitive layer is formed is placed in the deposition apparatus, and the leak valve 2935 is closed to deposit the target. After reducing the pressure inside the apparatus, argon gas is introduced until the inside of the deposition apparatus becomes about 0.015 to 0.02 Torr. High frequency power (1
A glow discharge is generated at a power of about 50 to 170 W), and the inorganic compound is sputtered to form a surface layer on the already formed photosensitive layer.

Example 1 A cylindrical At base (length 357wR) was used as a support.
, diameter 80 WrM) using a lathe to form a groove as shown in Fig. 30(A). The cross-sectional shape of the groove at this time is the 30th
(B) As shown in the figure. In addition, the 30th (A1
The figure is an overall view of the At support, and FIG. 30(B) is a view showing a cross-sectional shape of a part of its surface.

Next, a light-receiving layer was formed on the At support using the manufacturing apparatus shown in FIG. 4 under the conditions shown in Tables A and B below.

When the thickness of the photoreceptive layer of the thus obtained photoreceptive member was measured using an electron microscope, it was found that the surface of the photoreceptor layer was non-parallel to the surface of the support, and the surface of the photoreception layer was non-parallel to the surface of the support. The difference in average layer thickness between the end portion and the end portion was 2 μm.

Further, regarding the light receiving member, using the image exposure apparatus shown in FIG. 31, a wavelength of 780 nm and a spot diameter of 80 μm
Image exposure was performed by irradiating laser light, and development and transfer were performed to obtain an image. In the obtained image, no interference fringe pattern was observed, and an image showing good electrophotographic characteristics for practical use was obtained.

Note that FIG. 31(A) is a schematic plan view schematically showing the entire exposure apparatus, and FIG. 31(B) is a schematic side view schematically showing the entire exposure apparatus. In the figure, 3101 is a light receiving member, 3102 is a semiconductor laser, 31 (13 is fθ
A lens 3104 indicates a polygon mirror.

Example 2 A light-receiving layer was formed on the At support used in Example 1 under the conditions shown in Tables A and B.

When we measured the difference in the layer thickness of the photoreceptive layer within minute portions of the photoreceptive members thus obtained using an electron microscope, we found that the surface of the photoreceptor layer was non-parallel to the surface of the support. However, the difference in average layer thickness between the center and both ends of the photoreceptive layer was 2.3 μm.

Furthermore, when images were formed on these light-receiving members in the same manner as in Example 1, no interference fringes were observed in each image, and the images exhibited good practical electrophotographic properties. Ta.

Example 3 In the same manner as in Example 1, an Aj support (cylinder N[130
1-3 (13) were obtained.

A light-receiving layer was formed on the At support (cylinder NcL301-3 (13)) according to the layer forming conditions shown in Tables A and B.

For each of the light-receiving members thus obtained, the difference in layer thickness of the light-receiving layer within a minute portion was measured in the same manner as in Example ①. They were parallel.

However, the difference in average layer thickness between the center of the cylinder and both ends of the photoreceptive layer was 2.2 μm.

When images were formed on these light-receiving members in the same manner as in Example 1, no interference fringes were observed in each of the images obtained, indicating that they exhibited good electrophotographic characteristics for practical use. It was done.

Examples 4 to 26 A light-receiving layer was formed on the A4 support (cylinder N (1301 to 3 (13)) used in Example 3 according to the layer forming conditions shown in Tables A and B.

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 high quality.

Table A However, the numbers in the table represent the layer positive of Table B.

A table (continued) However, the numbers in the table represent the layer Nn of Table B.

B Table B Table (Continued 1) B Table (Continued 2) B Table (Continued 3) [Summary of Effects of the Invention] The light-receiving member of the present invention is composed of the amorphous silicon described above by having the layer structure as described above. All of the problems of light-receiving members having a light-receiving layer can be solved, and in particular, even when laser light, which is coherent monochromatic light, is used as a light source, interference fringe patterns in images formed due to interference phenomena can be solved. It is possible to significantly prevent the appearance of , and form an extremely high quality visible image.

In addition, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and still has excellent photosensitivity characteristics particularly 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 undertones, and high resolution.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing the layer structure of the light receiving member of the present invention, and FIGS. 2 to 4 are for explaining the principle of preventing the occurrence of interference fringes in the light receiving member of the present invention. FIG. 2 is a partially enlarged view of the support. FIG. Figure 4 is a diagram comparing the intensity of reflected light when the interfaces of the constituent layers provided above are parallel and non-parallel, and shows the interference when the layers constituting the photosensitive layer are two or more multilayers. FIG. 3 is a diagram illustrating prevention of the occurrence of stripes. FIG. 5 is a diagram showing a typical example of the surface shape of the support of the light-receiving member of the present invention. 6 to 10 are diagrams for explaining the generation of interference fringes in a conventional light receiving member (FIG. 6 shows the generation of interference fringes in the light receiving layer, and FIG. Generation of interference fringes in the receiving layer, Figure 8 shows the generation of interference fringes due to scattered light, Figure 9 shows the generation of interference fringes due to scattered light in the photoreceptive layer with a multilayer structure,
FIG. 1O shows the occurrence of interference fringes when the interfaces of the constituent layers of the photoreceptive layer are parallel. 11 to 19 are diagrams showing the distribution state of germanium atoms or tin atoms in the layer thickness direction in the photosensitive layer of the present invention, and FIGS. These are diagrams showing the distribution state of atoms, nitrogen atoms, Group II atoms, or Group V atoms in the layer thickness direction. In each diagram, the vertical axis indicates the layer thickness of the photosensitive layer, and the horizontal axis indicates the distribution of each atom. It represents the concentration. FIG. 4 is an example of a device for manufacturing the photosensitive layer and surface layer of the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing device using a glow discharge method. Figure 30 (A) is an overall view of forming a support for the light receiving member of the present invention formed by mechanical processing using a lathe, and Figure 30 (B) -
(E) is a diagram showing a cross-sectional shape of a part of the surface of the support. FIG. 31 is a diagram illustrating an image exposure apparatus using laser light. Regarding FIGS. 1 to 4, 100...light receiving member, 101...support, 1
02.202.302.402...Photosensitive layer, 1 (13
．． 2 (13.3 (13.4 (13... surface layer, 402
', 402''...Layer constituting the photosensitive layer, 104.20
4.304...Free surface, 2(15.3(15...
Regarding the interfaces between the photosensitive layer and the surface layer in FIGS. 6 to 10, 601...lower interface, 602...upper interface, 701
... Support, 702.7 (13... Photoreceptive layer, 80
1... Support, 802... Photoreceptive layer, 901...
Support, 902... first layer, 9 (13... second layer,
1001... Support, 1002... Photoreceptive layer, 10
(13...Support surface, 1004...Photoreceptive layer surface, 2901...Reaction chamber, 2902-2906...Gas cylinder, 2906'-5n (J, airtight container, 2907-
2911-f Souflo controller, 2912-291
6... Inflow valve 2917-2921... Outflow valve, 2922-2926...) ζ loop, 2927-2
931...Pressure regulator, 2932.2933...Auxiliary hull, 7', 2934...Main valve, 2935.
・・Leak valve, 2936・・Vacuum gauge, 2937・・
・Base cylinder, 2938...Heating heater, 29
39...Motor, 2940...High frequency power source Regarding Fig. 31, 3101...Light receiving member, 3102...Semiconductor laser, 31 (13...Fθ lens, 3104...Engraving of polygon mirror drawing (No change in content) Figure 3 (A) (B) (C) i. Position Q and eCt5 Q mouth position Figure 8 Figure 9 Figure 10 Position Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 □C Figure 17 Figure 18 Figure 20 Figure 21 Figure 23 Figure □C Figure 26 □C □C Figure 30 (Non-m) Figure 30 (C) (E) ( 477m) (Affi) Procedural amendment (method) % formula % 2 Name of investigation Light reception Member: 3 Relationship with the person making the amendment Patent applicant Office 3-chome, Shimomaruko, Ota-ku, Tokyo 30 number 2 name
(100) Canon Co., Ltd. 4 Agent address: 5 Kojimachi Green Building, 3-12-6 Kojimachi, Chiyoda-ku, Tokyo Date of amendment order: January 8, 1985 (shipment date: January 28, 1986) 6. Description and drawings to be amended 7, contents of amendments; engravings and attachments of the description and drawings originally attached to the application (no change in content)

Claims (19)

[Claims] (1) A photoreceptor comprising a photoreceptor layer having a photosensitive layer made of an amorphous material containing silicon atoms and at least one of germanium atoms or tin atoms, and a surface layer on a support. In the member, the surface layer has a multilayer structure having at least an abrasion resistant layer on the outermost shell and an antireflection layer inside, and the surface of the support has a plurality of minute peaks with subpeaks superimposed on the main peak. The light-receiving layer on the surface of the support has at least a pair of non-parallel interfaces within the short range, and the non-parallel interfaces are in the layer. A light-receiving member characterized in that a large number of light-receiving members are arranged in at least one direction within a plane perpendicular to the thickness direction. (2) Claim (1) in which the surface layer is made of an amorphous material containing silicon atoms and at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms. The light-receiving member described in . (3) The light-receiving member according to claim (1), wherein the surface layer is made of at least one selected from inorganic fluorides, inorganic oxides, and inorganic sulfides. (4) The light-receiving member according to claim (1), wherein the photosensitive layer contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms. (5) The light-receiving member according to claim (1), wherein the photosensitive layer contains a substance that controls conductivity. (6) Claim No. (1) in which the photosensitive layer has a multilayer structure.
The light-receiving member described in 2. (7) The light-receiving member according to claim (4), wherein the photosensitive layer has, as one of its constituent layers, a charge injection blocking layer containing a substance that controls conductivity. (8) the photosensitive layer has a barrier layer as one of the constituent layers;
A light receiving member according to claim (4). (9) The light-receiving member according to claim (1), wherein the non-parallel interfaces are regularly arranged. (10) The light-receiving member according to claim (1), wherein the arrangement of non-parallel interfaces is periodic. (11) The light receiving member according to claim (1), having a shot range of 0.3 to 500μ. (12) Claim No. 1, wherein the support body is cylindrical (
The light-receiving member according to item 1). (13) The light-receiving member according to claim (12), wherein the uneven shape provided on the surface of the support body forms a linear protrusion having a spiral structure. (14) The light-receiving member according to claim (13), wherein the spiral structure is a multi-spiral structure. (15) The light-receiving member according to claim (13), wherein the linear protrusion is divided in the direction of its ridgeline. (16) The light-receiving member according to claim (13), wherein the ridgeline direction of the linear protrusion is along the central axis of the cylindrical support. (17) The light-receiving member according to claim (1), wherein the unevenness provided on the surface of the support has an inclined surface. (18) The light-receiving member according to claim (17), wherein the inclined surface is mirror-finished. (19) The free surface of the light-receiving layer is provided with minute irregularities arranged at the same pitch as the minute irregularities provided on the support surface. Light-receiving member.