JPS6194052A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To obtain a photoreceptive member for laser light, etc. which is suitable for image formation by forming the photoreceptive member into multiple layers and providing a surface layer thereto to constitute said member and incorporating O, C and N atoms therein to provide the boundary face non- parallel within a short range. CONSTITUTION:The photoreceptive member layer 1000 is constituted on a base 1000. The 1st layer 1002 thereof is formed of amorphous silicon contg. Si and Ge in which Ge is uniformly distributed. The 2nd layer 1003 is formed of the amorphous silicon contg. Si to have photoconductivity. The surface layer 1006 is formed thereon to have moisture resistance, continuous use characteristic and electrical voltage resistance characteristic. The O, C, N atoms, etc. are incorporated into the layer 1000 to provide high light sensitivity and high dark resistance. The boundary face of these layers is made non-parallel in a short range and is formed with ruggedness to prevent interference. The resulted photoreceptor is therefore suitable for the image formation for which the laser light is used. Said photoreceptor eliminates interference fringes and spots in the stage of reversal development.

Description

[Detailed Description of the Invention] Field of Use of Ctlr Industry 1-] The present invention is directed to the use of light (light in a broad sense here, such as ultraviolet rays, visible light,
It relates to a light-receiving member that is sensitive to electromagnetic waves such as infrared rays, X-rays, gamma rays, etc. More specifically, the present invention relates to a light receiving member suitable for using coherent light such as laser light.

[Prior art]

To record digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is developed. A well-known method is to perform processing such as transfer and fixing as necessary to record an image. Among these, in the image forming method using electrophotography, image recording is generally performed using a small and inexpensive He--Ne laser or semiconductor laser (usually 650 to 650 nm).

In particular, as a light-receiving member for electrophotography that is suitable when using a semiconductor laser, it has a much better consistency in the photosensitivity region than other types of light-receiving members, and also has a Vickers hardness. For example, JP-A No. 54-88341 and JP-A No. 58-8
A light-receiving member made of an amorphous material containing silicon atoms (hereinafter abbreviated as "ra-9i") disclosed in Japanese Patent No. 3748 is attracting attention.

If the photoreceptive layer is a single-layer a-9i layer, in order to maintain its high photosensitivity and ensure a dark resistance of 1012 ΩCm or more required for electrophotography, hydrogen atoms, halogen atoms, or In addition to this, it is necessary to structurally contain poron atoms in a specific amount range in a controlled manner in the layer, so it is necessary to strictly control the layer formation, etc. There are considerable limitations on the tolerances in the design.

This design allows for greater tolerance. For example, Japanese Patent Application Laid-Open No. 54-12174 is an example of a device that makes it possible to effectively utilize the high light sensitivity even if the dark resistance is low to some extent.
Publication No. 3, JP-A-57-4053, JP-A-57-
As described in Japanese Patent Laid-open No. 4172, the photoreceptive layer may have a two-layer structure in which layers having different conductivity characteristics are laminated to form a depletion layer inside the photoreceptor layer, or as described in Japanese Patent Laid-Open No. 1983-1989.
No. 52178, No. 52179, No. 52180, No. 5
As described in Patent Publications No. 8159, No. 58180, and No. 58181, a multilayer structure in which a barrier layer is provided between the support and the photoreceptive layer or/and on a part of the surface of the photoreceptive layer may be used. Accordingly, light-receiving members with apparently increased dark resistance have been proposed.

Through such proposals, the a-3i light-receiving members have made dramatic progress in terms of commercialization design (L) tolerance, and in terms of ease of management and productivity in manufacturing. The speed of development towards this is accelerating.

When laser recording is performed using a light-receiving member with such a multilayered light-receiving layer, the thickness of each layer is uneven, and the laser light is coherent monochromatic light. Reflected from the free surface of the laser beam irradiation side, each layer constituting the light-receiving layer, and the layer interface between the support and the light-receiving layer (hereinafter, both the free surface and the layer interface are collectively referred to as the "interface"). Each of the incoming reflected lights can cause interference.

This interference phenomenon causes the so-called,
This appears as an interference fringe pattern and causes one image defect. Particularly when forming a half-tone image with high gradation, the image becomes noticeably unsightly.

Furthermore, as the wavelength region of the semiconductor laser light used becomes longer, the absorption of the laser light in the photoreceptive layer decreases, so the above-mentioned interference phenomenon is remarkable.

This point will be explained with reference to the drawings.

FIG. 1 shows light incident on a certain layer constituting the light-receiving layer of a light-receiving member. and the reflected light R1 reflected at the upper interface 102,
The reflected light R2 reflected at the lower interface +01 is shown.

Assuming that the average layer thickness of the layer is d, the refractive index is n, and the wavelength of light is λ, if the layer thickness of a certain layer is uneven with a gradual thickness difference of 71"- or more, the reflected light R1+R2 will be 2nd= m (
Depending on whether m is an integer, the reflected light strengthens each other) or 2nd-(m+1) (m is an integer, the reflected light weakens each other), the amount of light absorbed by a layer and the transmitted light change. arise.

In a light-receiving member having a multilayer structure, interference effects (as shown in FIG. 1) occur in each layer, and as shown in FIG. 2, a synergistic adverse effect occurs due to each interference. Therefore, interference fringes corresponding to the interference fringe pattern appear in the visible image transferred and fixed onto the transfer member, causing a defective image.

To solve this problem, the surface of the support is diamond-cut to provide a cutting edge of ±500A to ±too.

A method of forming a light-scattering surface by providing unevenness on the surface (for example, JP-A-58-182975). The surface of the aluminum support is treated with black alumite, or carbon, colored pigments, or dyes are dispersed in the resin. method of providing a light absorption layer (for example, Japanese Patent Application Laid-Open No. 11115845/1984),
A method of providing a light scattering and antireflection layer on the surface of an aluminum support by subjecting the surface of the support to a satin-like alumite treatment or by sandblasting to provide fine grain-like irregularities (for example, JP-A-57-18554). etc. have been proposed.

Unfortunately, these conventional methods have not been able to completely eliminate the interference fringe pattern that appears on images.・In other words, in the first method, only a large number of irregularities of a specific size are provided on the surface of the support, so although it does prevent the appearance of interference fringes due to light scattering effects, Since the specularly reflected light component still remains, in addition to the interference fringe pattern remaining due to the specularly reflected light, the irradiation spot spreads due to the light scattering effect on the support surface. This was the cause of a substantial reduction in resolution.

In the second method, complete absorption is impossible with the black alumite treatment, and the reflected light on the surface of the support remains. In addition, when a colored pigment dispersed resin layer is provided, when forming the a-9i layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed light-receiving layer is significantly deteriorated. 9i
It has disadvantages such as being damaged by plasma during layer formation, reducing its original absorption function, and adversely affecting the subsequent formation of the a-3i layer due to deterioration of the surface condition.

In the case of the third method of irregularly roughening the surface of the support, as shown in FIG. ,The rest,
The light enters the inside of the light-receiving layer 302 and becomes transmitted light I. Transmitted light 1. On the surface of the support 302, a part of the light is scattered and becomes diffused light, 2. 3..., the rest is specularly reflected and becomes the reflected light R2, and a part of it becomes the emitted light R3 and goes outside. Therefore, reflected light R1
Since the emitted light R3, which is a component that interferes with the light, remains, the interference fringe pattern cannot be completely erased.

Furthermore, in order to prevent interference and prevent multiple reflections inside the light-receiving layer, if the diffusivity of the surface of the support 301 is increased,
Another drawback was that the resolution was reduced because light was diffused within the light-receiving layer, causing halation.

In particular, in a light-receiving member having a multilayer structure, as shown in FIG. light R1
, the specularly reflected light R3 on the surface of the support 401 interferes with each other,
An interference fringe pattern occurs depending on the thickness of each layer of the light-receiving member.

Therefore, in a light-receiving member having a multilayer structure, the support 40
It has been impossible to completely prevent interference fringes by irregularly roughening the surface.

In addition, when the surface of the support is irregularly roughened by methods such as sandblasting, the degree of roughness varies greatly between lofts, and even in the same lot, the degree of roughness is uneven, making it difficult to manufacture. Management - ■ - I was not feeling well. In addition, relatively large protrusions are frequently formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer.

In addition, if the support surface 501 is simply roughened regularly, the fifth
As shown in the figure, the light-receiving layer 502 is usually deposited along the uneven shape of the surface of the support 501.
The sloped surface of the unevenness of the light-receiving layer 502 becomes parallel to the sloped surface of the unevenness of the light-receiving layer 502.

Therefore, in that part, the incident light satisfies 2ndl-m input or 2nd1=(m slave stations) λ, resulting in a bright part or a dark part, respectively. Further, in the entire photoreceptive layer, the layer thickness of the photoreceptive layer is d+, d2. d3. Due to the difference in d+, a bright and dark striped pattern appears.

Therefore, just by regularly roughening the surface of the support 501,
It is not possible to completely prevent the occurrence of interference fringes.

Furthermore, even when a multi-layered light-receiving layer is deposited on a support-L whose surface is regularly roughened, the specularly reflected light on the surface of the support as explained for the single-layered light-receiving member in FIG. In addition to the interference with the reflected light on the surface of the light-receiving layer, interference due to the reflected light at the interface between each layer is added, so that the degree of interference fringe pattern development becomes more complicated than that of a single-layered light-receiving member. [Object of the invention] The object of the present invention is to provide a new light-sensitive light-receiving member which eliminates the above-mentioned drawbacks.

Another object of the present invention is to provide a light-receiving member that is suitable for image formation using coherent monochromatic light and that is easy to control in manufacturing.

Still another object of the present invention is to provide a light-receiving member that can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development.

Another object of the present invention is to provide a light-receiving member that has high electrical pressure resistance, high photosensitivity, and excellent electrophotographic properties.

Yet another object of the present invention is to provide a light-receiving member suitable for electrophotography that can obtain high-quality images with high density, clear halftones, and high resolution.

Another object of the present invention is to provide a light-receiving member that has excellent mechanical durability, particularly abrasion resistance and light-receptivity on the surface of the light-receiving member.

[Summary of the invention]

The present invention provides a first layer made of an amorphous material containing silicon atoms and germanium atoms, a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity, and a second layer made of an amorphous material containing silicon atoms, and a second layer made of an amorphous material containing silicon atoms. and a surface layer made of an amorphous material containing carbon atoms are provided in order from the support side, and the photoreceptive layer has a surface layer made of an amorphous material containing carbon atoms. containing at least one selected from the following, having one or more pairs of non-parallel interfaces in one short range, and having a large number of non-parallel interfaces in at least one direction in a plane perpendicular to the layer thickness direction. It is characterized by being arranged.

Hereinafter, the present invention will be specifically explained with reference to the drawings.

FIG. 6 is an explanatory diagram for explaining the basic principle of the present invention.

The present invention has a light-receiving layer having a multilayer structure along the slope of the unevenness on a support (not shown) having an uneven shape smaller than the required resolution of the device, and the light-receiving layer is shown in FIG. As shown in a partially enlarged view, since the layer thickness of the second layer 602 changes continuously from ds to d6, the interface 603 and the interface 604 have a tendency toward each other. Therefore, the coherent light incident on this minute portion (short range) 1 causes interference in the minute portion 1, producing a minute fringe pattern.

Furthermore, if the interface 703 between the first layer 701 and the second layer 702 and the free surface 704 of the second layer 702 are non-parallel as shown in FIG. Since the reflected light R1 and the emitted light R3 for the light ro have different traveling directions, when the interfaces 703 and 704 are parallel (r
(B) The degree of interference is reduced compared to J).

Therefore, as shown in Figure 7 (C), when a pair of interfaces are non-parallel (r (A) J) than when they are parallel (r (B) J), even if they interfere, there is no interference. S becomes so small that the difference in brightness of the striped pattern can be ignored.

As a result, the amount of light incident on the minute portions is averaged.

This is true even if the thickness of the second layer 602 is macroscopically non-uniform as shown in FIG. 6, so the amount of incident light is uniform over the entire layer area. (See r (D)J in Figure 6).

Furthermore, to describe the effects of the present invention in the case where coherent light is transmitted from the irradiation side to the second layer when the light-receiving layer has a multilayer structure, as shown in FIG. ■. On the other hand, there are reflected lights R,, R2, R2H,, R5.

Therefore, in each layer, what is described above similar to FIG. 7 occurs.

Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer, so according to the present invention, as the number of layers constituting the photoreceptive layer increases, the interference effect can be further prevented. I can do it.

Further, interference fringes generated within the minute portion do not appear in the image because the size of the minute portion is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. Furthermore, even if it appears in the image, it will not substantially interfere with the answer because it is below the resolution of the eye.

In the present invention, the uneven inclined surface is desirably mirror-finished in order to reliably align the reflected light in one direction.

The size of the minute part is suitable for the present invention! (one period of the uneven shape) is l≦L, where L is the spot diameter of the irradiation light.

In addition, in order to more effectively achieve the purpose of the present invention, the difference in layer thickness (ds d6) in the minute portion l is expressed as follows, where the wavelength of the irradiation light is taken as 1 - ds d6≧2n (n: The refractive index of the second layer 602 is preferably as follows.

In the present invention, within the layer thickness of a microscopic portion l of a multilayered photoreceptive layer (hereinafter referred to as a "microcolumn"), at least any two layer interfaces are in a non-parallel relationship. Although the layer thickness of each layer is controlled within the microcolumn, any two layer interfaces may be in a parallel relationship within the microcolumn as long as this condition is satisfied.

However, the layers forming parallel layer interfaces must have a uniform layer thickness over the entire area so that the difference in layer thickness at any two positions is 2 n (refractive index of the n' layer) or less. preferably formed.

In order to more effectively and easily achieve the object of the present invention, the first layer and the second layer constituting the photoreceptive layer are formed using the following methods.
The plasma vapor phase method (PCVD method), photo-CVD method, and thermal CVD method are employed because the layer thickness can be accurately controlled at an optical level.

The unevenness provided on the surface of the support can be achieved by fixing a cutting tool having a 7-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or lathe, and rotating the cylindrical support according to a program designed in advance as desired. By moving the support member regularly in a predetermined direction, the surface of the support member can be accurately cut to form a desired uneven shape, pitch, and depth. The inverted ■-shaped linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The spiral structure of the inverted V-shaped protrusion may be a double, triple, multiple spiral structure, or a crossed spiral structure.

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

The longitudinal cross-sectional shape of the convex and convex portions provided on the surface of the support is determined by the controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and by the fact that they are provided directly on the support and the support -1-. In order to ensure good adhesion and desired electrical contact between the layers, it is formed into an inverted V shape, but preferably it is formed into a substantially isosceles triangle or right triangle shape as shown in FIG. is preferably a scalene triangle. Among these shapes, isosceles pentagons and right triangles are particularly desirable.

In the present invention, each dimension of the unevenness provided on the surface of the support in a controlled manner is determined by considering the following points.
- is set so that the object of the present invention can be achieved as a result.

That is, firstly, the a-9i layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the layer quality changes greatly depending on the surface condition.

Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the a-9i layer.

Secondly, if the free surface of the photoreceptive layer is extremely uneven, it becomes impossible to perform cleaning completely after image formation.

Further, when cleaning the blade, there is a problem that the plate becomes damaged.

As a result of examining the above-mentioned problems in layer deposition, problems in the electrophotographic process, and the properties to prevent interference fringes, the pitch of the four parts on the surface of the support is preferably 500 μm to 500 μm.
Desirably it is 0.3u, more preferably 200μ to 1)ua, optimally 50u to 5μ.

Further, the maximum depth of the four parts is preferably 0. IQ~5μ
, more preferably 0.3-~3μ, optimally 0.6u~
It is most likely that he will be classified as a 2nd star. If the pitch and maximum depth of the four parts on the surface of the support are within the above range, the four parts (or the line -L
The inclination of the inclined surface of the protruding portion is preferably 1 degree to 20 degrees,
More preferably, the angle is 3 degrees to 15 degrees, most preferably 4 degrees to 10 degrees.

Further, the maximum difference in layer thickness based on the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0.1 g to 2 μ, more preferably 0.1 μ to 1 μ, within the same pitch. .5g
, the optimum value is preferably 0.2~tg.

The photoreceptive layer in the photoreceptive member of the present invention is composed of a first layer made of an amorphous material containing silicon atoms and germanium atoms and an amorphous material containing silicon atoms, and has photoconductivity. It has a multilayer structure in which a second layer exhibiting a Indicates environmental 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, it is highly sensitive, and it has a high signal-to-noise ratio. As a result, high-quality images with high density, clear halftones, and high resolution can be stably and repeatedly obtained with excellent light fatigue resistance and repeated use characteristics.

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, so it is particularly suitable for matching with semiconductor lasers. Fast light response.

In the light-receiving member of the present invention, the surface layer made of an amorphous material containing silicon atoms and carbon atoms provided on the second layer functions as a protective layer for mechanical durability and for optical protection. can be made to primarily function as an antireflection layer.

The surface layer described above is suitable for functioning as the anti-reflection layer 11 when the following conditions are met.

That is, when the refractive index of the surface layer is n, the layer thickness is d, and the wavelength of the incident light is: When d=coin or an odd multiple thereof, the surface layer is suitable as an antireflection layer.

Moreover, when the refractive index of the second layer is Da, when the refractive index n of the surface layer satisfies n=fia and the layer thickness d of the surface layer satisfies d"4"n, the surface layer is most suitable as an antireflection layer.

a-9i: When H is used as the second layer, a-9i
:H has a refractive index of about 3.3, so a material with a refractive index of 1.82 is suitable for the surface layer.

a-9iC:)l can be made to have such a refractive index by adjusting the amount of C, and the mechanical durability, interlayer adhesion, and electrical properties are also sufficiently satisfied. Therefore, it is the most suitable material for the surface layer.

Further, when the surface layer is intended to serve as an antireflection layer, the thickness of the surface layer is preferably 0.05 to 2 μ.

Hereinafter, the light receiving member of the present invention will be explained in detail according to the drawings.

FIG. 1θ is a schematic configuration diagram schematically shown to explain the layer configuration of a light receiving member according to an embodiment of the present invention.

A light-receiving member 1004 shown in FIG. 1O has a light-receiving layer 1000 on the support toot 1- for the light-receiving member, and the light-receiving layer 1000 has a free surface 1005 on one end surface. There is.

The light-receiving layer 1000 is made of a support 1001 containing a-3i (hereinafter ra-SiGe (
A first layer (G) composed of H, X) (abbreviated as J)
a-9i (hereinafter referred to as ra-5i) containing 1002 and a hydrogen atom or/and a halogen atom (X) as necessary.
(H, It has a layered structure.

In the light receiving member 1004 shown in FIG. 10, the surface formed on the second layer 1003-1-! 100B has an [IFb surface and is provided to achieve the objects of the present invention mainly in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, mechanical durability, and light receiving characteristics.

The surface layer 1006 in the present invention is composed of silicon atoms (Si
), a carbon atom (C), and optionally a hydrogen atom (H) and/or a halogen atom (X) (hereinafter, 'a-(SiXC+ -x)y (+(,X )
+-y J, where 0 < x, y < 1).

The surface layer 1006 composed of a-(Six cl 4 ) y (H,
method, thermal CVD method, sputtering method, electron beam method, etc. 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 photoconductive member to be manufactured. Gua-a- A discharge method or a sputtering method is preferably employed.

Furthermore, in the present invention, the surface layer 1006 may be formed using a glow discharge method and a sputtering method in the same apparatus system.

Surface layer by glow discharge method! To form 006,
The raw material gas for forming a-(S+XC,-X)y(H,X)+-y is mixed with a dilution gas at a predetermined mixing ratio as needed, and then the deposition chamber where the support is installed is prepared. The introduced gas is turned into gas plasma by generating a glow discharge, and the first gas which has already been formed on the support is
on the second layer (n) from a−(S!x C+ −X
)y (11,X) It is good to deposit ty.

In the present invention, a-(S+, c, -X)y (
H, Most gaseous substances or gasified substances that can be gasified can be used.

When using a raw material gas having Si as a constituent atom as one of Si, C, H, and X, for example, a raw material gas having Si as a constituent atom, a raw material gas having C as a constituent atom, If necessary, a raw material gas containing ■ as a constituent atom and/or a raw material gas containing X as a constituent atom may be mixed at a desired mixing ratio, or a raw material gas containing Si as a constituent atom,
Raw material gas containing C and H as constituent atoms and/or C and X
Also, a raw material gas containing Si as constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing Si as constituent atoms and a raw material gas containing Si, C, and H as constituent atoms or A raw material gas containing Si, C, and X as constituent atoms can be used in combination.

In addition, separately, a raw material gas containing Si and H as constituent atoms,
A raw material gas containing C as a constituent atom may be mixed and used, or a raw material gas containing Si and X as a constituent atom may be mixed with a raw material gas containing C as a constituent atom.

In the present invention, suitable halogen atoms (X) contained in the surface layer 1006 are F, CI, Br.
, r, with F and Cl being particularly desirable.

In the present invention, raw material gases that can be effectively used to form the surface layer 1006 include gaseous materials or substances that can be easily gasified at room temperature and pressure. .

In the present invention, gases effectively used as raw material gases for forming the surface layer 1006 include SiH4, Si2H6, 5i3HB, and 5i4J whose constituent atoms are Si and ■.
silicon hydride gas such as silanes such as o,
C and H are constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylene hydrocarbons having 2 to 3 carbon atoms, simple halogen, hydrogen halides , interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, silicon hydrides, and the like. Specifically, the saturated hydrocarbon is methane (C
H4), ethane (C2H6), propa7 (C3H8
), n-butane (n-C4Ht.

), pentane (CsH+z), ethylene hydrocarbons include ethylene (C2H4), propylene (C3Hb
), butene-1 (C4H8), butene-2 (G4H8
), isobutylene (C4H8), pentene (C
5H+o ), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4),
Butyne (1EAH6), halogen gases such as fluorine, chlorine, bromine, and iodine as simple halogens, FH1, )ICf, HBr as hydrogen halides, BrF as interhalogen compounds.

C1F, ClF3, CI F5, BrF5, BrF3,
IF,, IF5, IC1, IBr, SiF4, Si2F6, Siα3Br as silicon halide
, 5iCf2Br2.5ill Br3 , 5ill
3ISiBr4, halogen-substituted silicon hydride, SiH2F2, SiH2α2.5ioct3.
SiH3α, 5iH3Br.

As 5iH2Br2, 5iHBr3 silicon hydride,
S i H4, 5i2HB, 5i3HB, 5i
Examples include silanes such as 4HH6, and the like.

In addition to these, CF4, CCl4, CBr4, C
HF,, C112F2, Cl3F, CH3Cj!
, CH3Br, CH31, C2H3C# and other halogen-substituted paraffinic hydrocarbons, SF4, SF6 and other fluorinated sulfur compounds; 5i(CH3)q, 5i(C2
Alkyl silicide such as Hs)+, SiC(CH3)3, S
Silane derivatives such as halogen-containing alkyl silicides such as iC#2(CH3)2 and Siα3CH3 can also be mentioned as effective.

These surface layer 1006 forming substances are used to form the surface layer 1006 so that silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are contained in the formed surface layer 1006 in a predetermined composition ratio. They are selected and used as desired during formation.

For example, inclusion of silicon atoms, carbon atoms, and hydrogen atoms can be easily achieved, and a layer with desired characteristics can be formed.
i(CH4)o and 5iHCI3, 5iH2Cf2, Siα4, SiH3α, etc. containing halogen atoms are introduced in a gas state into an apparatus for forming the surface layer 1006 at a predetermined mixing ratio to generate a glow discharge. By letting a−(””x Ctox )y (
A surface layer 1006 consisting of α+II)1-y can be formed.

To form the surface layer 100B by the sputtering method, a single-crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C is targeted, and these are treated with halogen atoms or/and as required. This may be performed by sputtering in various gas atmospheres containing hydrogen atoms as constituent elements.

For example, if a Si wafer is used as a target, the raw material gas for introducing C,
The gas may be diluted as necessary, introduced into a deposition chamber for sputtering, and a gas plasma of these gases may be formed to sputter onto the Si Milani.

Alternatively, Si and C may be used as separate targets, or by using a single mixed target of Si and CC7), a gas atmosphere containing hydrogen atoms and/or halogen atoms may be used. This is done by sputtering with 4R. As the material gas for introducing C, H and X, the material for forming the surface layer 1006 shown in the glow discharge example described above can also be used as an effective material in the sputtering method. .

In the present invention, as the diluent gas used when forming the surface layer 1006 by a glow discharge method or a sputtering method, so-called rare gases such as He, Me, Ar, etc. can be mentioned as suitable ones. .

The surface layer 100B in the present invention is carefully formed so as to provide the required properties as desired.

That is, a substance whose constituent atoms are Sl, C5, H or/and X as required, has a structure ranging from crystalline to amorphous depending on its preparation conditions, and has an electrical property of:
In the present invention, a-(SlX
In order to form c, -X)y (H,X)ty, the conditions for its formation are strictly selected according to desire. For example, when the surface layer 1006 is provided with the main purpose of improving electrical voltage resistance, a-(StXcl-X)y
(H,

In addition, when the surface layer 100B is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to a certain extent, and the sensitivity to the irradiated light is reduced to a certain extent. As an amorphous material having a-
(StXC,-X)y (H,X)+-y is created. On the surface of the second layer 1003, a-(SiX114
-x )y (H,X) +-y empty surface layer 10
During layer formation, the temperature of the support during layer formation is one of the important factors that influences the structure and properties of the formed layer. (
It is desirable that the temperature of the support during layer formation be strictly controlled so that Six c, -X )y (H,X) I-y can be formed as desired.

In the present invention. The formation of the surface layer 1006 is carried out by appropriately selecting the optimum range according to the method of forming the surface layer 1006 in order to effectively achieve the desired purpose, but preferably at a temperature of 20 to 400°C. The temperature is preferably 50 to 350°C, most preferably 100 to 300°C. For forming the surface layer 1006, it is advantageous to employ a glow discharge method or a sputtering method because delicate control of the composition ratio of atoms constituting the layer is relatively easy compared to other methods. However, when forming the surface layer 1006 using these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above.
This is one of the important factors that influences the characteristics of (H,X)+-y.

a'-(Six C+ -x)y (l(,X
The discharge power conditions for effectively creating Ly with high productivity are preferably lO to 100OW, more preferably 20 to 750W, and optimally 50 to 850W. .

The gas pressure in the deposition chamber is preferably 0. O1~l
Torr, preferably about 0.1 to 0.5 Torr.

In the present invention, the values in the above-mentioned ranges are listed as desirable numerical ranges for the support temperature and discharge power for creating the surface layer 1006, but these layer creation factors can be determined independently and separately. a of the desired property, rather than a
-(Six C+ -x)y (H,

The amount of carbon atoms contained in the surface layer 1006 in the photoconductive member of the present invention is the same as the conditions for forming the surface layer 1006.
Surface layer 1 that provides desired properties to achieve the object of the present invention
This is one of the important factors in the formation of 008.

The amount of carbon atoms contained in the surface layer 100B in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the surface layer 1006.

That is, the general formula a-(SiXC+ -x)y (H
,
An amorphous material composed of silicon raw material t and carbon atoms (hereinafter referred to as ra-8iaCI-aJ. However, O<
a<1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as ra-(Sib(
:+-b)cH+-C:J. However, Q<b, c<
1), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary (hereinafter referred to as ra
-(Si, 1 cl -d )e(H, XL-8]. However, it is classified as 0<d, e<1).

In the present invention, the surface layer 1006 is a-9+BCI-a
, the amount of carbon atoms contained in the surface layer +00fi is preferably from 1
mic%.

More preferably 1 to 80 ato layer ic%, optimally 1O to
It is desirable that it be 75ago recommended ic%.

That is, the previous a-9! If you use the expression a in aCI-a, a
is preferably 0.1 to 0. H2O2, more preferably 0.
2 to 0.99, optimally 0.25 to 0.9.

On the other hand, in the present invention, the surface layer 1006 is a-(Sfb
Cl-b) When composed of clll-0, the surface layer 1
The amount of carbon atoms contained in 00B is preferably lXl
0-3 to 80ato+sic%, more preferably 1 to 9Q6tomic%, optimally 10 to 80ato
It is desirable to set it to mic%. The content of hydrogen atoms is preferably 1 to 40 atomic%,
More preferably 2 to 35 ato+mic%, optimally 5
It is desirable that the hydrogen content be 30 atomic %, and a light receiving member formed with a hydrogen content in this range can be sufficiently applied as an excellent material in practice.

That is, the previous a-(Sib cl -b). Hl-1!
b is preferably 0.1 to 0.9138
139, more preferably 0.1 to 0.89, optimally 0.
15 to 0.8, C is preferably 0.6 to 0.99, more preferably 0.65 to 0.98, optimally 0.7 to 0.8
5 is desirable.

The surface layer 1006 has a−(SidC+−d)e(l(,
x), -, -'c', the surface layer 100
The content of carbon atoms contained in 6 is preferably 1X10' to 80 atomic%, more preferably 1 to 90 atomic%, and optimally 10 to 80 atomic%.
It is preferable to set it as ic%. The content of halogen atoms is preferably 1 to 20 atoms.
It is preferable that the halogen atom content be within this range, so that light-receiving members produced when the halogen atom content is in this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19 atoms.
It is desirable that the content be less than c%, more preferably less than 13atos+ic%.

That is, the previous a-(S4d C1-+). (■, XL-
If expressed as d of e, d is preferably 0.1
-0.99999, more preferably 0.1-0.89, optimally 0.15-0.9, e preferably 0.8-0.9
8, more preferably 0.82 to 0.99. Optimal is 0.8
It is desirable that it is 5 to 0.88.

The numerical range of the layer thickness of the surface layer 1006 in the present invention is one of the important factors for effectively achieving the object of the present invention.

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

The thickness of the first surface layer 100B also depends on the characteristics required for each layer, including the carbon atoms contained in the layer and the relationship between the thicknesses of the first and second layers. It is necessary to decide as appropriate based on the desired organic relationship.

In addition, it is desirable to consider the economical aspects including productivity and mass production.

The thickness of the surface layer 1006 in the present invention is preferably 0.003 to 30 scales, more preferably 0.004 to 2 scales.
It is desirable that the value be 0, most preferably 0.005 to +og.

The germanium atoms contained in the first layer (G) +002 are continuous and uniform in the thickness direction of the first layer (G) 1002 and in the in-plane direction parallel to the surface of the support. It is contained in the first layer (G) 1002 so as to have a distribution state.

In the present invention, the second layer (G) provided on the first layer (G)
The layer (S) does not contain germanium atoms, and by forming a light-receiving layer in such a layer structure, the entire wavelength range from relatively short wavelengths to relatively long wavelengths, including the visible light region, can be detected. The present invention provides a light-receiving member having excellent photosensitivity to light having wavelengths in the range.

In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed over the entire layer region, so when a semiconductor laser or the like is used, the second layer (S ) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed in the first layer (G).
Interference due to reflection from the support surface can be prevented by +1.

Further, in the light-receiving member of the present invention, each of the amorphous materials constituting the first layer (G) and the second layer (S) has a common constituent element of silicon atoms. Therefore, chemical stability is sufficiently ensured at the laminated interface.

In the present invention, the content of germanium atoms contained in the first layer (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 or more! 11.5X to5atomic ppm
, more feminine is 100~8×105105ato
It is desirable to set it as ppm.

In the present invention, the layer thickness of the first layer (G) and the second layer (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the light receiving member to ensure that the desired properties are fully imparted to the light receiving member.

In the present invention, the layer thickness T of the first layer (G) is preferably 30A to 50IL, more preferably 40A to 40IL.
It is desirable that μ is optimally set to 50A to 30IL.

Further, the layer thickness T of the second layer (S) is preferably 0.5 to 8
0 river, more preferably 1 to 8011. Optimally 2-50
It is preferable to call it a river.

Thickness of the first layer (G)■ The sum (TO+T) of the thickness B of the first layer (G) and the thickness T of the second layer (S) is determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. Based on the organic relationship between the
To be determined accordingly.

In the light receiving member of the present invention, -F (Ta+T)
The numerical range is preferably t-to.

River, more preferably 1 to 80 #1. , optimally 2-50I
It is desirable to set it to L.

In a more preferred embodiment of the present invention,! - The layer thickness TO and the layer thickness T are preferably Ta/T.
When satisfying the relationship ≦1, it is desirable that appropriate numerical values be selected for each.

In the case of -1-, when selecting the numerical values of the layer thickness 8 and the layer thickness T, it is more preferable that TB/T≦0.8.
Optimally, it is desirable that the values of the layer thickness 8 and the layer thickness T be determined so that the relationship 'ri+/T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer (G) is l x 105ato105at
o or more, it is desirable that the layer thickness of the first layer (G) (8) be considerably thinner, preferably 30IL.
Hereinafter, it is more preferably 25 pL or less, most preferably 20 pL or less.

In the present invention, the halogen atoms (X) optionally contained in the first layer (G) and second layer (S) constituting the photoreceptive layer include fluorine, chlorine, etc. , bromine, and iodine, with fluorine and chlorine being particularly preferred.

In the present invention, the first layer (G) composed of a-3iGe (H, done by law. For example, by glow discharge method, a S + G e
In order to form the first layer (G) composed of (H + Raw material gas for supplying Ge to be obtained and raw material gas for introducing hydrogen atoms (H) or/and halogen atoms (X) as necessary
A raw material gas for introduction is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber, thereby causing the gas to flow onto the surface of a predetermined support that has been placed at a predetermined position in advance. a-3iGe (H,
It is sufficient to form a layer consisting of X). In addition, when forming by sputtering method, for example, a target made of Si and a target made of Ge are formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. Using a sheet, or Si,! When sputtering using a mixed target of l:Ge,
Hydrogen atom (H) or/and halogen atom (
X) The introduction gas may be introduced into the deposition chamber for sputtering.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4 and Si2H6.

5i3HB, 5i4J. Silicon hydride (silanes) in a gaseous state such as
SiH4, Si2H6 in terms of supply efficiency, etc.

are listed as preferred.

As a material that can be a source gas for supplying Ge, GeH
4,Ge2H6,Ge3HB,Ge4H1(,,G
e5H12.

Ge6' 14 + Ge7' 1G + Ge8'
Germanium hydride in a gaseous state or that can be gasified, such as 1B + Ge9H20, can be effectively used. In particular, Get+4, Ge2H6, Ge
3HB is preferred.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

Moreover, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen X atoms as constituent elements, can also be mentioned as effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, iodine nohalogen gas, BrF, αF, ClF3, BrF5. B
17) Interhalogen compounds such as rF3, IF3, IF7, ICI, IBr, etc. can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4. Si2F6, 5iCI4, SiBr4
Preferred silicon halides include the following.

When forming the characteristic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. The first layer (G) made of a-8iGe containing halogen atoms can be formed on a desired support without using silicon oxide gas.

According to the glow discharge method, the first layer containing halogen atoms (
G), basically, for example, a predetermined mixture of silicon halide, which is a raw material gas for supplying Si, germanium hydride, which is a raw material gas for Ge supply, and gases such as Ar, H2, He, etc. The first layer (
The first layer (G) can be formed on the desired support by introducing the gas into a deposition chamber for forming the gas (G) and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

A first layer (H,X) made of a-SiGe (H,
In order to form G), for example, in the case of a sputtering method, two targets, one made of Si and the other made of Ge, or a target made of Si and Ge are used, and these are placed in a desired gas plasma atmosphere. In the case of sputtering and ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are respectively housed in the evaporation port as evaporation sources, and these evaporation sources are used by resistance heating method or This can be done by heating and evaporating the flying evaporated material using an electron beam method (EB method) or the like and passing the flying evaporated material through a desired gas plasma atmosphere.

At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber 41. It is sufficient to introduce the gas to form a plasma atmosphere of the gas.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of the gases.

In the present invention, a halogen compound indicated by -1- or a silicon compound containing a halogen is effectively used as a raw material gas for introducing a halogen atom, and in addition, HF, HCI, HBr.

Hydrogen halides such as HI, SiH2F2, SiH2
12.

5iH2Cj 2 , 5illCI13 , 5i) 12
Br2, 5iHBr3, etc. (7) Halogen-substituted silicon hydride, and GeHF3, GeHBr3, Ge)1
3F.

Ge1lCI3, GeH2Cl2, Ge1
lCI, GeHBr3.

GeHBr3, GeHBr3 Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides, GeF4゜GeCI4
, GaBr4, GeT4. GeF2. GeC12,
GeBr2.

Gaseous or gasifiable substances such as germanium halides such as Ge12 can also be mentioned as useful starting materials for forming the first layer (G).

Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the first layer (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen.

To structurally introduce hydrogen atoms into the first layer (G),
In addition to the above, H2, SiH4, Si2H6.

Germanium or germanium compound for supplying Ge to silicon hydride such as 5i3HB, 5i4H1゜,
Or GeH4, Ge2H6+ Ge3H131Ge
4H161Ge5H121Ge6H141Ge7H16
This can also be achieved by causing germanium hydride such as 1GeBH181GegH20 and silicon or a silicon compound for supplying Si to coexist in a deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of quantities ()l+X) is preferably 0. O1~4
0 atOzenic%, more preferably 0.05-30 a
atomic%, preferably 0.1 to 25 atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first R(G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms ( What is necessary is to control the flow of the starting material used to incorporate X) into the deposition system, the discharge force, etc.

In the present invention, in order to form the second layer (S) composed of a -3i (H, From the inside, using the 711 starting material (starting material (II) for forming the second layer (S)) excluding the starting material that becomes the raw material gas for supplying Ge, the first
This can be carried out according to the same method and conditions as in the case of forming layer CG).

That is, in the present invention, to form the second JFi' (S) composed of a -5i (H, It is made by a vacuum deposition method. For example, a-Si(H,
In order to form the second layer (S) composed of X), basically S
i Along with the raw material gas for supply, hydrogen atoms (H
) A raw material 4 gas for introduction and/or introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber. A layer consisting of a-9i(H,X) may be formed on the surface of a certain predetermined support. In addition, when forming by sputtering method, S
When sputtering a target composed of i, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering.

In the present invention, hl of hydrogen atoms (H) or stars of halogen atoms (X) or acids of hydrogen atoms and halogen atoms contained in the second layer (S) constituting the photoreceptive layer to be formed. The sum (H+X) is preferably 1 to 40 atomic%, more preferably 5 to 30 atomic%, optimally 5 to 25 atomic%.
Preferably, it is expressed as atomatous ic%.

In the light-receiving member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the light-receiving layer, the light-receiving layer contains , oxygen atoms, carbon atoms, and nitrogen atoms are contained in a uniform or non-uniform distribution state in the layer thickness direction. Such atoms (OGN) contained in the photoreceptive layer are
It may be contained in the entire layer region of the light-receiving layer, or it may be contained unevenly in only a part of the layer region of the light-receiving layer.

The distribution state of atoms (OCN) is such that the distribution concentration C (00%) is
It is desirable that the photoreceptive layer be uniform in a plane parallel to the surface of the support.

In the present invention, atoms (OCN) provided in the photoreceptive layer
When the main purpose is to improve photosensitivity and dark resistance, the layer area (OCN) containing OCN is provided so as to occupy the entire layer area of the photoreceptive layer, and the area between the support and the photoreceptive layer is When the main purpose is to strengthen the adhesion between layers, it is provided so as to occupy the end layer region of the light-receiving layer on the side of the support.

In the former case, the atoms (O
It is desirable that the content of CN) be relatively low in order to maintain high photosensitivity, and in the latter case, relatively high in order to ensure enhanced adhesion to the support.

In the present invention, a layer region (OCN
) The content of atoms (OCN) contained in the one-layer region (O
CN) itself or the layer region (OCN).
) is provided in contact with the support, it can be appropriately selected depending on the organic and organic relationships, such as the relationship with the properties at the contact interface with the support.

In addition, when another layer region is provided in direct contact with the layer region (00%), the characteristics of the other layer region and the characteristics at the contact interface with the other layer region are determined. The relationship is also taken into account,
The content of atoms (OCN) is selected appropriately.

The amount of atoms (OCN) contained in the layer region (OCN) is determined as desired depending on the properties required of the light receiving member to be formed, but is preferably 0.001 to 0.001.
50 atomic%, more preferably 0.002~
40ato ic%, optimally 0.003-30ato
It is desirable to set it to mic%.

In the present invention, whether the layer region (OCN) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is equal to the layer thickness TO of the layer area (OCN). When the proportion of atoms (OCN) in the layer region (OCN) is sufficiently large, it is desirable that the upper limit of the content of atoms (OCN) contained in the layer region (OCN) is sufficiently smaller than the above value.

In the case of the present invention, when the layer thickness TO of the layer region (OCN) accounts for two-fifths or more of the layer thickness T of the photoreceptive layer, the layer region (OCN) The upper limit of the atoms (OCN) contained therein is preferably 30 atoms.
c% or less, more preferably 20atos+ic% or less,
The optimum content is preferably 10 atomic% or less.

According to a preferred embodiment of the present invention, atoms (OCN) are preferably contained at least in the first layer provided directly on the support. clogging, atoms (OCN) are contained in the support side end layer region of the photoreceptive layer,
It is possible to strengthen the adhesion between the support and the light-receiving layer.

Furthermore, in the case of nitrogen atoms, for example, in the coexistence with boron atoms, it is possible to further improve dark resistance and ensure high photosensitivity, so it is desirable to contain a desired amount in the photoreceptive layer.

Further, a plurality of types of these atoms (OCN) may be contained in the photoreceptive layer. That is, for example, oxygen atoms may be contained in the first layer, or oxygen atoms and nitrogen atoms may be contained coexisting in the same layer region.

16 to 24 show typical examples in which the distribution state of atoms (OCN) contained in the layer region (OCN) of the light-receiving member according to the present invention in the layer thickness direction is non-uniform. .

In Figures 16 to 24, the horizontal axis represents atoms (OCN).
The vertical axis indicates the layer thickness of the layer region (OCN), tB indicates the position of the end surface of the layer region (0 (EN)) on the support side, and t indicates the layer region on the opposite side to the support side. The position of the end face of (OCN) is shown. That is, the layer region (OCN) containing atoms (OCN) is layered from the 1B side toward the 1T side.

Figure 16 shows atoms (
A first typical example is shown in which the distribution state of OCN) in the layer thickness direction is non-uniform.

In the example shown in FIG. 18, the surface where the layer region (OCN) containing atoms (QC:N) is formed and the layer region (OCN)
From the interface position tB where it contacts the surface of the CN) to the position tl, the distribution concentration C of the atoms (OCN) takes a constant value C, and the layer region (OCN) where the atoms (0ON) are formed takes a constant value C.
), and is contained at the position t, or from the concentration C2 at the interface position 1.
It is gradually and continuously reduced until it reaches Ding. Interface position 1. In the distribution of atoms (OCN), the concentration of C is assumed to be small.

In the example shown in FIG. 17, the contained atoms (O
The distribution concentration C of CN) forms a distribution state in which it gradually and continuously decreases from the concentration C4 from the position to to 1 block, and reaches the concentration at the position t□.

In the case of Fig. 18, the distribution concentration C of atoms (OCN) is kept at a constant value C6 from position ta to position t2, and gradually and continuously decreases between position t2 and position 1. , at one position, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 18, the distribution concentration C of atoms (OCN) is from position tB to position 1. The concentration is gradually decreased continuously from C8 until reaching , and becomes substantially zero at one position.

In the example shown in FIG. 20, the distribution concentration C of atoms (OCN) is a constant value of concentration C9 between position ta and position 13, and is set to concentration CIo at position 1. Between the position t3 and the position 1-2, the 1-distribution concentration C decreases in a linear function from the position t3 to the position 1-4.

In the example shown in FIG. 21, the distribution concentration C is at position 1.
From position B to position t4, the concentration C11 takes a constant value, and from position t4 to position NtT, the distribution state decreases linearly from concentration CI2 to concentration CI3.

In the example shown in FIG. 22, from position tB to position 1, the distribution concentration C of atoms (OCN) decreases linearly from the concentration CI4 to substantially zero.

In FIG. 23, position 1. Until the position t5 is reached, the distribution of atoms (OCN) C is 01 from the concentration CI5.
An example is shown in which the concentration CI6 is decreased in a linear function up to 6, and the concentration CI6 is kept at a constant value between the position t5 and the position tT.

In the example shown in FIG. 24, the distribution concentration C of atoms (OCN) is the concentration CI7 at the position 1B, and is gradually decreased from this concentration CI7 until reaching the position t6, and is gradually decreased near the position t6. , the concentration is rapidly decreased to a concentration CI8 at the position t6.

Between the position t6 and the position t7, the decrease is rapid at first, and then the decrease is slow and gradual until the position t7 is reached.
The concentration becomes CI9, and between position t7 and position t8,
It is gradually reduced very slowly and reaches a concentration C2° at t8. Between position t8 and position 1, the density is reduced from C20 to substantially zero according to a curve shaped as shown in the figure.

Therefore, according to FIGS. 18 to 24, the layer region (OCN
) As explained in some typical examples where the distribution state of atoms (OCN) contained in the layer thickness direction is non-uniform, in the present invention, the distribution state of atoms (OCN) contained in On the interface LT side, the distribution state of atoms (OCN) has a portion where C is considerably lower than on the support side.
It is set in.

The layer region (OCN) containing atoms (OCN) is provided as having a localized region (B) containing atoms (OCN) at a relatively high concentration on the support side as described above. In this case, the adhesion between the support and the light-receiving layer can be further improved.

The localized region (B) shown in - is preferably provided within 5#L from the interface position tB, if explained using the symbols shown in FIGS. 16 to 24.

In the present invention, the localized region (B) is the interface position 1
It may be the entire region (LT) up to 5 pL thick from B, or it may be a part of the layer region (Lr).

Whether the localized region (B) is a part or all of the layer region (L,) is determined as appropriate depending on the characteristics required of the light-receiving layer to be formed.

The localized region (B) has a distribution state of atoms (OCN) contained therein in the layer thickness direction such that the maximum icmax of the atomic (OCN) distribution concentration C is preferably 500 atomic.
pps+ or more preferably 800 atomic pp
It is desirable that the layer be formed in such a manner that a distribution state of at least 1,001,000 at ppm can be achieved.

That is, in the present invention, the layer region (QC:N) containing atoms (OCN) has the maximum value Cwax of the distribution concentration C within 5IL in layer thickness from the support side (layer region from til+ to 51L thickness). It is desirable that the structure be formed in such a way that it exists.

In the present invention, when the layer region (OCN) is provided so as to occupy a part of the layer region of the photoreceptive layer, the layer region (OCN)
) and other layer regions. It is desirable to form a distribution state of atoms (OCN) in the layer thickness direction so that the refractive index changes gradually.

By doing so, it is possible to prevent the light incident on the photoreceptive layer from being reflected at the layer contact interface, and to more effectively prevent the appearance of interference fringes.

Also, the change line of the distribution concentration C of atoms (OCN) in the layer region (OCN) is a point that gives a smooth refractive index change.

It is desirable to have continuous and gradual changes.

From this point, atoms (OC
N) is preferably contained in the layer region (OGN).

In the present invention, in order to provide a layer region (OCN) containing atoms (OCN) in the photoreceptive layer, the starting material for introducing atoms (00%) is added to the above-mentioned photoreceptor during the formation of the photoreceptor layer. It may be used together with the starting material for forming the receptor layer and contained in the formed layer while controlling its amount.

When the glow discharge method is used to form the layer region (OGN), the starting material for introducing atoms (OCN) into the starting material for forming the photoreceptive layer is selected as desired from among the starting materials for forming the photoreceptive layer. Most of the gaseous substances whose constituent atoms are at least atoms (OCN) or gasified substances that can be gasified are used.

Specifically, for example, oxygen (02), ozone (03) - nitrogen oxide (NO), nitrogen dioxide (802), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), trinitrogen tetraoxide (N20A), Nitrogen sesquioxide (N205), nitrogen trioxide (NO3), silicon atom (Si) and oxygen atom (0)
and a hydrogen atom (■1) as constituent atoms, such as disiloxane (N35iO9jH3) and tricycloxane (N35iO9jH3).
Lower cycloxanes such as 3SiOSiXia120SiH3), methane (CH4), ethane (C2H4), propane (
C3Ha), n-butane (n-Co H+o),
Saturated hydrocarbons having 1 to 5 carbon atoms such as penta7 (Cs H12), ethylene (C2+14), propylene (C3
H5), butene-1(1':,llb+).

Butene-2 (CJs), isobutylene (C4Hs)
, Ethylene hydrocarbons with 2 to 5 carbon atoms such as pentene (CsH+o), ethylene hydrocarbons with 2 to 5 carbon atoms such as acetylene (C2H2), methylacetylene (C3H4), butyne (Co H6), etc.
4 acetylenic hydrocarbons, nitrogen (N2), ammonia (NH3>, hydrazine (H2NNH2), hydrogen azide (HN3), ammonium azide (NH4N3),
Examples include nitrogen trifluoride (F3N) and nitrogen tetrafluoride (F4N).

In the case of the sputtering method, the starting materials for introducing atoms (OCN) include, in addition to the above-mentioned gasifiable starting materials listed for the glow discharge method, solidified starting materials:
5i02, Si3 H4, carbon black, etc. These are used as sputtering targets together with targets such as Si.

In the present invention, when forming the photoreceptive layer, atoms (OCN
), the distribution method If of the atoms (OCN) contained in the layer region (OCN) is provided.
By changing fC in the layer thickness direction, a desired distribution shape t in the layer thickness direction is obtained.
layer region (O
In order to form CN), in the case of a glow discharge, the gas of the starting material for introducing atoms (OCN) whose distribution concentration C is to be changed is changed while the gas flow rate is appropriately changed according to a desired rate of change curve. , by introducing it into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow system may be temporarily changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change of the flow rate does not need to be linear, and it is also possible to obtain a desired content rate curve by controlling it according to a rate of change curve designed in advance using, for example, a microcomputer.

When forming a layer region (OCN) by a sputtering method, the distribution concentration C of atoms (OCN) in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (depth profile) of atoms (OCN) in the layer thickness direction. In order to form Ie), firstly, as in the case of the glow discharge method, the starting material for introducing atoms is used in a gaseous state, and the gaseous acid flow when introducing the gas into the deposition chamber is This can be done by appropriately changing it as desired. Second, if a target for sputtering is used, for example, a mixed target of Si and 5i02, the mixing ratio of Si and 5i02 should be changed in advance in the layer thickness direction of the target. made by.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the electrically conductive support include NiCr, stainless steel, and At.

Cr, No, Au, Wb, Ta, V, Ti,
Examples include metals such as Pt and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr, AN,
Cr, No, Au, Ir, Nb, Ta, V,
Ti, Pt, Pd, In2O3, 5n02, IT
Conductivity is imparted by providing a thin film made of O(In2O3+ 5n02), etc., or if it is a synthetic resin film such as a polyester film, NiCr,
At, Ag, Pb, Zn, Ni, Au, C
r, No, Ir, Nb, Ta, V, Ti, P
Conductivity is imparted to the surface by providing a thin film of metal such as T on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the light-receiving member 1004 in FIG. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape. The thickness of the support is determined appropriately so that a desired light-receiving member is formed, but if flexibility is required as a light-receiving member, the thickness of the support may be determined appropriately. It is made as thin as possible within the range. However, in such a case, from the viewpoint of manufacturing and handling of the support and functional strength, it is preferably 1 OIL or more.

Next, an outline of an example of the method for manufacturing the light receiving member of the present invention will be explained.

FIG. 12 shows an example of a light-receiving member manufacturing apparatus.

Gas cylinders 2002 to 2006 in the figure are sealed with raw material gas for forming the light-receiving member of the present invention, and as an example, 2002 is SiH4 gas (purity 99. (abbreviated as) to Bonn, 20
03 is a G e H4 gas (purity 119.999%, hereinafter abbreviated as GeH4) cylinder, 2004 is NO gas (purity 9
9. H9% (hereinafter abbreviated as NO) cylinder, 2006 is H2
It is a gas cylinder (purity 119.999%).

In order to flow these gases into the reaction chamber 2001, valves 2022 to 2026 of gas cylinders 2002 to 2006,
Make sure the leak valve 2035 is closed,
In addition, inflow valves 2012 to 2016, outflow valve 201
After confirming that the auxiliary valves 2032 and 2033 are open, first open the main valve 2034 to exhaust the reaction chamber 2001 and each gas pipe. Next, the vacuum gauge 2036 reads approximately 5 X 10' torr.
At the point in time, close the auxiliary valves 2032 and 2033 and the outflow valves 2017 to 2021.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 2037, Si
114 gas, GeH4 gas from Gas Pombe 2003,
Open the valve 2022.2023.2024.2026 and apply NO gas from the gas pump 2004 and H2 gas from 2008 to the outlet pressure gauge 2027.2028.2029.2.
Adjust the pressure of 031 to 1 Kg/crn', gradually open the inflow valve 2012.2013.2014.201B, and open the mass flow controller 20 (17.2008.20
09.201+ respectively. Subsequently, the outflow valve 2017.2018.20!8.2021 and the auxiliary valve 2032.2033 are gradually opened to allow each gas to flow into the reaction chamber 2001. At this time, set the outflow valve 2017.2018 so that the ratio of SiH4 gas flow rate, GeH4 gas flow rate, NO gas flow rate and H2 gas flow rate becomes the desired value.
．． 2019.2021 and also reaction chamber 2001
Adjust the opening of the main pulp 2034 while checking the reading on the vacuum gauge 2036 so that the internal pressure reaches the desired value. After confirming that the temperature of the base 2037 is set to a temperature in the range of 50 to 400°C by the heater 2038, the power source 2040 is set to the desired power to generate glow discharge in the reaction chamber 2001. .

The glow discharge is maintained for a desired time in the manner described above, and the first layer (G) is formed on the base 2037 to a desired layer thickness. At the stage where the first layer (G) has been formed to a desired layer thickness, glow discharge is performed for a desired time according to the same conditions and procedures, except for completely closing the outflow valve 2018 and changing the discharge conditions as necessary. By maintaining the second layer (S) containing substantially no germanium atoms on the first layer (G)
can be formed.

In addition, each layer of the first layer (G) and the second layer (S) includes
By appropriately opening and closing the outflow valve 2018, oxygen atoms can be contained or not contained, or oxygen atoms can be contained only in a partial layer region of each layer. Further, when nitrogen atoms or carbon atoms are contained in the layer instead of oxygen atoms, the layer may be formed by replacing the NO gas in the gas pump 2004 with, for example, NH3 gas or CH4 gas. Furthermore, if the types of gas to be used are to be increased, a desired gas pump may be added and layers formed in the same manner. During layer formation, it is desirable that the substrate 2037 be rotated at a constant speed by a motor 2038 in order to ensure uniform layer formation.

Finally, after forming the second layer (S), for example 2006
Take the hydrogen (H2) gas cylinder to the methane (GH4) gas cylinder.Analysis, mass flow controller 20 (1)
7 and 2011 at a predetermined flow rate, but by following similar conditions and procedures to maintain the glow discharge for a desired time, a surface formed mainly of silicon and carbon atoms is formed in the second layer (S)l. layers can be formed.

” - When forming a surface layer mainly made of silicon atoms and carbon atoms by sputtering, for example, 200
Replace the hydrogen (■2) gas cylinder in B with an argon (Ar) gas cylinder, clean the deposition device, and place a sputtering target made of Si and a sputtering target made of graphite on the cathode electrode in a desired area ratio. Spread it all over the place like this. Thereafter, the layer formed up to the second layer (S) is placed in the apparatus, the pressure is reduced, and argon gas is introduced to generate a glow discharge and sputter the surface layer material 4 to a desired thickness. form.

Examples of the present invention will be described below.

Example 1 In this example, a semiconductor laser (wavelength: 780 nm) with a spot diameter of 80 nm was used. Therefore, a-9i:H is deposited on a cylindrical AI support (length L) 357 ■ diameter (r) 80 (pitch (P) 25) using a lathe.
A spiral groove was created with a depth of 0.88 μs. The shape of the groove at this time is shown in FIG.

Next, using the film deposition apparatus shown in FIG. 12 under the conditions shown in Table 1a, the surface layer was deposited according to the prescribed operating procedure.
A -9i-based electrophotographic light-receiving member was produced.

Note that the flow rate of NO gas is the same as the SiH4 gas flow rate and G
e The mass flow controller was set and introduced so that the initial value was 3.4 malo 1% with respect to the sum of H4 gas and m.

Further, the surface layer formed mainly of silicon atoms and carbon atoms was deposited as follows.

That is, after the deposition of the second layer, CH4
Gas flow rate is S i H4 gas flow sewing flow rate ratio is 5i
11. Set the mass flow controller corresponding to each gas so that 10H4 = 1/30, and increase the high frequency power to 3.
A surface layer was formed by generating a glow discharge at 00W.

Separately, the first layer, the second layer, and the surface prevention layer were formed on the same cylindrical At support with the same surface property under the same conditions and manufacturing method as in the case described above, except that the high-frequency power was 40 W. When the photoreceptive layer was formed on a support, the surface of the photoreceptive layer was parallel to the plane of the support 1301, as shown in FIG.

At this time, the difference in the total layer thickness between the center and both ends of the support was 1 μm.

Further, when the high frequency power was set to 160 W, the surface of the light receiving amount and the surface of the support 1401 were non-parallel as shown in FIG. To this case! The difference in average layer thickness between the center and both ends of the support was 2 tiles.

Regarding the above two types of electrophotographic light receiving members, wavelength 7
80n Peng semiconductor laser with a spot diameter of 80μ
Image exposure is performed using the device shown in the figure, which is then developed and transferred to create an image (111). At high frequency power of 40 W during layer production, the first
In the superficial light-receiving member shown in FIG. 3, an interference fringe pattern was observed.

On the other hand, in the light-receiving member having the surface properties shown in FIG.
No interference fringe pattern was observed, and a product showing electrophotographic characteristics sufficient for practical use was obtained.

Example 2 The surface of a cylindrical M support was machined using a lathe as shown in Table 1. These (Samples 101 to 108) were placed on the cylindrical AI support under the conditions in which the interference fringe pattern of Example 1 disappeared (
Electrophotographic light-receiving members were produced under the same conditions as the high-frequency power (Leow) (Samples Ill to 11B).

At this time, the difference in average layer thickness between the center and both ends of the Af support of the electrophotographic light-receiving member was 2.2-.

When the cross sections of these electrophotographic light-receiving members were observed with an electron microscope and the difference in the pitch of the second layer was measured, the results shown in Table 2 were obtained. These light-receiving members were subjected to image exposure with a spot diameter of 80 .mu.m using the apparatus shown in FIG. 15 using a semiconductor laser having a wavelength of 780 nm in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 3 A light receiving member was produced under the same conditions as Example 2 except for the following points (Samples 121-128).
The layer thickness of the layer was set to 10-. At this time, the difference in average layer thickness between the center and both ends of the first layer was 1.2μ.

The average difference in the thickness of the second layer between the center and both ends is 2.3p.
Met. When the thickness of each layer of M6121 to M6128 was measured using an electron microscope, the results shown in Table 3 were obtained. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and the results shown in Table 3 were obtained.

Example 4 A cylindrical At support ((A
101-108) A light-receiving member having a first layer containing nitrogen was prepared under the conditions shown in Table 4 (sample positive 4).
0 to I08).

Manufactured under the above conditions 1. The cross section of the photoreceptor member was observed using an electron microscope. The average layer thickness of the first layer was 0.09u at the center and both ends of the cylinder. The average layer thickness of the second layer was 3μ in the center and at both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 5. When each of these light-receiving members was subjected to imagewise exposure with laser light in the same manner as in Example 1, the results shown in Table 5 were obtained.

Example 5 Cylindrical AI support CA 1 with the surface properties shown in Table 1
01 to 108), the first one containing nitrogen on the support
A light-receiving member provided with a layer was prepared under the conditions shown in Table 6 (Samples Nos. 501 to 508).

A cross section of the light receiving member produced under the above conditions was observed using an electron microscope. The average layer thickness of the first layer was 0.3- in the center and at both ends of the cylinder. The average layer thickness of the second layer was 3.2 tiles at the center and at both ends of the cylinder.

The difference in layer thickness within the short range of each layer of each light-receiving member is
The values were shown in Table 7. When each of these light-receiving members was subjected to image exposure with laser light in the same manner as in Example 1, the results shown in Table 7 were obtained. Example 6 Cylindrical M support CA 10 with the surface properties shown in Table 1
1 to 108), the first one containing carbon in the support 1-
A light-receiving member provided with a layer was prepared under the conditions shown in Table 8 (sample, 1aot to 808).

- The cross section of the light-receiving member produced under the conditions described above was observed with an electron microscope. The average layer thickness of the first layer was 0.08μ at the center and at both ends of the cylinder. The average layer thickness of the second layer was 2.5 tiles at the center and at both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 9. Each of these light-receiving members was image-wise exposed to laser light in the same manner as in Example 1, and the results are shown in Table 9.

Example 7 A cylindrical M support (a610
1-108), a light-receiving member in which a first layer containing carbon was provided on support-E was prepared under the conditions shown in Table 1θ (sample, /11101 to tto8).

A cross section of the light receiving member produced under the above conditions was observed using an electron microscope. The average layer thickness of the first layer was 1.1μ at the center and at both ends of the cylinder. The average layer thickness of the second layer was 3.4μ at the center and at both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 11. When these light-receiving members were subjected to imagewise exposure with laser light in the same manner as in Example 1, the results shown in Table 11 were obtained.

Example 8 When forming the first layer, the NO gas flow rate was changed with respect to the sum of the SiH4 gas meteor and the GeH4 gas meteor as shown in FIG. Except for making the total zero, the high frequency power of Example 1 was 1
An electrophotographic light-receiving member was produced under the same conditions as when the power was set to 80W. Apart from setting the high frequency power to 40W,
When the first layer and the second layer were formed on the support L using the same conditions and manufacturing methods as above, the surface of the light-receiving layer was formed on the plane of the support 1301 as shown in FIG. It was parallel to the At this time, the difference in the total layer thickness between the center and both ends of the AI support taot was Ig.

Further, when the high frequency power is set to 180W, the surface of the second layer 1403 and the support 140 are separated as shown in FIG.
It was non-parallel to the surface of 1. In this case, the difference in average layer thickness between the center and both ends of the M support was 2 degrees.

Regarding the above two types of electrophotographic light receiving members, wavelength 7
15th 80n conductor laser with spot diameter of 80μ
Image exposure was performed using the apparatus shown in the figure, and the image was developed and transferred to obtain an image. At a high-frequency power of 40 W during layer production, an interference fringe pattern was observed in the superficial light-receiving member shown in FIG.

On the other hand, in the light-receiving member having the surface properties shown in FIG.
No interference fringe pattern was observed, and a product showing electrophotographic characteristics suitable for practical use was obtained.

Example 9 The surface of a cylindrical M support was machined using a lathe as shown in Table 1. On these (m 101-108 ) cylindrical M supports, an electrophotographic light-receiving member was prepared under the same conditions as in Example 8 where the interference fringe pattern disappeared (high-frequency power: 160 W). (Samples 1201 to 1208).

At this time, the difference in average layer thickness between the center and both ends of the M support of the electrophotographic light-receiving member was 2.2 μm.

When the cross sections of these electrophotographic light-receiving members were observed with an electron microscope and the difference in the pitch of the second layer was measured, the results shown in Table 12 were obtained. These light-receiving members were subjected to image exposure with a spot diameter of 80 tiles using the apparatus shown in FIG. 15 using a semiconductor laser with a wavelength of 780 nm in the same manner as in Example 8, and the results shown in Table 12 were obtained.

Example 10 A light-receiving member was produced under the same conditions as in Example 9 except for the following points (final samples 130! to 130B). At that time the first
The layer thickness of the layer was defined as IOQ. At this time, the difference in average layer thickness between the center and both ends of the first layer was 1.2 g.

The average difference in the thickness of the second layer between the center and both ends was 2.3 tiles. When the thicknesses of the first and second layers of Taot~1308 were measured using an electron microscope, the results shown in Table 13 were obtained. Regarding these light receiving members, Example 1
As a result of image exposure using an image exposure device similar to
The results shown in Table 13 were obtained.

Example 11 A cylindrical M support (AIIL) with the surface properties shown in Table 1 was prepared.
No. 101 to 108) were used to produce a light-receiving member in which a nitrogen-containing first layer was provided on a support under the same conditions and procedures as in Example 9, except that the conditions shown in Table 14 were used (
Sample, IFL1501-1508).

A cross-section of a light-receiving member fabricated under the conditions of a serious crime was observed using an electron microscope. The average layer thickness of the first layer was 0.08 - at the center and at both ends of the cylinder. The average layer thickness of the second layer was 3 tiles at the center and at both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light receiving member (Samples 1501 to 1508) was the value shown in Table 15.

When each light-receiving member (sample positive 1501 to 1508) was image-exposed with laser light in the same manner as in Example 1, the 15th
The results shown in the table were obtained.

Example 12 A cylindrical AI support (at least 10
1-108), the nitrogen-containing first
The light-receiving member provided with the layer was prepared according to the same conditions and procedures as in Example 9, except that the conditions shown in Table 16 were changed (Samples No. 1701 to +708).

” - A light-receiving member produced under the following conditions (sample aM 170
1 to +708) was observed using an electron microscope. 1st
The average layer thickness of the layer was 0.3 tiles at the center and both ends of the cylinder. The average layer thickness of the photosensitive layer was 0.3 microns at the center and both ends of the cylinder.

The layer thickness differences within the short range of each layer of each light-receiving member (Samples 1701-1708) were the values shown in Table 17.

When each light-receiving member was subjected to image exposure with laser light in the same manner as in Example 1, the results shown in Table 17 were obtained.

Example 13 Cylindrical A with the surface properties shown in Table 1! Support (Al
A light-receiving member in which a nitrogen-containing first layer was provided on a support was prepared using the same conditions and procedures as in Example 9, except that the conditions shown in Table 18 were changed (sample , i tsot~tsoll).

1-The light-receiving member produced under the conditions described above (test vehicle 4 positive tao +
~1908) was observed using an electron microscope. The average layer thickness of the first layer is 0.081 at the center and both ends of the cylinder.
It was LIL. The average layer thickness of the photosensitive layer was 2.5 tiles at the center and both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light-receiving member (Samples 1901-1908) was the value shown in Table 18.

When each light-receiving member (sample 1901-1902) was image-exposed with laser light in the same manner as in Example 1, the 18th
The results shown in the table were obtained.

Example 14 A cylindrical M support (AIIL
101-108), and a light-receiving member in which a first layer containing nitrogen was provided on a support was prepared under the same conditions and procedures as in Example 9, except that the conditions shown in Table 20 were used (sample ai2101-210B).

Light-receiving members produced under the above conditions (sample positive 2101-2
108) was observed using an electron microscope. The average layer thickness of the first layer was 1.1 μs at the center and at both ends of the cylinder. The average layer thickness of the second layer was 3.4 microns at the center and both ends of the syringe.

The difference in layer thickness of the second layer of each light-receiving member (samples at2101 to 2108) within the Show I range was the value shown in Table 21.

When each light-receiving member (sample aM2101 to 2108) was image-exposed with laser light in the same manner as in Example 1, the second
The results shown in Table 1 were obtained.

Example 15 A cylindrical At
The support (cylinder positive 105), L- was compared to the gas flow of NO and SiH4 according to the change rate curves of the gas meteor ratio shown in Figs. 25 to 28 under the conditions shown in Tables 22 to 25. By changing the layer formation time with the elapsed layer formation time, each of the light-receiving members for electrophotography (sample 2202-
2204) was obtained.

When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention.

Example 16 A cylinder-shaped A
The gas flow rate ratio of NO and SiH4 was changed with the elapsed layer formation time according to the change rate curve of the gas flow ratio shown in FIG. Layer formation was performed to obtain an electrophotographic light-receiving member.

When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention.

Example 17 Using the manufacturing apparatus shown in FIG.
Under each condition shown in Table 8, the gas flow rate ratio of NH3 and SiH4 and C
) 14 and SiH4 with the elapsed layer formation time to obtain each of electrophotographic light-receiving members (samples 162208 to 22 (17)).

When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention.

Example 18 Al support used in Example ■ (length L) 357 mm
, diameter (r) of 80 layers), and following the same conditions and procedures as in Example 1, except that the surface layer was formed by sputtering, an a-5i-based electrophotographic light-receiving material was prepared (sample 2801-290?). At this time, the areas of the Si target and the C target were changed, and the contents of Si and C were changed as shown in Table 28.

Note that the surface layer was formed as follows. That is, after forming the second layer, the support formed up to the second layer is transferred to the first layer.
Take out the hydrogen (H2) from the deposition device shown in Figure 2 and remove it from the deposition device.
Replace the gas cylinder with an argon (Ar) gas cylinder,
Clean the inside of the device, and place a sputtering target made of Si with a thickness of 5 mm and a sputtering target made of graphite with a thickness of 5 mm on the cathode electrode L so that their area ratios are as shown in Table 29. Spread it all over. After that, the support formed up to the second layer was installed in the device, the pressure was reduced, and argon gas was introduced.
The surface layer was formed by sputtering the surface layer material on the sword electrode by generating a glow discharge using a high frequency power of 300 W.

Regarding these electrophotographic light-receiving members, an image exposure apparatus shown in FIG. 15 (laser light wavelength: 780 nm) was used.

After performing image exposure with a spot diameter of 80 mm and repeating the steps of image formation, development, and cleaning 50,000 times, image evaluation was performed, and the results shown in Table 28 were obtained.

Example 18 When forming the surface layer, the interference fringes of Example 1 disappeared except that the streamline ratio of SiH4 gas and CH4 gas was changed to change the content ratio of silicon atoms and carbon atoms in the surface layer. Each of the electrophotographic light-receiving members was produced under the same conditions as above. For each of the electrophotographic light-receiving members obtained in this way, the process of image exposure with a laser and transfer was repeated approximately 50,000 times in the same manner as in Example 1, and then image evaluation was performed, as shown in Table 30. Got the results.

Example 20 When forming the surface layer, SiH4 gas, SiF4 gas, C1 (
Electrophotographic light reception was carried out in exactly the same manner as in Example 1 under which the interference fringes disappeared, except that the streamline ratio of the four gases was changed and the content ratio of silicon atoms and carbon atoms in the surface layer was changed. Each member was produced.

For each of the electrophotographic light-receiving members thus prepared, the process of image exposure with a laser and transfer was repeated approximately 50,000 times in the same manner as in Example 1, and then image evaluation was performed.
The results shown in Table 31 were obtained.

Example 21 Electrophotographic light-receiving members were produced in exactly the same manner as in Example 1 under which the interference fringes disappeared, except that the layer thickness of the surface layer was changed. For the electrophotographic light-receiving member thus obtained, the steps of image formation, development, and cleaning were repeated in the same manner as in Example 1, and the results shown in Table 32 were obtained.

Example 22 The discharge power when creating the surface layer was 300 W, and the average layer thickness was 2
An electrophotographic light-receiving member was produced in exactly the same manner as in Example 1 under which the interference fringes disappeared, except that u was used. The surface layer of the electrophotographic light-receiving member thus obtained had an average layer floating cap of 0.5#IjI at the center and both ends. Further, the difference in layer thickness at minute portions was 0.1-.

No interference fringes were observed in such a light-receiving member for electrophotography, and although the steps of image formation, development, and cleaning were repeated using the same device as in Example 1, the durability was sufficient for practical use. Obtained.

〔Effect of the invention〕

As explained in detail below, the present invention is suitable for image formation using coherent monochromatic light, easy to manufacture and manage, and is capable of eliminating interference fringe patterns that appear during image formation and during reversal development. It is possible to provide a light-receiving member which can simultaneously and completely eliminate the appearance of spots, and which has excellent mechanical durability, particularly abrasion resistance and light-receptivity.

[Brief explanation of the drawing]

FIG. 1 is a general explanatory diagram of interference fringes. FIG. 2 is an explanatory diagram of interference fringes in the case of a multilayer light receiving member. FIG. 3 is an explanatory diagram of interference fringes due to scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. FIG. 5 is an explanatory diagram of interference fringes when the interfaces of each layer of the light receiving member are parallel. FIGS. 6A, 6B, 6C, and 6B are explanatory diagrams showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIGS. 7(A), (B), and (C) are explanatory diagrams for comparing the intensity of reflected light when the interfaces of each layer of the light-receiving member are parallel and non-parallel. FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. FIGS. 9(A), (B), and (C) are explanatory diagrams of the surface conditions of typical supports, respectively. FIG. 1θ is an explanatory diagram of the layer region of the light receiving member. FIG. 11 is an explanatory diagram of the surface state of the M support used in Examples. FIG. 12 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 13 and FIG. 14 are explanatory diagrams showing the layer structure of the light-receiving member produced in the example. FIG. 15 is an explanatory diagram of the image exposure apparatus used in the example. 16 to 24 show atoms (
0, C, N) is an explanatory diagram for explaining the distribution state. FIG. 25 to FIG. 28 are explanatory diagrams showing changes in gas flow rate in the example. 1000・・・・・・・・・・・・・・・Photoreceptive layer 1001・・・・・・・・・・・・・・・AI
Support body 1002・・・・・・・・・・・・・・・
First layer 1003・・・・・・・・・・・・・・・
・Second layer 1004・・・・・・・・・・・・・・・
・・Light receiving member 1005・・・・・・・・・・・・・・
...Free surface 2601 of light-receiving member...
......Light receiving member for electrophotography 2602
・・・・・・・・・・・・・・・・・・Semiconductor laser 2603・・・・・・・・・・・・・・・Fθ lens 2804・・・・・・・・・・・・・・・・・・Polygon mirror 2605・・・・・・Pa・・・・・・・
... Plan view of exposure device 2606 ......
・・・・・・・・・Side view of exposure device Patent applicant: Canon Co., Ltd. No. 1II Figure 2 Figure 3 Figure 4 ρ(l Figure 8 (A) (B) (C) Figure 9 Figure 13 Figure 14 Figure 15 -AζQ- = Figure 19 Figure 20 Figure 2T Figure 22 Figure 23 □C Figure 24 Fig. 26 η ° Su waterfall amount IE.

Claims (21)

[Claims] (1) A first layer made of an amorphous material containing silicon atoms and germanium atoms, a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity, and a silicon atom and a surface layer made of an amorphous material containing carbon atoms. containing at least one selected from among them, and having one or more pairs of non-parallel interfaces within a short range, and a large number of the non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction. A light-receiving member characterized by: (2) The photoreceptor layer according to claim 1, wherein the photoreceptor layer contains at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform state in the layer thickness direction. Element. (3) The light according to claim 1, wherein the photoreceptive layer contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms in a nonuniform state in the layer thickness direction. Receptive member. (4) The light receiving member according to claim 1, wherein the arrangement is regular. (5) The light receiving member according to claim 1, wherein the arrangement is periodic. (6) The light receiving member according to claim 1, wherein the short range is 0.3 to 500μ. (7) The light-receiving member according to claim 1, wherein the non-parallel interface is formed based on regularly arranged irregularities provided on the surface of the support. (8) The light-receiving member according to claim 7, wherein the unevenness is formed by an inverted V-shaped linear protrusion. (9) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially an isosceles triangle. (10) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a right triangle. (11) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a scalene triangle. (12) Claim 1, wherein the support body is cylindrical.
The light-receiving member described in 2. (13) The light-receiving member according to claim 12, wherein the inverted V-shaped linear protrusion has a spiral structure within the plane of the support. (14) The light receiving member according to claim 13, wherein the spiral structure is a multi-spiral structure. (15) The light-receiving member according to claim 8, wherein the inverted V-shaped linear protrusion is divided in the direction of its ridgeline. (16) The light receiving member according to claim 12, wherein the ridgeline direction of the inverted V-shaped linear protrusion is along the central axis of the cylindrical support. (17) Claim 7: The unevenness has an inclined surface.
The light-receiving member described in 2. (18) The light-receiving member according to claim 17, wherein the inclined surface is mirror-finished. (19) The light-receiving member according to claim 7, wherein the free surface of the light-receiving layer has projections and depressions arranged at the same pitch as the projections and depressions provided on the surface of the support. (20) The light-receiving member according to claim 1, wherein at least one of the first layer and the second layer contains hydrogen atoms. (21) Claim 1, wherein at least one of the first layer and the second layer contains a halogen atom.
The light-receiving member according to item 2 and item 20.