JPS62116944A - Photo receptive material - Google Patents

Abstract

PURPOSE:To obtain a photo receptive material which is stable in various characteristics, has excellent photofatigue resistance, durability and moisture resistance, has no residual potential, has high photosensitivity and SN ratio and is fast in optical response by successively laminating an a-Si layer made into multi-layered structure contg. specific atoms and a-Si layer contg. specific atoms on a substrate having a prescribed surface characteristic. CONSTITUTION:The 1st layer 102 having the multi-layered structure successively laminated with the layer 102' consisting of the a-Si contg. at least either of Ge or Sn atoms, more preferably contg. at least either of H and X(halogen) atoms and the layer 102'' consisting of the a-Si contg. at least either of H and X atoms is formed on the base 101 of which the sectional shape of the surface has plural very small rugged shapes superposed with auxiliary peaks on the main peaks. The light receiving material 100 is obtd. by providing the 2nd layer 103 consisting of the a-Si contg. at least one kind of O and N atoms and contg. at least one kind of H and X atoms thereon.

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, ultraviolet rays, reproduction light,
It relates to a light-receiving member that is sensitive to electromagnetic waves such as infrared rays, X-rays, gamma rays, etc.

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

[Description of prior art]

A method for recording digital image information as an image is to form an electrostatic latent image by optically scanning a light-receiving member with laser light modulated according to the digital image information; There are known methods of recording images by developing them or performing further processes such as transfer and fixing as necessary.Among them, in the electrophotographic image forming method, a small and inexpensive He-Ne laser is used as a laser. Alternatively, image recording is generally performed using a semiconductor laser (usually having an emission wavelength of 650 to 820 nm).

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

However, in the light-receiving member, if the light-receiving layer is a single-layer a-Si layer, it is difficult to maintain its high photosensitivity while ensuring a dark resistance of 1012Ω or more required for electrophotography. , it is necessary to structurally contain hydrogen atoms, halogen atoms, or poron atoms in addition to these in a specific amount range in a controlled manner in the layer, so various conditions are required during layer formation. There are considerable limitations on the design tolerances of the light-receiving member, such as the need to strictly 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-57-4053, and 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 increased apparent dark resistance.

However, in such a light-receiving member whose light-receiving layer has a multilayer structure, the thickness of each layer varies, and when performing laser recording using this material, the laser light is coherent monochromatic light, so the light reception is difficult. The free surface of the layer on the laser beam irradiation side, each layer constituting the light-receiving layer, and the layer interface between the support and the light-receiving layer (
From now on, the term "free surface" and "layer interface" will be used together.
It is called "interface". It often happens that the reflected light beams that are reflected from each other cause interference.

This interference phenomenon causes the so-called,
This appears as an interference fringe pattern and causes image defects. Particularly in the case of forming a half-tone image with high gradation, a blurred 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 light ro incident on a certain layer constituting the light-receiving layer of the light-receiving member and reflected light R reflected at the upper interface 602.
Reflected light R2 reflected at the lower interface 601 is shown.

If the average layer thickness of a layer is d, the refractive index is n, and the wavelength of light is λ, then the thickness of a certain layer is uneven with a thickness difference of clearly π or more. Reflected light R1+
The absorption of a certain layer depends on whether R2 satisfies the following conditions: 'l nd == mλ (m is an integer, reflected light strengthens each other) or 2nd = (m+1)λ (m is an integer, reflected light weakens each other). A change in the amount of light and the amount of transmitted light occurs. That is,
When the light-receiving member has a two or more layer (multilayer) structure as shown in FIG. 7, interference effects as shown in FIG. 6 occur for each layer.
As a result, the respective interferences act synergistically to form an interference fringe pattern, which directly affects the transfer member, and the interference fringes appear on the member. There is a problem in that interference fringes corresponding to the pattern appear in the transferred and fixed visible image, 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 ±500X to ±10,000X to form a light scattering surface (for example, as described in Japanese Patent Laid-Open No. 5
8-162975), (b) A method of providing a light absorption layer by treating the surface of an aluminum support with black alumite, or by dispersing carbon, color pigments, and dyes in a resin (for example, Japanese Patent Application Laid-Open No. 57-165845), (C') The surface of the aluminum support is treated with satin-like alumite, and the surface of the support is treated with fine grain-like irregularities by sandblasting to form a light scattering and anti-reflection layer on the surface of the support. A method of providing such a structure (for example, see Japanese Unexamined Patent Publication No. 57-16554) has been proposed.

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

That is, in method (a'), a large number of irregularities of a specific size are provided on the surface of the support, and although this prevents the appearance of interference fringes due to light scattering effects to some extent, Since the specularly reflected light component still remains, in addition to the interference fringe pattern caused by the specularly reflected light remaining, the irradiation spot spreads due to the light scattering effect on the support surface, resulting in a substantial decrease in resolution. This will cause

Regarding method (b), complete absorption is not possible with black alumite treatment, and the reflected light on the support surface remains. In addition, when providing a colored pigment dispersed resin layer,
When forming the a-Si layer, a degassing phenomenon occurs in the resin layer and the layer quality of the formed photoreceptive layer is significantly deteriorated, and the resin layer is damaged by the plasma during the formation of the a-3i layer. As a result, the original absorption function is reduced,
There are problems such as deterioration of the surface condition which adversely affects the subsequent formation of the a-Si layer.

For method (C), as shown in FIG. A part of the light is reflected by the surface of the light-receiving layer 802 and becomes reflected light R8, and the remainder enters the inside of the light-receiving layer 802 and becomes transmitted light I.

A part of the transmitted light (1) is scattered on the surface of the support 801 and becomes diffused light Kl r K2 r K3...
・The remaining light is specularly reflected and becomes the reflected light R2, and a part of it becomes the emitted light R8 and goes outside, but the emitted light R8 is a component that interferes with the reflected light R. In any case, the interference fringe pattern remains, so the interference fringe pattern does not completely disappear.

By the way, in order to prevent interference in this case, the support 8010 is
Some attempts have been made to increase the diffusivity of the surface, but in such cases, light is instead diffused within the photoreceptive layer, causing halation, which ultimately results in a decrease in 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.
Since the photoreceptive layer 1002 is deposited along 003K,
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 1003' and 1004'.

Therefore, the incident light in that part is 2nd.

= mλ or 2 n d + = (m+ ”/2)
The relationship λ is established, resulting in a light pongee area or a dark area, respectively. In addition, the layer thickness of the photoreceptive layer as a whole is dI+'2+d3+
Since there is non-uniformity in the layer thickness such that the maximum difference in each of the λ'4 is 5 or more, a bright and dark striped pattern appears.

Therefore, even if the surface of the support 1001 is regularly roughened, 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, there is also interference due to the reflected light at the interface between each layer, so the degree of interference fringe pattern expression becomes more complicated than that of a single-layered light-receiving member.

[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-Si, 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, almost independent of the usage environment, 9 with excellent resistance to light fatigue, and to prevent deterioration even after repeated use. To provide a light-receiving member having a light-receiving layer composed of a-3i, 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 composed of a-3i, 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 43i.

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-Si and capable of obtaining a high-quality image with no blur, high density, clear halftones, and high resolution. It is in.

[Structure of the invention]

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

That is, the present invention provides a first layer made of an amorphous material containing silicon atoms, on a support,
A light-receiving layer comprising a second layer composed of an amorphous material containing atoms selected from oxygen atoms and nitrogen atoms and atoms selected from hydrogen atoms and halogen atoms. The receiving member has a multilayer structure in which the first layer includes, in order from the support side, a layer containing at least one of germanium atoms or tin atoms, and a layer containing neither germanium atoms nor tin atoms. The surface of the support has a cross-sectional shape in which a main peak and a sub-peak are superimposed to form a plurality of minute irregularities, and the light-receiving layer on the surface of the support is A light having at least one pair of non-parallel interfaces in a short range, and a large number of non-parallel interfaces arranged in at least one direction in a plane perpendicular to the layer thickness direction. Relating to a receiving member.

By the way, as a result of extensive research by the present inventors, the findings obtained are summarized as follows: In a light-receiving member having multiple layers on a support, irregularities that are finer than the resolution required for the light-receiving member. is formed on the surface of the support, and at least one pair of non-parallel interfaces is formed in a minute portion (hereinafter referred to as "short range") within one period of the uneven shape, and the non-parallel interfaces are formed on the surface of the support. When a large number of the interference fringes are arranged in at least one direction in a plane perpendicular to the layer thickness direction, the problem of interference fringes that appear during image formation can be solved. The vertical cross-sectional shape 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.

This knowledge is based on facts obtained through various experiments conducted by the present inventors.

This will be explained below using drawings to facilitate understanding.

FIG. 1 is a schematic diagram showing an example of the layer structure of the light-receiving member according to the present invention, and 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
03.

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) is an enlarged view of a part of the first layer and second layer of the light receiving member shown in FIG.
The figure shows the brightness in the same part, and in the figure, 20
2 is the first layer, 203 is the second layer, 204 is the free surface,
205 indicates the interface between the first layer and the second layer. As shown in FIG. 2A, the layer thickness of the second layer 203 changes continuously from '21 to '22 within the short range l, so that the free surface 204 and the interface 205 are different from each other. It has a slope. Therefore, coherent light such as laser light incident within this short range l is
Interference occurs in the short range 1, and a minute interference fringe pattern is generated.

However, the interference fringes generated in the jaw train DI do not appear in the image because the size of the short range l is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. 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, in FIG. 3 (in the figure, 302 is the first layer, 303 is the second layer, 304 is the free surface, 305 is the first layer 302
The interface between and the second layer 303 is shown. ), when the interface 305 between the first layer 302 and the second layer 303 and the free surface 304 are non-parallel (see FIG. 3(A)), the incident light I. Since the reflected light R1 and the emitted light R2 have different traveling directions, the interface 305 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 As a result, the amount of incident light is averaged out.

This means that as shown in FIG. 2(C), the second layer 20
3 is macroscopically non-uniform, that is, the layer thickness d23 + of the second layer at any two different positions
The same is true even when '24 is d23=d24, and the amount of light incident on the entire layer region is uniform as shown in FIG. 2(D).

The case where the first layer and the second layer are laminated on the support has been described above, but when the first layer of the light receiving member of the present invention has a multilayer structure, for example, As shown in FIG. 4, two constituent layers 402' and 402' are formed on the support.
A first layer 402 and a second layer 403 consisting of
Even if the layers are stacked, the amount of incident light. For,
Reflected lights R1, R2, R3, R4 and R6 are present, 402'.

In each layer 402' and 403, a phenomenon occurs in which the amount of incident light is averaged as explained with reference to FIG.

Moreover, the interface of each layer in the Jotren iZl acts as a kind of slit, causing diffraction phenomena there.

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

Therefore, when considering the entire light-receiving layer, interference is a synergistic effect in each layer, so in the light-receiving member of the present invention, as the number of layers constituting the first layer increases, the interference becomes more pronounced. influence can be prevented.

Based on the above experimentally confirmed facts, the support for the light receiving member of the present invention having the above-described structure has a surface that has minute irregularities that exceed the resolving power required for the light receiving member. The cross-sectional shape of the unevenness is such that a sub-peak is superimposed on a main peak.

The use of a support having such a surface shape allows the light that has passed through the photoreceptive layer to interfere with the photoreceptive member on which the photoreceptive layer is formed and is reflected on the surface of the support, resulting in an image being formed. This effectively prevents striped patterns and leads to the formation of excellent images.

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

Further, the light-receiving layer of the light-receiving member of the present invention is composed of a first layer and a second layer, and the first layer is made of silicon fjl (
Si), germanium atom (Ge) or tin atom (
An amorphous material containing at least one of Sn) and preferably at least one of a hydrogen atom (H) or a halogen atom (X) [hereinafter referred to as "a"
It is written as -8i (Ge, 5n)(H,X)J.

], an amorphous material containing silicon atoms (Si) and preferably at least one of hydrogen atoms (H) or halogen atoms (X) [
Hereinafter, it will be written as [a-8i (H,X) J. This is a multilayer structure in which the layers consisting of ] are provided in order from the support side. The second layer may contain atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms, and which are not contained in the second layer, and may further contain a substance that controls conductivity. can. Particularly preferably, it has a charge injection blocking layer containing a substance that controls conductivity as one of the constituent layers, and/or a barrier layer as one of the constituent layers.

Further, the second layer includes silicon atoms (Si), at least one selected from oxygen atoms (0) and nitrogen atoms (N), and at least one of hydrogen atoms (rH) and halogen atoms (X). An amorphous material containing one or the other [
Hereinafter, it is written as "a S r (0+N')+(H,X)J".

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 first layer and a second layer laminated on a support, and the first layer has a layer which will be described in detail later. For the purpose of preventing interference, a localized region containing a relatively large amount of germanium atoms and/or tin atoms is formed at the end of the first layer on the support side, or/and the first layer contains a relatively large amount of germanium atoms and/or tin atoms. a localized region containing a relatively large amount of a conductivity controlling substance (i.e. a charge blocking layer) is formed at the end of the first layer on the support side, or/and the end of the first layer on the support side. It is desirable to form a barrier layer on the substrate, and in the light-receiving member of the present invention having such a structure, a plurality of interfaces are formed by a plurality of layers on the support. There are at least one pair of non-parallel interfaces within range l.

In order to achieve the object of the present invention more effectively, the difference in layer thickness in the short range l, for example, the difference between d2□ and d2□ in FIG. When the wavelength is λ, it is desirable to satisfy the following formula: '21 '2□≧π (n: refractive index of the constituent layer). The upper limit of the difference in layer thickness is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 1.5 pm, most preferably 0.
．． It is desirable to set it as 2 micrometers - 1 micrometer.

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 the short range l.
As long as this condition is satisfied, parallel interfaces may exist. However, in that case, if we take any two positions of the parallel interfaces, let the difference in layer thickness at those positions be Δl, let the wavelength of the irradiated light be λ, and let the refractive index of the layer be n. It is desirable to form the layer or layer region so as to satisfy the following formula: .

Regarding the creation of the first layer and the second 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. Vacuum deposition methods such as glow discharge method, sputtering method, and ion blating method are usually used, but in addition to these methods, optical CVD method, thermal CVD method, etc. can also be employed.

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 first layer, 102' is a layer containing at least one of germanium atoms or tin atoms; 102' is a layer containing neither germanium atoms nor tin atoms; 103 is a second layer;
4 indicates the free surface.

Support The support 101 in the light-receiving member of the present invention has minute irregularities on its surface that are better than the resolving power required for a 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 back surface of the support can be formed by a chemical method such as chemical etching or electroplating, a physical method such as vapor deposition or sputtering, or a mechanical method such as lathe processing, but production control is easy. In order to do this,
Mechanical processing methods such as lathes are preferred.

For example, when machining the surface of a support with a lathe, a cutting tool having 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 machined in advance with a desired design. By regularly moving in a predetermined direction while rotating according to a program, the surface of the support is accurately cut to form a desired uneven shape, pitch, and depth. The linear protrusion produced 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 best to use a mixture of both.

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, a-5i(H,X
) or a-8t (Ge,an)(H,X) layer is
The structure is 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, a-8i(H,X) or a-8i(Ge,
5n) 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 (H,X) layer.

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

Further, when cleaning the blade, 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, and even more preferably 5 μm to 50 μm.

Further, the maximum depth of the recess is preferably 0.1 μm to 5 μm.
, preferably 0.3 μm to 3 μm, optimally 0.6 μm
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 slope of the recess (or linear protrusion) is preferably 1 degree to 20 degrees, more preferably 3 degrees. ~15 degrees, optimally 4 degrees to 10 degrees.

The support 101 used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, kl,
Cr, Mo, Au%Nb, Ta, V, 'pi
, PT, PB, or alloys thereof.

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

For example, if it is glass, NiCr, kl
, Cr, Mo, Au, Ir, Nb, Ta
%V, Ti.

pt, pd, In2O3, sno□, ITO (
Conductivity can be imparted by providing a thin film made of In203 +5n02), or if it is a synthetic resin film such as polyester film, NiCr,
Al, Ag, Pb, Zn, Ni, Au%C
r, Mo, Ir, Nb, Ta, V.

TA! , Pt or the like is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal to impart conductivity to the surface. The shape of the support can be any shape such as a cylinder, a belt, a plate, etc., and the shape can be determined as appropriate depending on the purpose and desire. For example, if the light-receiving member 100 of FIG. 1 is used as an electrophotographic image forming member, it is preferable to use an endless belt or a cylindrical shape for continuous high-speed copying. The thickness of the support is determined as appropriate so as to form a light-receiving member of the desired thickness, but if flexibility is required as a light-receiving member, the support can sufficiently function as a support. It can be made as thin as possible within the range. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

First Layer In the light-receiving member of the present invention, the first layer 102 is provided on the support 101 described above, and the second layer is provided on the support 101.
On the 1st side, germanium atoms (Ge) or tin atoms (S
a-8i (hereinafter referred to as "a-8i (Ge, 5n) (H
,X)J. ] and a-8i (hereinafter referred to as [a-8i(H,
X) Written as J. ] It has a multilayer structure in which the layers 102' are laminated in order. Furthermore, the -th layer 102
may contain atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms that are not contained in the second layer, and may further contain a substance for controlling conductivity as necessary. can.

Specific examples of the halogen atom (X) contained in the first layer include fluorine, chlorine, bromine, and iodine,
Particularly preferred are fluorine and chlorine. Then, the hydrogen atoms contained in the first layer 102 (
The amount of H) or the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is usually 1 to 40
atomic%, preferably 5-30 atomic%
It is desirable to do so.

In addition, in the light-receiving member of the present invention, the layer thickness of the first layer is one of the important factors for efficiently achieving the object of the present invention.
In order to give the light-receiving member the desired characteristics, it is necessary to pay sufficient attention when designing the light-receiving member. 8
0μ, more preferably 2 to 50μ.

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

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

In the first layer in the present invention, germanium atoms and/or tin atoms are present in the layer 102 in contact with the support 101.
102' in a uniformly distributed state, or in a non-uniformly distributed state (here, a uniformly distributed state means that the distribution concentration of germanium atoms and/or tin atoms is It means that it is uniform in the plane direction parallel to the surface of the support and is also uniform in the layer thickness direction of the layer 102', and the state of non-uniform distribution means that the distribution concentration of germanium atoms and/or tin atoms is uniform. However, layer 102'
Although the layer 10 is uniform in the plane parallel to the surface of the support,
2' is non-uniform in the layer thickness direction. ) In the layer 102' of the present invention, it is particularly desirable to contain germanium atoms and/or tin atoms so that they are more distributed on the support side than on the layer 102' side. By making the distribution concentration of germanium atoms and/or tin atoms extremely large at the end on the support side, when a long wavelength light source such as a semiconductor laser is used, almost no light is absorbed in the layer 102'. The pure 5 long wavelength light can be substantially completely absorbed in the layer 102', and interference by reflected light from the support surface is prevented.

Furthermore, in the light-receiving member of the present invention, since the amorphous materials constituting the layer 102' and the layer 102' each have a common constituent element of silicon atoms, chemical stability is achieved at the laminated interface. are sufficiently secured.

Below, germanium atoms contained in the layer 102' and/or
Or some typical examples of the distribution state of tin atoms in the layer thickness direction of the layer 102', using germanium atoms as an example.
This will be explained with reference to FIGS. 1 to 19.

In FIGS. 11 to 19, the horizontal axis represents the distribution concentration C of dalmanium atoms, and the vertical axis represents the layer thickness of the layer 102'.
tB indicates the position of the end of the layer 102' on the side of the support, and t7 indicates the position of the end surface of the layer 102' on the side opposite to the support. That is, the layer 102' containing germanium atoms is 1. The layer is formed more toward the tT side than the tT side.

In addition, in each figure, if the layer thickness and concentration are shown as they are, the differences between each figure will not be clear, so please note that these figures are shown in extreme form for ease of understanding. This is a schematic diagram for explanation.

FIG. 11 shows a first typical example of the distribution state of germanium atoms contained in the layer 102' in the layer thickness direction.

In the example shown in FIG. 11, the distribution concentration C of germanium atoms is from the interface position tB where the layer 102' and the support surface where the layer 102' containing germanium atoms is formed to the position t1. Germanium atoms are contained in the layer 102' with a constant concentration C1, and the germanium atoms are located at the position t1.
The concentration is gradually and continuously decreased from the concentration C2 to the interface position tT. At the interface position t7, the distribution concentration C of germanium atoms is substantially zero.

(Here, "substantially zero" means that the amount is less than the detection limit.) In the example shown in FIG. A distribution state is formed in which the concentration gradually and continuously decreases from 1 to 2 to reach the concentration C at position tT.

In the case of FIG. 13, from position tB to multiple positions t2, the distribution concentration C of germanium atoms is constant at the concentration C3, and gradually and continuously increases between position [2 and position t7. , and the distribution concentration C is substantially zero at position t7.

In the case of Figure 14, the distribution concentration C of kelmanium atoms
is continuously and gradually decreased from the concentration C6 until reaching the multiple positions IT from the position tB, and is rapidly and continuously decreased from the position t3 until it becomes substantially zero at the position tT.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a constant value C7 between the positions tB and Rt, and the distribution concentration C is zero at the position t7. be done. Between position t4 and position t7, the distribution density C is linearly decreased from position t4 to position t7.

In the example shown in FIG. 16, the distribution concentration C is at the position t
A constant value of concentration C8 is taken from position B until position t.
, up to one position, the distribution state is such that the concentration C1o'J decreases linearly from the concentration C0.

In the example shown in FIG. 17, from position tB to position tT, the distribution concentration C of germanium atoms is the concentration C1t.
It decreases in a linear fashion to zero.

In FIG. 18, from position tB to multiple positions t6, the distribution concentration C of germanium atoms decreases linearly from concentration C2 to concentration C1, and from position t to position t.
7, an example is shown in which the concentration C13 is set to a constant value.

In the example shown in FIG. 19, the distribution concentration C of dalmanium atoms is a concentration C14 at position IB, and this concentration C14 is gradually decreased at first until reaching position t, and then at position t7. In the vicinity, the concentration decreases rapidly and becomes the concentration CtS at position t7.

Between position t 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 t,
The position t is gradually decreased.

At this point, the concentration reaches C17. Between position t and position tT, the concentration is reduced from C07 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 layer 102' in the layer thickness direction, the photoreceptor of the present invention In the member, on the support side, there is a part where the distribution concentration C of dalumanium atoms and/or tin atoms is high, and on the interface ty side, there is a part where the distribution concentration C is slightly lower than on the support side. It is desirable that the distribution state of germanium atoms and/or tin atoms is provided in the constituent layer 102'.
Preferably, as described above, 2' has a localized region containing damanium atoms and/or tin atoms at a relatively high concentration toward 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 a thickness of 5 μm from the interface position tB, or may be a part of the layer region.

Whether the localized region is a part or all of the layer 102' is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region contains dalmanium atoms or/
And, as the distribution state of tin atoms in the layer thickness direction, the maximum value CmaX of the distribution concentration of dalmanium atoms and/or tin atoms is preferably 1000 atoms with respect to silicon atoms.
IC ppm or more, preferably 5000 atoms
c ppm or higher, optimally IXIQ' atomic
It is desirable that the layers be formed in such a way that a distribution state of ppm or more can be achieved.

That is, in the light-receiving member of the present invention, the layer 102' containing dalmanium atoms and/or tin atoms has a layer thickness of within 5 μm from the support side (layer region of 5 μ layers from tn).
It is preferable that the distribution density be formed such that the maximum value Cmax of the distribution concentration exists at .

In the light-receiving member of the present invention, the content of dalmanium atoms and/or tin atoms contained in the layer 102' is as follows:
It is necessary to appropriately decide according to the requirements so as to efficiently achieve the object of the present invention, and usually 1 to 6 x 10' at
omic ppm, preferably 10-3
10' atomic ppm, preferably I
102~'2 x 105105ato ppm.

In the light-receiving member of the present invention, the first layer 102 can contain at least one kind of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms, and which is not contained in the second layer. Specifically, when the second layer is composed of a-8i (H,X) containing oxygen atoms,
The first layer may contain carbon atoms and/or nitrogen atoms, and the second layer may contain nitrogen atoms.
(H,X), the first layer can contain carbon atoms and/or oxygen atoms, and the second layer can contain 8i(H,X), the first layer can contain carbon atoms.

The purpose of causing the first layer of the light-receiving member of the present invention to contain at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms (hereinafter referred to as "atoms (0, CN)") is to Mainly increasing the light sensitivity and dark resistance of the light receiving member,
Another advantage is improved adhesion between the support and the first layer.

In the first layer of the present invention, when atoms (0, C, N) are contained, are they contained in a uniform distribution state in the layer thickness direction, or are they contained in a non-uniform distribution state in the layer thickness direction? The amount varies depending on the above-mentioned objectives and expected effects, and therefore the amount to be included also varies.

That is, when the purpose is to increase the photosensitivity and dark resistance of a light-receiving member, the atoms contained in the first layer are uniformly distributed in the entire layer area. The amount of (0,C9N) may be relatively small.

In addition, if the purpose is to improve the adhesion between the support and the first layer, it may be contained uniformly in a part of the layer area at the end of the first layer on the support side, or it may be contained in the first layer. The atoms (0, C2N) are contained in a distributed state such that the concentration of the atoms (0, C2N) is high at the end on the support side. In this case, the amount of atoms (O2C2N) contained in the first layer is relatively large. be done.

In the light-receiving member of the present invention, the amount of atoms (0, CN) to be contained in the first layer is determined, however, in addition to considering the properties required for the first layer as described above. It is determined by taking into consideration the organic relationship such as the characteristics of
tomic%, preferably 0.002-40 atoms
ic%, optimally 0.003 to 30 atomic%.

By the way, when atoms (0, C9N) are contained in the entire layer region of the first layer, or when the proportion of the layer thickness of a part of the layer region in which they are contained in the layer thickness of the first layer is large, The upper limit of the above-mentioned content is set lower. That is, in that case, for example, when the layer thickness of the layer region to be contained is the same as that of the first layer, the amount to be contained is usually 30 atomic% or less, preferably 20 atomic% or less, Optimally IQ atom
ic% or less.

Next, atoms (0, C2N
) is relatively large on the support side, decreases from the end on the support side to the end on the second layer side, and near the end of the first layer on the second layer side. In this section, some typical examples of cases in which the distribution is relatively small or substantially close to zero are given in the 20th to 2nd sections.
This will be explained with reference to Figure 8. However, the present invention is not limited to these examples.

In FIGS. 20 to 28, the horizontal axis represents atoms (O, C.

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

Figure 20 shows atoms (0, C,
A first typical example of the distribution state of N) in the layer thickness direction is shown. In this example, from the interface position tB where the first layer containing atoms (0, C, N) and the support surface are in contact with each other to the position t1, the distribution concentration C of atoms (0, c, N) is C1. Assuming a constant value, from the position 1° to the interface position tT with the second layer,
The distributed concentration C of atoms (O2C2N) decreases continuously from the concentration C2, and at the interface position fiftT, the atoms (O, C2N) are concentrated.

The distribution density C of N) becomes 03.

FIG. 21 shows one of the other typical examples.

In this example, atoms (O, C.

The distribution density C of N) continuously decreases from the density C4 from the position tB to the position t7, and reaches the density C3 at the position t7.

In the example shown in FIG. 22, the distribution concentration C of atoms (0, C, N) maintains a constant value of concentration C6 from position tB to position t2, and from position t2 to position tT, the distribution concentration C of atoms (0, C, N) maintains a constant value of concentration C6.
, C2N) gradually and continuously decreases from the concentration C7, and at position t7, the distributed concentration C of atoms (0, C2N) becomes substantially zero. However, here, "substantially zero" refers to a case where the amount is less than the detection limit amount.

In the example shown in FIG. 23, the distribution concentration C of atoms (0, C9N) gradually decreases from the concentration C8 from position tB to position 1T, and at position 1T, the distribution concentration C of atoms (0, C9N) gradually decreases from the concentration C8 to position 1T.
The distribution concentration C of CtN') becomes substantially zero.

In the example shown in FIG. 24, the distribution concentration C of atoms (0, c, N) is the concentration C0 between position tB and position t3.
The concentration is at a constant value between the position t3 and the position tT, and decreases in a -order function from the concentration C0 to the concentration C1o.

In the example shown in FIG. 25, the distribution concentration C of atoms (0, C2N) is C11 from position tB to position t4.
At a constant value of , the concentration C□ from position t4 to position tf
It decreases linearly from 2 to the concentration C□3.

In the example shown in FIG. 26, the distribution concentration C of atoms (O2C2N) decreases linearly from the concentration C□4 to substantially zero from the position tB to the position t7.

In the example shown in FIG. 27, the distribution concentration C of atoms (0, C, N) decreases in a -order function from the concentration C1 to the concentration Cta from the position 1B to the position t.
From B to position t! Until then, the concentration C16 is maintained at a constant value.

Finally, in the example shown in Figure 28, atoms (O, C.

The distribution concentration C of N) is a concentration C17 at position tB, and from position tB to position t6, the concentration C1 decreases slowly at first, and then rapidly decreases near position t6,
At position t, the concentration becomes Cta.

Next, from position t6 to position t, the concentration decreases rapidly at first, and then gradually decreases, and reaches the concentration C111 at position 1f. Furthermore, between position t7 and position t, it gradually decreases very slowly, and reaches the density C20 at position t8. Further, from position t8 to position tT
The concentration gradually decreases from C20 to substantially zero.

As in the examples shown in FIGS. 20 to 28, the first layer has a portion with a high distribution concentration C of atoms (OtC, N) at the end on the support side, and the surface layer side of the first layer If the distribution concentration C has a very low part or a part with a concentration substantially close to zero, the atoms (O2C9N ), preferably the localized region is located at the interface position tB between the support surface and the first layer.
By providing the thickness within 5μ, the adhesion between the support and the first layer can be improved even more efficiently.

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

The amount of atoms (O2C2N) contained in the localized region is such that the maximum value of the molecular concentration C of atoms (OtC9N) is 500 at
omic ppm or more, preferably 800 atomic
cppm or more, optimally 1000 atomic ppm
It is desirable to have a distribution state in which the number is m or more.

In the light-receiving member of the present invention, the first layer can contain a substance that controls conductivity in the entire layer region or in a part of the layer region in a uniform or non-uniform distribution state.

Examples of the substance that controls conductivity include so-called impurities in the semiconductor field, such as atoms layered in group Ⅰ of the periodic table that provide P-type conductivity (hereinafter simply referred to as ``first impurities'').
"group atoms". ), or atoms belonging to Group V of the periodic table that provide n-type conductivity (hereinafter simply referred to as "Group V atoms").

) is used. Specifically, as the Group 1 atoms, B
(boron), Al (aluminum), Ga (gallium)
, In (indium), TJ (talicum), etc., but particularly preferred are B and Ga. Group V atoms include P (phosphorus) and As (arsenic).
, sb (antimony), Bi (bismane), etc., but particularly preferred are p and sb.

When the first layer of the present invention contains Group 1 atoms or Group V atoms, which are substances that control conductivity, it is determined whether they are contained in the entire layer region or in a part of the layer region. As will be described later, the amount to be included will vary depending on the intended purpose or expected effect.

That is, when the main purpose is to control the conductivity type and/or conductivity of the first layer, it is contained in the entire layer region of the first layer, and in this case, Group 1 atoms or V The content of group atoms may be relatively small, usually I
""~I X 103ato103ato, preferably 5
ppm) Optimally I x 10-” to 2 x 10
It is 2102ato ppm.

In addition, the Group Ⅰ atoms or the 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 1 atoms or the Group V atoms in the layer thickness direction may be When the content is high in concentration on the side in contact with the support, a constituent layer containing Group Ⅰ atoms or Group V atoms, or a layer containing Group 1 atoms or Group V atoms in high concentration. The region is where it will function as a charge injection blocking layer. That is, 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 improved. In addition, when Group V atoms are contained, when the free surface of the photoreceptive layer is charged to O polarity, it is injected into the photoreceptor layer from the support side. It is possible to more efficiently block the movement of holes caused by In such a case, the content is relatively large, specifically, 30 to 5 x 10' atoms.
c ppm, preferably 50 to I x 10' at
omic ppm, optimally IX 102-5
10" atomic ppm.Furthermore, in order to efficiently produce the effect of the charge injection blocking layer,
When the layer thickness of the layer or layer region provided at the end of the support containing Group 1 atoms or Group V atoms is t, and the layer thickness of the photoreceptive layer is T, t/T≦0.4 It is desirable that the following relationship holds true, and more preferably the value of the relational expression is 0.35.
Hereinafter, it is preferable to optimally set it to 0.3 or less. Further, the layer thickness t of the layer or layer region is generally 3
X 10"" to 10μ, preferably 4XIO-
It is desirable that the thickness be 3 to 8 microns, most preferably 5 x 10-'' to 5 microns.

Next, the amount of group V atoms or group V atoms contained in the first layer is relatively large on the support side and decreases from the support side toward the second layer side, and A typical example of distributing Group II atoms or Group V atoms so that the amount is relatively small or substantially close to zero near the interface with the first layer is as follows. oxygen atom,
This can be explained using examples similar to those shown in FIGS. 20 to 28, which are exemplified in the case where at least one selected from carbon atoms and nitrogen atoms is contained. However, the present invention is not limited to these examples.
As in the examples shown in FIGS. 20 to 28, the first layer has a portion with a high distribution concentration C of Group 1 atoms or Group V atoms on the side closer to the support, and the second layer and On the interface side of
If the distribution concentration C has a part with a very low concentration or a part with a concentration substantially close to zero, the distribution concentration of Group 1 atoms or Group V atoms is relatively large in the part close to the support side. By providing a localized region with a high concentration, preferably within 5μ from the interface position in contact with the support surface, the distribution concentration of Group 1 atoms or Group V atoms can be increased. The above-mentioned effect that a certain layer region forms a charge injection blocking layer can be achieved more efficiently.

As mentioned above, regarding the distribution state of Group 1 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 1 atoms or Group V atoms and the content in the first layer are important. The amount of Group V atoms or Group V atoms used can be used in appropriate combinations as necessary.
Needless to say. For example, when a charge injection blocking layer is provided at the end of the first layer on the support side, a substance that controls conductivity contained in the charge injection blocking layer is added to the first layer other than the charge injection blocking layer. A substance that controls conductivity of a polarity different from the polarity may be contained, or a substance that controls conductivity of the same polarity may be contained in a much smaller amount than that contained in the charge injection blocking layer. It may also be included.

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 inorganic electrically insulating materials such as Al2O3, 5102, Si3N, and organic electrically insulating materials such as polycarbonate.

Second layer The second layer 103 of the light-receiving member of the present invention is a layer provided on the above-described first layer 102 and having a free surface 104, that is, a surface layer, containing oxygen atoms, oxygen atoms, and nitrogen atoms. Amorphous silicon containing at least one selected from the group consisting of at least one of hydrogen atoms and halodane atoms in a uniform distribution state [hereinafter referred to as "a-8i(0,N)"]
(H#X) Written as J. ].

The purpose of providing the second layer 103 in the light receiving member of the present invention is to
The aim is to improve moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, and durability. This is achieved by containing at least one selected from the following.

Furthermore, in the light receiving member of the present invention, each of the amorphous materials constituting the first layer 102 and the second layer 103 is
Since they have a common constituent atom, silicon atoms, chemical stability can be ensured at the interface between the first layer 102 and the second layer 103.

The second layer 103 contains at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniformly distributed state, and as the amount of these atoms contained increases. , the above-mentioned characteristics are improved. but,
If it is too high, the layer quality deteriorates and the electrical and mechanical properties also deteriorate. For this reason, the content of these atoms is usually 0.001 to 90 atomic%, preferably 1 to 9Q a10ffllc%, and optimally 10 to 80 atomic%.
Let atOmiC%.

The second layer contains at least either a hydrogen atom or a hydrogen atom, but the amount of hydrogen atoms (H) contained in the second layer, the amount of halodane atoms (X), or The sum of the amounts of hydrogen atoms and halodane atoms (H+X
) is usually 1 to 40 atomic%, preferably 5 to 3 atomic%
0 atomic%, optimally 5-25 atomic
%.

The second layer 103 must be carefully formed to achieve the desired overall properties. That is, a substance whose constituent atoms are at least one selected from silicon atoms, oxygen atoms, and nitrogen atoms, and hydrogen atoms and/or halodane atoms has a crystalline form depending on the content of each constituent atom and other production conditions. electrical properties range from conductivity to semiconductivity to insulating properties, and photoelectric properties range from photoconductive properties to non-photoconductive properties. It is important to select the content of each constituent atom, production conditions, etc. so that the second layer 103 having desired characteristics depending on the purpose can be formed.

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

Furthermore, in the present invention, the layer thickness of the second layer is also one of the important factors for efficiently achieving the purpose of the present invention, and is determined as appropriate depending on the intended purpose. , the amount of oxygen atoms, nitrogen atoms, halodane atoms, and hydrogen atoms to be contained in the layer, or the properties required for the second layer, and must be determined 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 second layer is usually 3 x 10-3 to 30μ, more preferably 4 x 10-3 to 20μ, particularly preferably 5
X 10”-3 to lOμ.

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 radar light, which is monochromatic light of

Furthermore, 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.
Therefore, it is particularly excellent in matching with semiconductor lasers, has a fast optical response, and also exhibits extremely excellent electrical, optical, and photoconductive properties, electrical voltage resistance, and use environment characteristics.

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, and it has high sensitivity and a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

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

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

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

For example, by glow discharge method, a-8i(H).

In order to form a layer composed of X), basically a raw material gas for supplying Si that can supply silicon atoms (Si), and a material gas for introducing hydrogen atoms (H) and/or halogen atoms (
X) A raw material gas for introduction is introduced into a deposition chamber whose interior can be made to have a reduced pressure, a glow discharge is generated in the deposition chamber, and a-Si
(H.

A layer consisting of X) is formed.

The raw material gas for supplying Si is 5IH4, S r
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as 2 Ha, S i 3H8, S + 4H1°, etc., are mentioned, and in particular, S iH,, S+2H6 is preferred.

In addition, as the raw material gas for introducing the helocene atoms,
Many halodane compounds may be mentioned, with gaseous or gasifiable halodane compounds being preferred, such as e.g. evahalogen gas, halodanides, interhalogen compounds, halodane-substituted silane derivatives, in particular fluorine, chlorine, bromine. , iodine hexadangas, BrF XC11F% C
AF3, BrF, , BrF3, IF7, ICII,
HaO)f7 intercompounds such as IBr, and S r F
4.5f2F6, S i C14,5iBr.

Examples include silicon halides such as. When using silicon halide in a gaseous state or that can be gasified as described above, a layer composed of a-Si containing halogen atoms can be formed without using a separate raw material gas for supplying Si. It is particularly effective because it can be formed.

Further, as the raw material gas for supplying hydrogen atoms, hydrogen gas, HFXHCl, HBr, halodanide such as HI, S iH,, S i 2 Ho, SilHg, s'4
Silicon hydride such as H10, or SiH2F2.5iH
2I2.5IH2C12, 5iHCJ3.5iH2Br
Gaseous or gasifiable materials such as 2.5iHBr3 and other 2-logon substituted silicon hydrides can be used, and when these raw material gases are used, there are problems in terms of controlling electrical or photoelectric properties. This is effective because the content of hydrogen atoms (H), which is extremely effective, can be easily controlled. When the above-mentioned hydrogen octochloride or the above-mentioned halodane-substituted silicon hydride is used, hydrogen atoms (H) are also introduced at the same time as the halogen 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 halodane atoms, a gas of the above-mentioned halodane compound or a silicon compound containing the above-mentioned octarodane 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 H2 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, a Si target is used, and a plasma atmosphere is created by introducing a gas for introducing halogen atoms and H2 gas, including an inert gas such as HeXAr as necessary, into the deposition chamber. , K on the support by sputtering the Si target.
A layer consisting of a-Si (H,X) is formed.

To form a layer composed of a-8iGe (H,
) and hydrogen atoms (H
) or/and halogen atoms (hydrogen atoms (
A raw material gas for supplying H) or/and 8-rodan 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 to place it at a predetermined position in advance. a-8iG on a predetermined support surface.
A layer composed of e(H,X) is formed.

As a material that can be used as the raw material gas for supplying 8i, the raw material gas for supplying 8-rodan atoms, and the raw material gas for supplying hydrogen atoms, a layer composed of the above-mentioned a-8i (H, X) is formed. The one used in the case will be used as is.

In addition, the substances that can be the raw material gas for supplying Ge include GeH, Ge2H6, Ge, H, Ge, H
lo.

Ge 5 H12, Ge6H14, C) e7H16, G
Germanium hydride in a gaseous state or capable of being gasified can be used. especially,
GeH, Ge 2 H6 and Ge3H are preferred from the viewpoint of ease of handling during layer creation work and good Ge supply efficiency.

a-8iGe (H,X) by sputtering method
To form a layer consisting of a silicon target and a germanium target, or a silicon target and a germanium target, sputtering is performed in a desired gas atmosphere. It is done by

a-8iGe(H,X
), for example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated using a resistance heating method or This can be accomplished by heating and evaporating by an electron beam method (E, B, method) or the like, 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 halodane 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 H2 or the above gases such as hydrogenated silanes and/or damanium hydride, is introduced into the deposition chamber for sputtering. A plasma atmosphere of gases such as the like may be formed. Further, as the raw material gas for supplying 8r/atoms, the above-mentioned helogonides or halogen-containing silicon compounds are effective, but in addition, HP.

HC11XHBr, hydrogenated hydrogen such as HI, 5IH
2F2.5iH2I2.5iH2CA! 2.5iHCA
Halodane-substituted silicon hydride such as 3.5iH2Br2.5iHBr3, and GeHF3, GeH2F2, GeH
3F, GcHC113, GeH2Cd, ,GeH3
ClsGeHBr3, GeH2Br2, GeH3Br,
GeHI3, (JeH2I2, ()eH3I, etc.), hydrogenated halodanium dermanium, etc., Gem, ()ec74
, GeBr, , GeI4, GeF2, GeCJ? 2,
Gaseous or gasifiable substances such as GeBr2, GeI2, etc. t7) Dalmanium halide, etc. can also be used as effective starting materials.

Forming a photoreceptive layer made of amorphous silicon containing tin atoms (hereinafter referred to as "a-8iSn(H,X)J") using a glow discharge method, sputtering method, or ion blating method. To do so, a-8iGc':H as described above.

When forming a layer consisting of This is done by making it contain.

Substances that can be used as the raw material gas for supplying tin atoms (Sn) include tin hydride (snH+), SnF2, and SnF2.
,,5nC7z,S nC114,S n B r 2
, SnBr4. A gaseous or gasifiable tin halide such as SnI2, SnI, etc. can be used, and when tin halide is used, it is composed of a-8i containing halogen atoms on a predetermined support. Of these, 5nlJ+ is preferable from the viewpoints of ease of handling during layer formation work, good Sn supply efficiency, etc., which is particularly effective.

When 5nC114 is used as a starting material for supplying tin atoms (Sn), in order to gasify it, solid 5nC1l+ is heated and an inert gas such as Ar1He is blown into the inert gas. The gas thus generated is preferably introduced into a deposition chamber with a reduced pressure inside at a desired gas pressure.

a-8i(H) using a glow discharge method, sputtering method, or ion blating method.

X) or a-Si (Ge, Sn) (H,
) to form a layer composed of an amorphous material further containing Group V atoms, nitrogen atoms, oxygen atoms, or carbon atoms, a-8i (H, −
When forming a layer of 8i (Ge, 5n) (H, Alternatively, the starting material for introducing carbon atoms may be the a-8i (H,
) or a-8i (Ge, 5n) (H,

For example, using the glow discharge method, atoms (0, C.

A layer composed of a-8i (H,X) containing N) or a-8i (Ge,
5n) (H,X), the layer composed of a-8i (H,
e, 5n) (H,
The starting material for introducing atoms (0, C, N) is a - Si
(H,X) or a-Si (Ge, S
n) (H,

As the starting material for such introduction of atoms (0, C9N), almost any gaseous substance or substance that can be gasified can be used, as long as it has at least an atom (0#C1N) as a constituent atom.

Specifically, as a starting material for introducing oxygen atom (0),
For example, oxygen (02), ozone (03), -nitrogen oxide (
No□), -nitrogen dioxide (N20), nitrogen sesquioxide (
N2O3), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N205), nitrogen trioxide (NO), silicon atom (S
i), an oxygen atom (0), and a hydrogen atom (H) as constituent atoms. For example, disiloxane (H3S iO81H3), To! J Shiroki”j 7
Examples include lower siloxanes such as (H3SiO81H203iH3), and starting materials for the introduction of carbon atoms include, for example, methane (CH4), eta7 (C2H6), propa7 (C3H8), n-butane ("-04HIO )
, C1-5 saturated hydrocarbons such as pentane (C3H12), ethylene (C2H4), propylene (C3H6)
, butene-1 (C4H8), butene-2 (c4Hg),
Isobutylene (C4H11), Pentene (C3HIO)
Ethylene hydrocarbons having 2 to 5 carbon atoms, such as acetylene (
C2H2), methylacetylene (C3H4), butyne (
Examples of starting materials for introducing nitrogen atoms (N) include nitrogen (N2), ammonia (NH,), hydrazine (NH2NH2), Hydrogen azide (HN3), ammonium azide (NH4N5), nitrogen trifluoride 0's
N), nitrogen tetrafluoride (F4N), and the like.

For example, using a glow discharge method, sputtering method or ion grating method, a-8t (H,X) or a-8i (G
e, 5nXH,X), the above-mentioned a-8i(H,X) or a-8i
When forming a layer composed of (Ge, 5n) (H,
a-8i (H,X) or a-8t (Ge, 5n
) (H,

Specifically, starting materials for introducing group (III) atoms include B2H6, B4HI01BsHo, B4HI01BsHo, and
s HII, Be Ht. , B6HIm, B6H14, and boron halides such as BF, , BCI, and Blur8. In addition, All Clls
, GaC65, Qa (CHs )z, InC65, T
lCe5 etc. can also be mentioned.

As starting materials for introducing Group V atoms, specifically for introducing phosphorus atoms, hydrogen ratios such as PH3, PtH6, etc., and PH4
I, PFs, PF PCl,, PC6s1PB r,,
Examples include halogen ratios such as PBr, PI, etc. In addition, ASHs, AsF5, ASCIs, ASB
r3, A S F3, S b Hs, 5bFs, 5
l) Fs, 5bC6s% 5bC6s, BiH,
B1Ce1, B+13r5, etc. 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 (St), a raw material gas containing oxygen atoms (0), and hydrogen atoms (H) or/and halogen atoms (X) as necessary.
A raw material gas containing constituent atoms is mixed with sulfur at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and oxygen atoms (0) and hydrogen atoms (H) are used. Either the raw material gas containing constituent atoms is mixed at a desired mixing ratio, or the raw material gas containing silicon atoms (Si) and silicon atoms (Si), oxygen atoms (
0) and hydrogen atoms (F()) can be mixed and used.

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), ozone (0,), -
Nitric oxide (NO), nitrogen dioxide (Nov), -nitrogen dioxide (N20), nitrogen sesquioxide (N20.), trinitrogen tetraoxide (N204), nitrogen sesquioxide (N20S), nitrogen trioxide (NOx), silicon The constituent atoms are an atom (Si), an oxygen atom (0), and a hydrogen atom (H), for example,
Examples include lower siloxanes such as DUSHIROKI+j/(HsSjOSiH3-trisiloxane (H3SiO8iX0Si)L).

K, which forms the oxygen atom-containing layer or layer region by the Me/Cuttering method, is a monocrystalline or polycrystalline Si wafer or S10. Wafer or Sl and S
This can be carried out by using a wafer containing a mixture of IO□ as a target and sintering the wafer in an atmosphere of various gases.

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. The S1 wafer may be sputtered by introducing these gases into the atmosphere and forming a gas plasma of these gases.

Alternatively, Si and Sin may be used as separate targets, or by using a mixed target of Sl and Sin, in an atmosphere of dilution gas as a sputtering gas or at least It can be formed by sputtering in a gas atmosphere containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms.

As the raw material gas for introducing acid and elementary atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example mentioned above is Suno J? It can also be used as an effective gas in the case of vine ring.

For example, in order to form a layer made of amorphous silicon containing carbon atoms by a glow discharge method, a raw material gas containing silicon atoms (Sl) as constituent atoms and a raw material gas containing carbon atoms (C) as constituent atoms are used. A raw material gas containing hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms may be mixed at a desired mixing ratio, or silicon atoms (Si) may be used. The raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms is mixed at a desired mixing ratio, or the raw material gas containing silicon atoms (Sl) as constituent atoms is mixed at a desired mixing ratio. A raw material gas containing atoms and a raw material gas containing silicon atoms (Si), carbon atoms (C), and hydrogen atoms (H) are mixed, or furthermore, silicon atoms (Si) and hydrogen atoms (H) are mixed. A raw material gas containing carbon atoms (C) as constituent atoms and a raw material gas containing carbon atoms (C) as constituent atoms are mixed and used.

3i is effectively used as such raw material gas.
and H as constituent atoms 5LH4, S2H6, S's
Silicon hydride gas such as silanes such as Hg, Si, H, etc., saturated hydrocarbons having 1 to 4 carbon atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, and ethylene series having 2 to 4 carbon atoms. Examples include hydrocarbons and acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, as a saturated hydrocarbon, methane (CH4)
, eta:/ ((4Ha l property (C3H1l)
, n-butane ("C4HIG), pentane (CsH
tt), ethylene hydrocarbons include ethylene (ct
u4).

Propylene (C3H6), butene-1 (c4Hs), butene-2 (C4HA), isobutylene (C,H,), pentene (C5HIO), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C,H
, ), butyne (c, t Ha ), and the like.

As a raw material whose constituent atoms are Si, C, and H, s
Alkyl silicides such as I(c H3) and Si (C2us)4 can be mentioned. 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-8iC (H,
This is carried out by sputtering a wafer mixed with these materials in a desired gas atmosphere as a target.

For example, when using a Si wafer as a target, ArJ (e
SI is diluted with a diluent gas such as, and introduced into a deposition chamber for sputtering to form a gas plasma of these gases.
All you have to do is sputter the wafer.

In addition, when Si and C are used as separate targets, or when Si and C are used as a mixed target, the raw material for introducing hydrogen atoms and/or halogen atoms is used as a gas for sumi 4 tsuttering. The gas may be diluted with a diluting gas as necessary, introduced into a deposition chamber for sputtering, and gas plasma may be formed to perform sputtering. As the raw material gas for introduction of each atom used in the sintering 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 containing silicon atoms (Si) k constituent atoms, a raw material gas containing nitrogen atoms (N) constituent atoms, hydrogen atoms (H) or/and halogen atoms (X
) with a raw material gas having constituent atoms at a desired mixing ratio, or a raw material gas having silicon atoms (Sl) with nitrogen atoms (N) and hydrogen atoms (H).
This can also be used by mixing it with a raw material gas having constituent atoms at 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).

The starting material that is effectively used as a raw material for introducing nitrogen atoms (N) used when forming a layer or layer region containing nitrogen atoms has N as a constituent atom or a mixture of N and H.
For example, nitrogen (N2), ammonia (
NUS), hydrazine (NH, NHz), hydrogen azide (HN, ), ammonium azide (NH4Ng)
Mention may be made of nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides and asoxides. In addition to this,
Nitrogen halides such as nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4 r'r ) are mentioned because in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced. be able to.

In order to form a layer or layer region containing nitrogen atoms by the sintering or stumbling method, monocrystalline or polycrystalline SL
Wafer or Si, N, wafer or Si and S
Sputtering may be performed using a wafer containing a mixture of i and N as a target in an atmosphere of various gases.

For example, if a Si 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 diluting gas as necessary, and a deposition chamber for sputtering is prepared. 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 Si and 5J3N4 as separate targets or using a single mixed target of Sl and S'3N4, it is possible to use at least one hydrogen atom in an atmosphere of dilution gas as a sputtering gas. It can be formed by sputtering in a gas atmosphere containing (H) or/and halogen atoms (X)' (c as constituent atoms. As the raw material gas for introducing nitrogen atoms, the raw materials shown in the glow discharge example described above can be used. The raw material gas for introducing nitrogen atoms into the gas can also be used as an effective gas in the case of starch ringing.

As described above, the light-receiving layer of the light-receiving member of the present invention is formed using a glow discharge method, a sputtering method, etc. Alternatively, the content of Group V atoms, oxygen atoms, carbon atoms, nitrogen atoms, or hydrogen atoms and/or halogen atoms can be controlled by controlling the gas flow rate of each atom-supplying starting material flowing into the deposition chamber or each of them. This is done by controlling the gas flow ratio between the starting materials for supplying the atoms.

In addition, conditions such as the support temperature, gas pressure in the deposition chamber, and discharge power during formation of the photosensitive layer and surface layer are important factors in obtaining a light-receiving member with desired characteristics, and the conditions for forming the layer. It is selected appropriately taking into consideration the function. Furthermore, these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be included in the photosensitive layer and surface layer, so they are determined by taking into consideration the type and amount of atoms to be included. There is also a need to do so.

Specifically, when forming a photoreceptive layer made of a-8i (H, Particularly preferably, the temperature is 50 to 250°C. The gas pressure in the deposition chamber is usually 0.01 to 1'l'orr, particularly preferably 0.1 to 0.5 Torr. Also,
The discharge nozzle is usually 0.005 to 50 W/cm2, but more preferably 0.01 to 30 W/cm2,
Particularly preferably, it is O1 old to 20 W/cm'.

When forming a photosensitive layer consisting of a-3iGe (H, The support temperature is usually 50 to 350°C, more preferably 50 to 300°C, particularly preferably 100 to 300'C. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, particularly preferably 0.00 Torr.
1 to 1 Torr. Also, the discharge power is 0.005
~50 W/art! It is usually 0.01 to 30 W/a!, but preferably 0.01 to 30 W/a! and particularly preferably 0
, 01 to 20 W/cm'.

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

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

The discharge power and gas pressure vary depending on the type of gas used, the material of the support, the shape of the support surface, 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 halodan atoms contained in the photosensitive layer of the present invention is uniform. In order to achieve this, 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 1 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 gas flow rate can be changed by using any commonly used method, such as manually or using an externally driven motor, or by opening a predetermined needle pulp provided in the middle of the gas flow path system. What is necessary is to perform an operation to gradually change the value. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

In addition, when forming the photoreceptive layer using a sputtering method, the distribution concentration in the layer thickness direction of germanium atoms, tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, group 1 atoms, or group V atoms is determined in the layer thickness direction. In order to form a desired distribution state in the layer thickness direction, germanium atoms, tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, group The starting material for introducing group V atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is varied according to the desired rate of change.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to Examples 1 to 11, but the present invention is not limited thereto.

In each example, the photoreceptive layer was formed using a glow discharge method. FIG. 29 shows an apparatus for manufacturing a light-receiving member of the present invention using a glow discharge method.

2902, 2903, 2904, 2905 in the diagram
, 2906 is sealed with raw material gas for forming each layer of the present invention.
99%) cylinder, 2903 is B2H diluted with H2,
Gas (purity 99.999%, hereinafter abbreviated as BzHe/Hz) cylinder, 2904 is CH, gas (purity 99.9
99%) H7, 2905 is GeF, gas (purity 99.
999%) cylinder, 2906 is inert gas (He)
It's a cylinder.

2906' is a sealed container containing S nCt)4.

In order to flow these gases into the reaction chamber 2901, the gases 292 to 292 are supplied to the pulp 2922 of the gas cylinders 2902 to 2906.
6. Confirm that the IJ-Kvalp 2935 is closed, and also check that the inflow pulps 2912 to 2916 and the outflow pulp 2
917-2921, auxiliary pulp 2932, 2933
Make sure that the main pulp 29 is opened and
34 is opened to exhaust the inside of the reaction chamber 2901 and gas piping.

Next, an example of forming the first layer and the second layer on the vacuum A6 cylinder 2937 will be described below.

First of all, gas cylinder 2902, S i F, gas gas pump 2903! l) Bt Ha /Hz gas, each of GeF4 gas from Subinpe 2905 2922.2923.

Open 2925 and outlet pressure gauges 2927, 2928
.

2930 pressure! /cIIL2 and gradually open the inflow pulps 2912, 2913, 2915, mass 70 controller, 2907, . 2908,
2910. Subsequently, outflow pulp 2
917, 2918.

2920 , the auxiliary pulp 2932 is gradually opened to allow gas to flow into the reaction chamber 2901 . S i H at this time
4 gas flow rate, GeF4 gas flow rate, and BtHa/Hz gas flow rate to the desired values.
, 2918 , 2920 , and the reaction chamber 29
Adjust the opening of the main pulp 2934 while checking the reading on the vacuum gauge 2936 so that the pressure inside the main pulp 2934 reaches the desired value. 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 and glow discharge is caused in the reaction chamber 2901. At the same time, using a microcomputer (not shown), the S
While controlling the gas flow rates of iF gas, GeF4 gas, and Bt H6/Hz gas, the base cylinder 293
First, a layer 102' containing silicon atoms, germanium atoms, and boron atoms is formed on the substrate 7. At the stage when the layer 102' has been formed to a desired thickness, the effluent pulp 29
18, 2920'r completely closed, and by continuing glow discharge according to the same procedure except changing the discharge conditions as necessary, a layer 102'' that does not substantially contain germanium atoms is formed on the 9th layer 102'. can be formed.

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, Ar, or H2 as necessary. This is accomplished by flowing the gas into the reaction chamber 2901 at a desired flow rate and generating glow discharge according to desired conditions.

It goes without saying that all the outflow pulps other than the outflow pulp for the gas necessary to form each layer are closed, and when all the layers are formed, the gas used to form the previous layer is inside the reaction chamber 2901 and the outflow pulp is closed. In order to avoid remaining in the gas pipe leading from the pulps 2917 to 2921 into the reaction chamber 2901, the outflow pulps 2917 to 2921 are closed and the auxiliary pulp 2932 is removed.

2933, fully open the main pulp 2934, and temporarily evacuate the system to high vacuum, as necessary.

In addition, when containing tin atoms in the first layer and using a gas containing S n C1 as a starting material, the solid 5 in the 2906'
nCl is heated using a heating means (not shown), and an inert gas of % Ar and He is blown into the 5nC 14 from an inert gas cylinder 2906 such as Ar s He to cause bubbling. The generated 5nCe and gas are
The aforementioned SiF, gas, GeF, gas and B2H6/H2
It is made to flow into the reaction chamber using the same procedure as gas etc.

Example 1 A cylindrical A6 base (length 357 mm) was used as a support.
-, a diameter of 80 mm) was formed with 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 (
It was shown in Figure 0. Note that FIG. 30(A) is an overall view of the A4 support, and FIG. 30(A) is a view showing a cross-sectional shape of a part of its surface.

Next, on the Al support, under the conditions shown in Table 1 below,
A light-receiving layer was formed using the manufacturing apparatus shown in FIG.

When the layer 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. The difference in average layer thickness between the center and both ends was 2 μm.

Further, regarding this light-receiving member, using the image exposure apparatus shown in FIG.
Image exposure was performed by irradiating a laser beam of m, 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 radar+, 3103 is an fθ lens, and 3104 is a polygon mirror.

Example 2 A photoreceptive layer was formed on an Al support in the same manner as in Example 1, except that the photoreceptive layer was formed according to the layer forming conditions shown in Table 2. At this time, Ge at the time of forming the first layer
Changes in the F, gas, and SiF gas flow rates were automatically adjusted by microcomputer control according to the flow rate change line shown in FIG.

When the difference in the layer thickness of the photoreceptive layer within the microscopic portion of the photoreceptive member thus obtained 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. Further, the difference in average layer thickness between the center of the cylinder and both ends of the photoreceptive layer was 2.3 μm.

Furthermore, when images were formed on this light-receiving member in the same manner as in Example 1, no interference fringes were observed in each image, and an image showing good practical electrophotographic properties was obtained. .

Example 3 In the same manner as in Example 1, the 30th (A6 support body (cylinder depths 301 to 303) having the cross-sectional shape shown in Figures Q to ■) was prepared.
I got it.

A photoreceptive layer was formed on the A6 support (cylinders 301 to 303) according to the layer forming conditions shown in Table 3.

Incidentally, the gas flow rates of GeH, gas, stH, gas, and NH3 gas during the first layer formation were automatically adjusted by a microcomputer according to the flow rate change line shown in FIG.

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.

Further, 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 11 AJ support (
A photoreceptive layer was formed on the cylinders 11 & L301 to 303). At this time, in each Example, the gas flow rate of the gas used during the first layer formation was automatically adjusted by microcomputer control according to the flow rate change lines shown in FIGS. 34 to 41, respectively. Further, in each example, the boron atoms contained in the first layer are Bz Ha /S i F
4 +GeF4, and approximately 200 ppm was introduced into the entire layer.

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

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

, [Summary of Effects of the Invention] The light-receiving member of the present invention has the above-described layer structure, thereby solving all of the problems of the light-receiving member having a light-receiving layer made of amorphous silicon. In particular, even when laser light, which is coherent monochromatic light, is used as a light source, it significantly prevents the appearance of interference fringes in images formed due to interference phenomena, and forms extremely high-quality visible images. be able to.

Furthermore, 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. It responds quickly and also exhibits extremely excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment characteristics.

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

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing the layer structure of the light-receiving member of the present invention, and FIGS. 2 to 4 illustrate 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 FIG. 2, and FIG. The figure compares the intensity of reflected light when the interfaces of the constituent layers provided on the support are parallel and non-parallel. Figure 4 shows that the first layer has two or more layers. FIG. 3 is a diagram illustrating prevention of occurrence of interference fringes in the case of zero multilayers. 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. 6th to 10th
The figures are diagrams illustrating the generation of interference fringes in a conventional light-receiving member, in which FIG. 6 shows the generation of interference fringes in the photoreceptive layer, and FIG. Generation, Figure 8 shows the generation of interference fringes due to scattered light, and Figure 9 shows the generation of interference fringes due to scattered light.
Generation of interference fringes due to scattered light in a multilayer photoreceptive layer. FIG. 10 shows the generation of interference fringes when the interfaces of the constituent layers of the photoreceptor layer are parallel. 11th to 19th
The figure shows the distribution state of germanium atoms or tin atoms in the layer thickness direction in the first layer of the present invention. It is a diagram showing the distribution state of at least one selected from carbon atoms and nitrogen atoms, or Group 1 atoms or Group V atoms in the layer thickness direction, and in each diagram, the vertical and horizontal directions indicate the layer thickness of the first layer. , and the horizontal axis represents the distribution concentration of each atom. FIG. 29 is an example of an apparatus for manufacturing the first layer and second layer of the light-receiving member of the present invention, and is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. Figure 30 is an overall view of forming the support of the light receiving member of the present invention by mechanical processing using a lathe, and Figures 30) to [F] show the cross-sectional shape of a part of the surface of the support. FIG. FIG. 31 is a diagram illustrating an image exposure device using laser light. 32 to 41 are diagrams showing changes in gas flow rate in the first layer formation of the present invention, where the vertical axis shows the layer thickness of the first layer, and the horizontal axis shows the gas flow rate of the used gas. There is. Regarding FIGS. 1 to 4, 100... Light receiving member 101... Support body 10
2, 202, 302, 402...first layer 10
2'... Layer 102 containing at least one of germanium atoms or tin atoms''... Layer 103, 203, 303, 403... Second layer 402 containing neither germanium atoms nor tin atoms ', 402''...Layer 1 constituting the first layer
04, 204, 304...free surface 205, 3
05... Interface between the first layer and the second layer Regarding Figures 6 to 10, 601... Lower interface 602... Upper interface 7
01...Support 702, 703...Photoreceptive layer 801...Support 802...Photoreceptive layer 9
01...Support 902...First layer 903...
Second layer 1001...Support 1002...Photoreceptive layer 1003...Support surface 1004...Photoreceptive layer surface Regarding FIG. 29, 2901...Reaction chambers 2902-2906...Gas cylinder 2906 '-sncga airtight containers 2907 to 2911...mass flow controller 291
2-2916... Inflow pulp 2917-2921... Outflow pulp 2922-2926... Valve 2927-2931... Pressure regulator 2932, 2933... Auxiliary pulp 2934...
Main pulp 2935...Leak pulp 2936...
...Vacuum gauge 2937...Base cylinder 29
38... Heater 2939... Motor 29
40... High frequency power source Fig. 31, 3101... Light receiving member 3102... Semiconductor laser 3103... fθ lens 3104...
Polygon mirror Figure 3 (A) (B) (C)
^Q
Rono

Figure 8 Figure 9 Figure 10 Location Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 □C Figure 17 Figure 18 □C Figure 20 Figure 21 □C Figure 26 Figure 30 (IE) (Shiom) (j/m) (AII) Procedural amendment (method) February 20, 1985 Mr. Michibu Uga, Commissioner of the Patent Office■, Indication of the case 1985 patent Application No. 256647 2 Name of the invention Photoreceptor member 3 Relationship to the amended case Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo 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 (Shipping date: January 28, 1986) 6 , Description and drawings to be amended 7, Contents of amendment A copy of the original description and drawings attached to the application (no change in content)

Claims (17)

[Claims] (1) A first layer composed of an amorphous material containing silicon atoms, silicon atoms, atoms selected from oxygen atoms and nitrogen atoms, hydrogen atoms and halogen atoms, on a support. and a second layer made of an amorphous material containing atoms selected from the group consisting of germanium atoms or tin atoms, the first layer comprising germanium atoms or tin atoms. It has a multilayer structure including a layer containing at least one of germanium atoms and a layer containing neither germanium atoms nor tin atoms in order from the support side, and the surface of the support has a plurality of sub peaks superimposed on the main peak. 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 A light-receiving member characterized in that a large number of interfaces are arranged in at least one direction within a plane perpendicular to the layer thickness direction. (2) Claims in which the second layer is made of an amorphous material containing silicon atoms, at least one type selected from oxygen atoms, and nitrogen atoms in a uniform distribution state. The light-receiving member described in item (1). (3) The light according to claim (1), wherein the first layer contains atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms, and which are not contained in the second layer. Receptive member. (4) The light-receiving member according to claim (1), wherein the first layer contains a substance that controls conductivity. (5) The light-receiving member according to claim (1), wherein the first layer has as one of the constituent layers a charge injection blocking layer containing a substance that controls conductivity. (6) The light-receiving member according to claim (1), wherein the first layer has a barrier layer as one of the constituent layers. (7) The light-receiving member according to claim (1), wherein the non-parallel interfaces are regularly arranged. (8) The light-receiving member according to claim (1), wherein the arrangement of non-parallel interfaces is periodic. (9) The light receiving member according to claim (1), which has a short range of 0.3 to 500μ. (10) Claim No. 1, wherein the support body is cylindrical (
The light-receiving member according to item 1). (11) The light-receiving member according to claim (10), wherein the uneven shape provided on the surface of the support body forms a linear protrusion having a spiral structure. (12) The light receiving member according to claim (11), wherein the spiral structure is a multi-spiral structure. (13) The light-receiving member according to claim (11), wherein the linear protrusion is divided in the direction of its ridgeline. (14) The light-receiving member according to claim (11), wherein the ridgeline direction of the linear protrusion is along the central axis of the cylindrical support. (15) The light-receiving member according to claim (1), wherein the unevenness provided on the surface of the support has an inclined surface. (16) The light-receiving member according to claim (15), wherein the inclined surface is mirror-finished. (17) The free surface of the photoreceptive layer is provided with minute irregularities arranged at the same pitch as the minute irregularities provided on the support surface. Light-receiving member.