JPS6195360A - Light receiving material - Google Patents

Abstract

PURPOSE:To obtain an image freed of fringes using a light liable to interference by incorporating a specified element and a specified distribution of Ge in a light receiving layer specified in multilayer structure and formed on a substrate, forming nonparallel planes in minute areas, and arranging a number of said planes in one direction perpendicular to the film thickness direction. CONSTITUTION:The first layer 1002 made of a-SiGe, the second photoconductive layer 1003 made of a-Si, and a surface layer 1006 made of a-SiC are laminated on a conductive substrate 1001 in succession from the side of the substrate 1001 to from the light receiving layer 1000 of multilayer structure. Ge is incorporated in the layer 1002 in a distribution nonuniform in the film thickness direction, and at least one kind of O, C, and N elements is incorporated in the layer 1000. One pair or more of nonparallel planes formed in each minute area are arranged in a large number in at least one direction perpendicular to the film thickness direction. The use of such a light receiving layer 1000 permits interference fringes not to occur in the case of using monochromatic light liable to interference, therefore, this light receiving material to be adapted to image formation using such a light, to cause no spot at the time of reversing the image, and to be enhanced in mechanical characteristics and light receptive characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is directed to the use of light (light in a broad sense here, including 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]

As a method of recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is developed and A well-known method is to record one image by performing processes such as transfer and fixing depending on the image. Among them, in the image forming method using electrophotography, image recording can be performed using a small and inexpensive Ha-=)l- laser or a semiconductor laser (usually having an emission wavelength of 850 to 882-0n+). General.

In particular, as a light-receiving material for electrophotography that is suitable for use with semiconductor lasers, Vickers High hardness.

For example, Japanese Patent Laid-Open No. 54-811
Amorphous materials containing silicon atoms (hereinafter referred to as ra-
5tJ) is attracting attention.

However, if the photoreceptive layer is a single-layer a-9i layer, in order to maintain the high photosensitivity and ensure the dark resistance of 1G"001 or more required for electrophotography, it is necessary to Because it is necessary to structurally contain halogen atoms, boron atoms, and boron and ron atoms in a specific amount range in a controlled manner in the layer, it is necessary to strictly control the layer formation. There are considerable limitations on the tolerances in the design of the light-receiving member.

For example, Japanese Patent Laid-Open No. 54-121743 is an example of a system that can expand this design tolerance and make effective use of high light sensitivity even if the dark resistance is low to some extent.
Publication No. 5.7-4. ,,Q 5. ．． Publication No. 3,
As described in Japanese Unexamined Patent Publication No. 57-4172, the pre-passage layer may have a layer structure of two or more layers with different conduction characteristics, and a depletion layer may be formed inside the photoreceptive layer, or a special layer may be formed. 57,52178, 521711, 52.
No. 180, No. 51115119, No. 58. leO issue,
As described in each publication of No. 58181, a multilayer structure with a barrier layer provided between the support and the light-receiving layer and/or on the upper surface of the light-receiving layer is used to improve the appearance. A light-receiving member with increased dark resistance has been proposed. 5. Through such proposals, it is possible to improve the commercialization design and planning tolerances of a-'Ji-based light receiving and receiving members, or the ease of manufacturing management and productivity. Rapid progress has been made, and the speed of development toward commercialization 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 image defects. 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 IO incident on the layer constituting the light-receiving layer of the light-receiving member, reflected light R1 reflected at the upper interface 102,
It shows reflected light R2 reflected at the lower interface 10.1.

If the average layer thickness of the layer is d, the refractive index is n, and the wavelength of the light is uneven due to the thickness difference, then the reflected lights R1 and R2 are 2nd = mλ (m is an integer, the reflected lights strengthen each other) and 2nd = (m+-) entered (m
is an integer and the reflected light weakens each other), the amount of light absorbed and transmitted by a certain layer changes depending on which condition is met.

In a light-receiving member' having a multilayer structure, the interference effect shown in FIG. 1 occurs 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 (for example, Japanese Patent Application Laid-Open No. 58-162875). The surface of the aluminum support is treated with black alumite, or carbon, colored pigments, or dyes are dispersed in the resin. A method of providing a light absorption layer (for example, Japanese Patent Application Laid-Open No. 57-185845), a method of applying a satin-like alumite treatment to the surface of an aluminum support,
A method has been proposed in which a light scattering and antireflection layer is provided on the surface of a support by providing fine roughness in the form of grains by sandblasting (for example, JP-A-57-18554).

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, the surface of the support is simply provided with a large number of irregularities of a specific size, so although it does prevent the appearance of interference fringes due to the light scattering effect, it does not affect the light scattering. Since the specularly reflected light component still remains, in addition to the remaining interference fringe pattern due to the specularly reflected light, the irradiation spot is broadened due to the light scattering effect on the support surface, and the irradiation spot is substantially This caused a significant decrease in resolution.

The second method involves black alumite treatment.

Complete absorption is impossible, and the light reflected on the support surface remains. In addition, when providing one colored pigment-dispersed resin layer, a-9
When forming the i-layer, there is a degassing phenomenon from the resin layer, which significantly reduces the quality of the photoreceptive layer formed, and the resin layer is damaged by plasma during the formation of the a-9i layer. This has disadvantages such as reducing the original absorption function and adversely affecting the subsequent formation of the a-5i 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. teeth,
The light enters the inside of the light-receiving layer 302 and becomes transmitted light 11. On the surface of the support 302, a part of the transmitted light 11 is scattered and becomes diffused light Kl sK2 *3..., and the rest is specularly reflected and becomes reflected light R2, and part of it is reflected light R2. It becomes the emitted light R3 and goes outside, so the reflected light R
Since the emitted light R, which is a component that interferes with 1, remains, the interference fringe pattern cannot be completely erased.

Furthermore, if the diffusivity of the surface of the support 301 is increased in order to prevent interference and multiple reflections within the light-receiving layer, the light will be diffused within the light-receiving layer. There is also a drawback that the resolution is lowered due to the occurrence of ln. .

In particular, in a multilayered light-receiving member, even if the surface of the support 49.1 is irregularly roughened, as shown in FIG.
Reflected light R2m on the surface of calendar 402 Reflected light R on the second layer
1'+Support 4.0.1. , specular reflection light on a surface 1゛? husband"
"""F#=L'c, - the thickness of each layer of the receiving member 0, and therefore an interference fringe pattern occurs. Therefore, in a light receiving member with a multilayer structure, it is not necessary to irregularly roughen the surface of the support 4o1. , 1 tsubo Hf t to completely prevent interference fringes! ? $
> 5 f-・-Also, when the surface of the support is irregularly roughened by a method such as sandblasting, the roughness varies widely between lofts, and even in the same lot there is no difference in roughness. There was uniformity, which was bad in terms of manufacturing control. 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, water is usually deposited on the light-receiving layer 502 in stripes on the surface of the support +01.
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 2ndt = m or 2ndt = (m + 34)λ, which becomes a bright part or a dark part, respectively. Further, in the entire photoreceptive layer, a light and dark striped pattern appears due to the difference in the layer thickness dt ndt sd3 *d4 of the photoreceptive layer.

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

Also, when a multi-layered light-receiving layer is deposited on a support 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.

[Purpose 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 manufacture and manage.

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

Another object of the present invention is electrical voltage resistance -wL-
-ML--M☆J Massage C Jitsuneho-Uramumu Lazy^b It is also to provide members.

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 and resolution. There is also.

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

[Summary of the invention]

The light-receiving member of the present invention includes a first layer made of an amorphous material containing silicon atoms and germanium atoms, and a first layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. 2 and a surface layer made of an amorphous material containing silicon atoms and carbon atoms are provided in order from the support side, and in the first layer, The distribution state of germanium atoms in the layer thickness direction is nonuniform, and the photoreceptive layer contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and It is characterized in that it has 11 diagonal interfaces, and a large number of these non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction.

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 ds, the interface 803 and the interface 804 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 interference fringe pattern.

In addition, as shown in FIG. 7, if the interface 703 between the first layer 7.01 and the second layer 702 and the free surface 7G4 of the second calendar 702 are non-parallel, then as shown in FIG. Similarly, since the traveling directions of the reflected light R1 and the emitted light R3 for the incident light IO are different from each other, the degree of interference is lower than when the interfaces 703 and 704 are parallel (r (B) J in Fig. 7). decreases.

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. The difference in brightness of the striped pattern becomes negligible.

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 (dy(do) as shown in FIG. 6), so the amount of incident light is uniform in 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. 1o, reflected light R1+R2+R3'□R4JS exists. In the ninth layer what has been 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.

Furthermore, interference fringes that occur within minute portions 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, and even if they do appear in the image. However, since the resolution is below the resolution of the eye, there is virtually no problem.

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

If the spot diameter of the irradiation light is L, the size l (one period of the uneven shape) of the minute portion suitable for the present invention is as follows! ≦L.

Also, in order to achieve the purpose of the present invention more effectively, minute parts! It is desirable that the difference in layer thickness (ds ds) in the irradiation light is as follows, where λ is the wavelength of the irradiation light, λ ds −d,≧ □ n (n: refractive index of the second layer 8G2).

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. As long as the thickness of each layer is controlled within the microcolumn and this condition is satisfied, any two layer interfaces may be in a parallel relationship within the microcolumn.

However, it is desirable that the layers forming parallel layer interfaces be formed to have a uniform layer thickness over the entire region so that the difference in layer thickness at any two positions is λ or less.

Plasma gas is used to form the first layer and second layer constituting the photoreceptive layer because the thickness of each layer can be precisely controlled at the optical level in order to more effectively and easily achieve the object of the present invention. A phase method (PCVD method), a photo CVD method, and a thermal CVD method are employed.

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 an inn. By regularly moving in a predetermined direction while rotating, the surface of the support is accurately cut to form a desired uneven shape, pitch, and depth. The inverted 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-shaped protrusion may be a double, triple, multi-end structure, or a crossed spiral structure.

Alternatively, in addition to the spiral structure, a linear structure along the central axis may be introduced. The vertical cross-sectional shape of the uneven convex portion provided on the surface of the support is determined by the layer thickness within the microcolumn of each layer formed. In order to ensure controlled non-uniformity and good adhesion and desired electrical contact between the support and the layer provided directly on the support, it is preferably inverted. is shown in Figure 9.
It is preferable that the shape is substantially an isosceles triangle, a right triangle, or a scalene triangle, so that the shape is preferably an isosceles triangle or a right triangle.

In the present invention, each dimension of the unevenness provided on the surface of the support in a controlled manner is set such that the object of the present invention can be achieved as a result, taking into consideration the following points. .

That is, '1' is the a-8i layer that constitutes the photoreceptive layer.

It is very sensitive to the condition of the surface on which the layer is formed, and the quality of the layer varies greatly depending on the surface condition.

Therefore, it is necessary to set the degree of unevenness provided on the surface of the support so as not to cause a deterioration in the layer quality of the a-9i layer. -Secondly, if the free surface of the radiation-receiving layer has extreme irregularities, it becomes impossible to perform complete cleaning □ in cleaning after forming a single-picture urn.

Further, when cleaning the blade, there is a problem that the blade gets damaged quickly.

As a result of examining the above-mentioned ``problems in layer deposition'' and ``process problems in electrophotography'' and conditions for preventing interference fringes, the pitch of the recesses on the surface of the support is preferably 5.
00u −0,3u, more preferably 200− to [1
m, optimally 501 m to 5-.

Further, the maximum depth of the recess is preferably 0.1-5-9
More preferably 0.3u~3-・, optimally 0, Bμ~
When the pitch and maximum depth of the recesses on the surface of the support, which is preferably 2μ, are within the above range, the slope of the slope of the recesses (or linear protrusions) is preferably 1 degree to Desirably, the angle is 20 degrees, more preferably 3 degrees to 15 degrees, most preferably 4 degrees to 14 degrees.

In addition, variations in the thickness of each layer deposited on such a support may
The maximum difference in layer thickness based on gender is preferably O
0lμs to 2 scales, more preferably 0, IJLII-1
, 5g, optimally 0.21m, ~1JIJ+.

Furthermore, 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 exhibits photoconductivity. It has a multilayer structure in which a second layer and a surface layer made of an amorphous material containing silicon atoms and carbon atoms are provided in order from the support side, and the germanium atoms in the first layer are Because the distribution state of the layer is non-uniform in the layer thickness direction, it exhibits extremely excellent electrical, optical, and photoconductive properties - electrical voltage resistance and use environment characteristics.
' - In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high signal-to-noise ratio. It has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

Furthermore, the light-receiving member of the present invention has high photosensitivity in the entire visible light range. In particular, it has excellent photosensitivity characteristics on the long wavelength side, so it is particularly suitable for matching with semiconductor lasers, and has a fast optical 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 has a function as a protective layer for mechanical durability;
Optically, it can primarily function as an antireflection layer.

The above surface layer is suitable to function as an antireflection layer when the following conditions are met.

That is, the refractive index n1 layer thickness of the surface layer is d, and the wavelength of the incident light is λ.
Then, when λ d = - n or an odd multiple thereof, the surface layer is suitable as an antireflection layer.

Also, when the refractive index of the second layer is h, the refractive index n of the surface layer satisfies n=I, and the layer thickness d of the surface layer satisfies d=-, then 1 surface The layer is suitable as an anti-reflection layer.

When a-Si:H is used as the second layer, a-Si
: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:H can have a refractive index of such a value by adjusting the amount of C, and also satisfies mechanical durability, adhesion in the living room, and electrical properties. Therefore, it is the most suitable material for one surface layer.

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

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

FIG. 10 is a schematic diagram schematically showing the layer structure 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 100G on a support 1001 for the light-receiving member.
However, the photoreceptive layer 1000 has a free surface 1005 on one end surface.

The photoreceptive layer 1000 is made of a-Si (hereinafter referred to as ra-9iGe (
H, X) A first layer CG composed of
) 1002 and, if necessary, a hydrogen atom or/and a halogen atom (X) (hereinafter referred to as ra-Si
(H, It has a layered structure.

In the light-receiving member 1004 shown in FIG. 1O, the surface layer 1006 formed on the second layer 1003 has a free surface and mainly has moisture resistance, continuous greening usage characteristics, electrical pressure resistance, It is provided in order to achieve the object of the present invention in terms of mechanical durability and light receiving properties.

The surface layer 1006 in the present invention is composed of silicon atoms (Si
), a carbon atom (C), and, if necessary, a hydrogen atom (I()
and/or an amorphous material containing a halogen atom (X) (hereinafter referred to as 'a-(StXc, -X)y (H,X)
Written as I-y J, where 0 < x, y < 1)
Consists of.

a-1'Jix Cs -x )y (I(,X) s
The formation of the table TIfim100B consisting of -v te is performed by a plasma vapor phase method (PCVD method) such as a glow discharge method, a photo CVO method, a thermal CVD method, a sputtering method, an electron beam method, or the like. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, manufacturing scale, and the desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control manufacturing conditions for manufacturing a photoconductive member having the above-mentioned photoconductive member. The glow discharge method or the sputtering method is preferably employed because of the advantages that it is easy to introduce carbon atoms and halogen atoms together with silicon atoms into the surface layer 1006 to be formed.

Furthermore, in the present invention, a glow discharge method and a sputtering method may be used together in the same apparatus system to form the surface layer 100B.

To form the surface layer 100B by the glow discharge method,
a-(Six cl+ll)y (H,X) ty
The raw material gas for formation is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a deposition chamber installed with a support.The introduced gas is caused to generate a glow discharge. d-' (SLtCt-
x) y(H, XL-y 11"1ttL4f Good.

In the present invention, a-(Six c, +llll)y
(H, Most gaseous substances containing gaseous substances or gasified substances that can be gasified may be used.

When using a raw material gas having Si as a constituent atom as one of Si, 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, '5 raw material gas containing H as a constituent atom and/or 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 may be used. , - A raw material gas containing C and H and/or a raw material gas containing C and X as constituent atoms are also mixed at a desired mixing ratio, or Si is used as a constituent atom A raw material gas 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, preferable halogen atoms (X) contained in the surface layer 100B are F, α'', Br,
In particular, F and α are desirable.

In the present invention, raw material gases that can be effectively used to form the surface layer 100B include those in a gaseous state at normal temperature and pressure, or substances that can be easily gasified. can.

In the present invention, 5iH41, Si2H6, 5i3H6, 5i4H1 containing Si and H as constituent atoms are effectively used as the raw material gas upper plate for forming the 6 surface layer 100B.
Silicon hydride gas such as silanes such as No. 6,
1 whose constituent atoms are C and H, for example, carbon atom/number of atoms 1-
4 saturated hydrocarbons/elements, engineering/tyrene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, halogenated silicon, Specific examples include halogen substitution, silicon hydride, and silicon hydride.

Saturated hydrocarbons include methane (CH4) and ethane (
C2H6), propa7 CC5H3), n-butane (s-CJI to), pentane (C5H12),
Ethylene hydrocarbons include ethylene (C2H4)
, propylene (CJI6)', b+7-1' (CaH
a) 4 Butene-2 (04HII), inbutylene (CJIs), pentene (CsHs), acetylene hydrocarbons include acetylene (02H2)
, methylacetylene (sHa), butyne (CJ(6)
,・Halogen gases include fluorine, chlorine, bromine, and iodine, and hydrogen halides include FH,
H[, Hα* HBr, interhalogen compounds are BrF, αF, αF3, αF5, BrF5, BrF
3. IF7, IF5. Iα, far, silicon halide is SiF4,” 5i2F 6.,
Siα3Br, Siα28 r2, S[(jBr3,
Siα31. SiBr4, halogen-substituted silicon hydride includes SiH2, F2, SiH2α2, Si
Hα3゜SiH3α, 5iH3Br, 5iH2Br2
As 1.5iHBr3 silicon hydride, SiH, Si
2H6, 5i3H6, 5iaHto Shiran (Sil)
ane), etc.

In addition to these, CF4. Cα4. CBr4, CHF3
, Cl2F2 , 0H3F, CH3Cj', CH3
Halogen-substituted paraffinic hydrocarbons such as Br, CH31, C2H5α, fluorinated sulfur compounds such as SF4, SF6; alkyl silicides such as 5l(CH3)4, Si(C2H5)4, and Siα(CH3)! , Siα2(IJ
3) Silane derivatives such as halogen-containing alkyl silicides such as 2 and 5iC13CH3 can also be mentioned as effective.

These surface layer 100B forming substances are used to form the surface layer 100B so that the formed surface layer 1008 contains silicon atoms, carbon atoms, 9 halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. It is selected and used as desired when forming the .

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((J3)4 and SiHαs, SiH2α2, Siα4, or SiH2α2 as those containing halogen atoms at a predetermined mixing ratio and introduced in a gas state into an apparatus for forming the surface layer 1006 to generate a glow discharge. By causing a-(Six Cs −x )
A surface layer 1006 consisting of y(α+H)J-a 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, H and/or
What is necessary is just to dilute it as needed, introduce it into the deposition chamber for sputtering, and form a gas plasma of these gases to sputter the Si wafer.

Alternatively, by using separate targets for Si and C or a single target containing a mixture of Si and C, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be used as needed. This is done by sputtering in the medium. As the material gas for introducing C, H, and X, the material for forming the surface layer 1006 shown in the glow discharge example mentioned above can also be used as an effective material in the case of the sputtering method.

In the present invention, the diluent gas used when forming the first surface layer 100B by a glow discharge method or a sputtering method is a so-called rare gas, such as He or Me.

Suitable examples include Ar and the like.

The surface layer 1008 in the present invention is carefully formed to provide the desired properties.

It will be done.

In other words, a substance whose constituent atoms are Si, C, and optionally H or/and properties ranging from conductivity to semiconductivity to insulating properties,
In addition, since they exhibit both photoconductive and non-photoconductive properties, in the present invention, a-(
Six c, -X )y (H, a-(Six C
1-x )v (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 degree of electrical insulation described above is relaxed to some extent, and the surface layer 100B is provided with a non-woven material having a certain degree of sensitivity to the irradiated light. As a crystalline material a-(
Six c, -X)y (H,X)sy is created. a-(SixC1
When forming the surface layer 100B consisting of (H, In the present invention, a-(Six
It is desirable that the temperature of the support during layer formation be strictly controlled so that C1-)l)y(H,X)ty can be formed as desired.

In the present invention, the formation of one surface layer 100B is carried out by appropriately selecting an optimal range in accordance with the method of forming the surface layer 100B in order to effectively achieve the desired purpose, but preferably 20 to The temperature is preferably 50 to 350°C, more preferably 100 to 300°C than 400°C.To form the surface layer 100B, delicate control of the composition ratio of the atoms constituting the layer is required. It is advantageous to adopt a glow discharge method or a sputtering method because it is relatively easy compared to the method described above. However, when forming the surface layer 100B using these layer forming methods, Similar to the body temperature, the discharge power during layer formation is created by a-(Sf, cl-)l
)y CH, X) It is one of the important factors that influences the characteristics of ty.

a-(Sfx Ct -x)y (H,X) having the characteristics to effectively achieve the purpose of the present invention
The discharge power conditions for effectively creating t-y with good productivity are preferably 10 to too low, more preferably 20 to 750 W, and optimally 50 to 850 W. .

The gas pressure in the deposition chamber is °, preferably 0.01 to I
Torr, preferably about 0.1 to 0.5 To''rr.

In the present invention, the above-mentioned values are listed as the preferable value ranges for the support temperature and discharge power for creating the surface layer o+oe. The desired characteristics a−(9i, ('CI −X )v (H−X) t
It is desirable that the optimum value of each layer formation factor be determined based on the mutual permissive association so that a surface layer 1 (1'o11) consisting of -y is formed.

- The amount of carbon atoms contained in the surface layer orae of the yet-to-be-discovered photoconductive member is the same as the conditions for forming the surface layer 100B, so that the surface can obtain the desired characteristics to achieve the object of the present invention. This is one of the important factors in the formation of layers.

The amount of carbon/carbon atoms contained in the surface layer 100'8 of the present invention can be determined as desired depending on the type and characteristics of the amorphous material constituting the surface layer 100B. be.

That is, the general formula a-(Six c, -X)y (
H, However, O < a < 1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as 'a-
Written as C3kb Ct -h )e Ht -c J,
However, 0 < b, c < 1), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as r a-(Si7 Ct -a)
).

(H,X)1-@J, where O< d, e<
It is classified as 1).

In the present invention, the surface layer 1006 is made of a-Si, CB-,
, the amount of carbon atoms contained in the surface layer 1ooe is preferably I
*ic%, more preferably 1 to 80 atoms
ic%, preferably 10 to 75 ic% of the ato layer. That is, the previous a-5i, C1-
, then a is preferable and < is 0.1 to 0
．． 111911199. More preferably 0.2 to o,
9s, optimally 0.25-0.9.

'', in the present invention, the surface layer 10''j is a-(S
When composed of LCt-h) cut-a, the amount of carbon atoms contained in the surface layer 100B is preferably lX10=~3°atomij'%, more preferably r4' 9 (latomic%, optimally lO
It is preferable that the range is between 80% and 80%. The content of hydrogen atoms is preferably 1 to 40% by weight, more preferably 2 to 35% by weight.
atomic%, preferably 6 to 30 atos+ic%, and the light-receiving member formed when the hydrogen content is in this range is considered to be excellent in terms of Can be fully applied.

That is, the above a-(SilCi-+-). ) If it is expressed as It-e, b is preferably 0.1 to 0.93889
, □ more preferably 00l-0.99, optimally 0.15
~G, 9. c is preferably 0.8 to 0.99, more preferably o, e+5=lo, so, optimally 0.7 to 0.
95 is desirable.

□The surface layer 1008 is a-(Si, Ct-i)*(H,
In the case of X) t-*te, the content of carbon atoms contained in the surface layer 100e is preferably as follows:
IXIG'~Hatomic%, more preferably 1-9
0 atomic%, optimally 10-10 atomic%
It is desirable that this is the case. The content of halogen atoms is preferably 1 to 20 atomic%, and the light-receiving member produced when the halogen content is in this range is sufficiently applicable to practical applications. It's something you get. Contained as necessary □
The content of waterfowl atoms is preferably 18 atoms.
It is desirable that the content be 13 ato*ic% or less, more preferably 13 ato*ic% or less.

That is, the above a-(Si4Ct-). (H,X)1-'@
If it can be done by displaying d and e, d is preferably 0.
1 to 0.99999, more preferably 0.1 to 0.89, most preferably 0.15 to 0.9, e is preferably 0.8 to 0.
88, more preferably 0.82-o, ss, optimally 0.88, more preferably 0.82-o, ss.
It is desirable that it is 85 to 0.88.

In the present invention, the numerical range of the layer thickness of the surface layer 1006 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 amount of carbon atoms contained in the layer and the thickness of the first to second layers. It is necessary to decide as appropriate based on the organic relationship depending on the desired situation.

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

The layer thickness of the surface layer 100B in the present invention is preferably 0.003 to 30 scales, more preferably 0.004 to 2 scales.
It is desirable that the time be 0 μs, and optimally 0.005 to 10 μs.

The germanium atoms contained in the first layer (G) 10G2 are continuous in the thickness direction of the first layer (G) 1002 and are different from the side on which the support 1001 is provided. Opposite side (surface 10a5 side of photoreceptive layer 1001)
It is contained in the first layer (G) 1002 so that it is more distributed on the support 1001 side than on the support body 1001 side.

In the light-receiving member of the present invention, the distribution state of germanium atoms contained in the first layer (G) is as described above in the layer thickness direction, and the distribution state is parallel to the surface of the support. It is desirable to have a uniform distribution in the in-plane direction.

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, it can be used for light from relatively short wavelengths to relatively short wavelengths, including the visible light region. This can be used as a light-receiving member that has excellent photosensitivity to light of all wavelengths.

In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed in the entire layer region,
Since the distribution concentration C of germanium atoms in the layer thickness direction is given a change that decreases from the support side toward the second layer (S), the first layer (G) and the second layer (S) By making the distribution concentration C of germanium atoms extremely large at the edge of the support, as will be described later, the second layer can be used when a semiconductor laser or the like is used. The first layer (G) can substantially completely absorb light on the long wavelength side that is almost completely absorbed by (S), and can prevent interference due to reflection from the support surface. .

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, the laminated interface is sufficiently acidified to ensure chemical stability.

4 FIGS. 11 to 19 show typical examples of the distribution state of germanium atoms contained in the first layer (G) of the light-receiving member in the present invention in the layer thickness direction. In addition, in each figure, the display of one layer thickness and concentration is shown in an extreme form because if the values are shown as they are, the differences between each figure will not be clear. I want to be understood,
As for the actual distribution, the purpose of the present invention can be achieved,
Ti (1≦i
≦8) or C1 (1≦i≦17), or the value obtained by multiplying the entire distribution curve by an appropriate coefficient should be taken.

In FIGS. 11 to 19, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the layer thickness of the first layer (G). is the position of the end surface of the first layer CG) on the support side,
The digit indicates the position of the end face of the calendar (G) on the side opposite to the support side, that is, the position of the first layer (G) containing germanium atoms.
) is 1. Layer formation is performed from the side toward the tl side.

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

In the example shown in FIG. 11, the surface on which the first layer CG containing germanium atoms is formed and the first layer CG
) is in contact with the surface of the first layer (G
), and the concentration C2 is higher than the interface position t than the position tl.
It is gradually and continuously decreased until T. At one interface position, the distribution concentration C of germanium atoms is substantially zero (substantially zero here means that the concentration is below the detection limit).

In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms is at position 1. A distribution state is formed in which the concentration gradually and continuously decreases from .alpha. to the concentration C at position MLr up to position 1.

In the case of FIG. 13, position 1. From higher to altz,
The distribution concentration C of germanium atoms is kept constant throughout the concentration, gradually and continuously decreases between positions t2 and 11, and decreases gradually and continuously between positions t2 and 11. In the case of FIG. 14, where the distribution concentration C is substantially zero, the distribution concentration C of germanium atoms is at position 1. From position 1 to position 1, the concentration is first gradually and continuously reduced from C6, and from position t3, it is rapidly and continuously reduced until it becomes substantially zero at position 1.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is C7 between the position tB and the position ta.
is a constant value, and the distribution concentration C is zero at position 1. Between 0 position t4 and position 11, the distribution concentration C decreases linearly from position t4 to position 1. has been done.

In the example shown in FIG. 18, the distribution concentration C is at position 1.
．． From position t5, the concentration CB takes a constant value, and from position t5 to position 1, the distribution state decreases linearly and functionally from concentration C9 to concentration CIG.

In the example shown in FIG. 17, the distribution concentration C of germanium atoms from the 1st position ta to the 1° position is the concentration CO
It decreases continuously in a linear function so as to reach zero more substantially.

In FIG. 18, position 1. Up to position 6, the distribution concentration C of germanium atoms decreases linearly from the concentration C2 to 013, and between position t6 and position 1T, the concentration C13 is a constant value. An example is shown.

In the example shown in FIG. 18, the distribution concentration C of germanium atoms is the concentration Cta at position a[tO,
Until reaching position t7, the density is gradually decreased from this concentration Cta, and in the vicinity of position t7, it is rapidly decreased to a concentration of 015 at position t7.

Between position 1 and position t8, it is rapidly decreased at first, and after 7, it is gradually decreased to position t8.
The concentration becomes 01 & between the position device t8 and the position t9, and the concentration is gradually decreased to 01& at the position t9.
Between the 0 position t9 and the position t7, which reaches 7, the density is reduced from CS7 to substantially zero according to a curve shaped as shown in the figure.

As described above with reference to FIGS. 11 to 19, some typical examples of the distribution state of germanium atoms contained in the first layer (G) in the layer thickness direction, in the present invention, , on the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface tτ side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. It is preferable that the first layer (G) be provided with the same amount.

The first layer (G) constituting the light-receiving member in the present invention preferably has a localized region (A) containing germanium atoms at a relatively high concentration and concentration on the support side as described above.
It is desirable to have .

In the present invention, the localized region (A) is
The following can be explained using the symbols shown in Figure 8: 1. It is preferable that the interface position be provided within 5IL from day to day.

In the present invention, the localized region (A) is located at the interface position t8.
It may be the entire layer region (L) up to 51L thick, or it may be a part of the 1# bond castle (1,).

Whether the localized region (A) is a part or all of the layer region (L) depends on the light-receiving layer to be formed! It is determined as appropriate according to the required characteristics.

The localized region (A) is preferably 1000 atosgjcpp with respect to silicon gX+, as the distribution state of germanium and nium atoms contained therein in the layer thickness direction. [:that's all,
It is desirable that the layer be formed in such a manner that the distribution state can be more preferably 5000 atomic ppm or more, most preferably 1×10 4 atomic ppm or more.

That is, in the present invention, the first layer CG containing germanium atoms has a layer thickness of 5 layers or less (CG) from the support side.
The maximum value of the distribution concentration Cma!
It is preferable that it be formed so that there is.

In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the amounts 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 l −40atoi+jc
%, more preferably 5 to 30 ato fat ic%, optimally 5
It is desirable that the content be 25 atomic%.

In the present invention, the first J! The content of germanium atoms contained in (G) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9.5X 105105ato pps+
, more preferably 100-8X10 Satom
It is preferable to wear ic PP shoes.

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 of the first layer (G) is 8.

Preferably 30A to 50%, more preferably 40A to 50%
40IL, optimally 50A to 30IL.

Further, the layer thickness T of the second layer (S) is preferably 0.5 to 9
It is desirable that the diameter be 0, more preferably 1 to 80 liters, most preferably 2 to 50 liters.

The sum (T8+T) of the layer thickness Tl of the first layer (G) and the layer 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, the numerical range of (T++T) is preferably 1 to 100 p, more preferably 1 to 80 p, and most preferably 2 to 50 p. .

In a more preferred embodiment of the present invention, the above layer thickness ra and layer thickness T are preferably Ti+/T≦1
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

In selecting the numerical values of layer thickness T8 and layer thickness T in the above case, it is more preferable that Ta/T≦0.9. Optimally, it is desirable that the values of the layer thickness 1 and the layer thickness T be determined so that the relationship T, /T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer CG) is l x 10' atomic
In the case of PPM or more, it is desirable that the layer thickness (G) of the first calendar (G) be made quite thin, preferably 30
p, below, more preferably below 25, optimally below 20
It is desirable that it be JL or below.

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-9iGe (H, done by law1
For example, a-SiGe (H,
X) To form the first layer (G) composed of Introducing the raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (H) and/or the raw material gas for introducing halogen atoms (X) into the deposition chamber in which the internal pressure can be reduced at the desired gas pressure state. A glow discharge is generated in the deposition chamber, and the distribution concentration of germanium atoms contained on the surface of a predetermined support, which has been set in advance at a predetermined position, is controlled according to a desired rate of change curve. It is sufficient to form a layer consisting of (H, When sputtering is performed using two targets, one made of Si and one made of Ge, or a mixed target of Si and Ge, hydrogen atoms (H) or/and It is sufficient to introduce a gas for introducing halogen atoms (X) into the deposition chamber for sputtering.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH, 5izH & eSi
Gaseous silicon hydride (silanes) such as 3H6, 5i4H16, etc., which can be gasified or gasified, can be effectively used, especially because of their ease of handling during calendar preparation work, good Si supply efficiency, etc. In this respect, 5iHa and S cage 2H6° are preferred.

Substances that can be used as raw material gas for Ge supply include:
GeHa, Ge2H'6, Ge
3Hg, Ge2H'6, Ge5
H12.

(ie6H14, Ge7H16, Ge6) I I81
Germanium hydride in a gaseous state or capable of being gasified, such as Ge5H2o, can be effectively used, especially in terms of ease of handling during calendar preparation work and good Ge supply efficiency.

Preferable examples include GeH4, Ge2)16, and Ge3HB.

In the present invention, many halogen compounds are effective as raw material gases for introducing halogen atoms, such as halogen gases, halogenides, interhalogen compounds, and halogen-substituted gases. Preferred examples include silane derivatives and other gaseous or gasifiable nitrogen compounds.

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, αF, αF3+ Br F5 *B
Examples include interhalogen compounds such as rF3, IF3, IF7, Iα, and IBr.

Examples of silicon compounds containing a halogen atom, so-called halogen atom-substituted silane derivatives include 5jFa, 5if6, '5il14.5iBra.
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, a raw material gas that can supply Si together with a raw material gas for supplying Ge is used. a-5iGe containing halogen atoms on a desired support without using silicon hydride gas.
It is possible to form a first layer (G) consisting of:

According to the glow discharge method, the first layer containing human rogen atoms (
When preparing G), basically 1, for example, a predetermined mixture of silicon halide, which is a raw material gas for Si supply, 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 first layer (G) into a deposition chamber for forming the gas and generating a glow discharge to form a plasma atmosphere of these gases. However, in order to more easily control the ratio of hydrogen atoms introduced, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases to form a layer.

In addition, each gas may be used not only as a single type but also as a mixture of multiple types at a predetermined mixing ratio.

In order to form the first calendar (G) made of a-5iGe (H, Using two targets made of Ge, or a target made of Si and Ge, sputtering is performed in a desired gas plasma atmosphere. In this method, single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and these evaporation sources are heated and evaporated by a resistance heating method, an electron beam method (EB method), or the like. This can be done by passing flying evaporates 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. 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, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, Hα, Her, 'H1, etc. Hydrogen halide, SiH2F2, SiH212.

SiH2α2, 5iHC13, 5jH2Br2, 5
Halogen-substituted silicon hydride such as iHBr3, and Ge)H
F3, GeHBr3, GeH3F.

Gelα3, GeHBr3, GeH3α, G
eHBr3.

GeHBr3, GeHBr3, a halide containing a hydrogen atom as one of its constituent elements, such as germanium hydrogenation halide, GeF4゜Geα4. G
eBr4, GeIa* GeF2. Geα2,
Gaseous or gasifiable substances such as germanium halides such as GeBr2*Ge I2 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 during the first formation (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, 82 + or SiH4, 5i2H6, S
+3HB #5I4H16 or other silicon hydride with germanium or germanium compound for supplying Ge, or GeH4t Ge2H & r Ge3HB I
GeaH10* Ge5H12+Ge6Hta + G
This can also be carried out by causing germanium hydride such as etHI6 # GeaHsa e Ge9H2o 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 calendar (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 0.01 to 40
ato ic%, more preferably 0.05 to 30 at
It is desirable that the content be 0.1 to 25 atomic%, most 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 calendar (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms ( The amount of the starting material used to contain X) introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the second
To form the layer (S), a starting material [second It can be carried out according to the same method and conditions as in the case of forming the first layer (G) using the starting material (II)) for forming the layer (S).

That is, in the present invention, to form the second layer (S) composed of a-5i (H, For example, in order to form the second layer (S) composed of a-Si (H, ), as well as a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary.
Introduce it into a deposition chamber whose interior can be reduced in pressure.

A glow discharge is generated in the deposition chamber, and a -5i(H,X
), it is sufficient to form a calendar consisting of

When forming by sputtering method, for example, Ar, H
When sputtering a target composed of St in an atmosphere of an inert gas such as e or a mixed gas based on these gases, a gas containing hydrogen atoms (H) or/and halogen atoms (X) iX is used. may be introduced into the deposition chamber for sputtering.

In the light-receiving member of the present invention, two light-receiving layers are used for the purpose of increasing photosensitivity, increasing dark resistance, and further improving the adhesion between the support 7 and the light-receiving layer. inside.

contains at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform or non-uniform distribution state in the layer thickness direction. Such atoms (m-cπ) contained in a light-receiving layer may be contained in the entire layer region of the light-receiving layer, or may be contained only in a part of the layer region of the light-receiving layer. It is also possible to make them unevenly distributed.

The distribution state of atoms (OCN) is distribution, distribution concentration C (100M)
However, 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 containing Ocm is provided so as to occupy the entire layer area of the photoreceptive layer, and the layer area between the support and the light-receiving layer is When the main purpose is to strengthen the adhesion between the light-receiving layer and the support layer, the light-receiving layer is provided so as to occupy the end layer region on the side of the support.

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

In the present invention, a layer region (OCN
) The content of atoms (0ON) contained in the layer region ((
IcII) itself or the layer region (O
When CN) is provided in contact with the support, it can be appropriately selected depending on the organic relationship, 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 (OCN), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. is also taken into account,
The content of atoms (OCN) is selected appropriately.

The amount of pendulum (OCa) contained in the layer region (0(:N)) is determined as desired depending on the characteristics required of the light receiving member to be formed, but is preferably 0.001
~50 atomic%, more preferably 0.002~
- 40 atomic%, optimally 0-003 NHa
It is preferable to set it as TEHOIC%.
.

In the present invention, whether one 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 TK of the photoreceptor layer is the layer thickness To of the layer area (OCN). When the proportion is sufficiently large, it is desirable that the upper limit of the content of atoms (OCN) contained in one layer region (0 to 11) is sufficiently smaller than the above value.

In the case of the present invention, when the ratio of the layer thickness To of the layer region (OCN) to the layer thickness T of the photoreceptive layer is two-fifths or more, Atoms contained in (
OCN) is preferably 30ato@ic
% or less, more preferably 20 atomic % or less, optimally 1 oatosrc % or less. According to a preferred embodiment of the present invention, 1. Atom (OCN)
The first layer provided directly on the support preferably contains at least an atom (0ON) at the end layer of the support side of the photoreceptive layer. By doing so, 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.

In addition, multiple types of these atoms (OCjl) may be contained in the photoreceptive layer. For example, oxygen atoms and nitrogen atoms may be contained together.

20 to 28 show typical examples in which the distribution state of atoms (OCN) contained in the layer region (OCN) of the light-receiving member in the present invention is non-uniform in the layer thickness direction. .

In Figures 20 to 28, the horizontal axis represents atoms (OCN).
The vertical axis indicates the layer thickness of the layer region (00%), ttl indicates the position of the end surface of the layer region (octt) on the support side, and ttl indicates the layer region (octt) on the opposite side to the support side. In other words, the layer region (OCN) containing atoms (OCN) is 1. Layer formation is performed from the side toward the first side.

FIG. 20 shows the first case where the distribution state of atoms (OCN) contained in the layer region C0CN") in the layer thickness direction is non-uniform.
A typical example is shown.

In the example shown in FIG. 20, the surface where the layer region (OCN) containing atoms (OCN) is formed and the layer region (OCN)
From the interface position LB where it contacts the surface of N) to the position t8, the distribution concentration C of atoms (OCN) takes a constant value of 01, and the layer region (OCN) where atoms (OCN) are formed.
The concentration is gradually and continuously reduced from position t1 to interface position tT. Interface position fit
At τ, the distribution concentration C' of atoms (OCN) is taken to be the concentration .

In the example shown in FIG. 21, the contained atoms (
OCN) distribution concentration C is at position 1. The density gradually decreases continuously from C4 until it reaches position 1. A distribution state is formed such that the concentration is small at .

In the case of Fig. 22, the distribution concentration C of atoms (0111:N) from position ta to position t2 is a constant value of concentration C6, and gradually and continuously between position t2 and position 1. At one reduced position ty, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 23, the distribution concentration C of atoms (OCN) is at position 1. The concentration is gradually decreased from the concentration CB until it reaches the position 1T, and becomes substantially zero at the position 1T.

In the example shown in FIG. 24, the distribution concentration C of atoms (OCN) is a constant value of concentration C9 between position L8 and position 13, and at position 1, the concentration is 0 position t3, which is the concentration CIO. The distribution density C is linearly linearly distributed from position t3 to position 1. It has decreased to .

In the example shown in FIG. 25, the distribution concentration C is at position fi
l From LB to position t4, the concentration C□ is a constant value, and from 1 position t4 to position 1jty, the concentration is from 012 to C
The distribution state decreases linearly up to I3.

In the example shown in FIG. 26, position 1. Up to the position 1T, the distribution concentration C of atoms (0ON) decreases in a linear function from the concentration C14 to substantially zero.

In FIG. 27, from position t8 to position t5, the distribution concentration C of atoms (OCN) is lower than the concentration CIS by C1.
An example is shown in which the density is linearly decreased to 6 and the density is kept at a constant value of 016 between position t5 and position 1.

In the example shown in the tJJ28 diagram, atoms (OCN)
The distribution concentration C of is the concentration C11 at the 1st position tB, and this concentration CI? until the position t6 is reached. At first, it is gradually decreased, and around the position t, it is rapidly decreased to reach the concentration ate at the position t6.

Between the position t6 and the position Nt7, the value is decreased rapidly at first, and then gradually decreased until the position 7 is reached.
The concentration becomes C19, and between position t7 and position t8,
In E8, it was gradually reduced very slowly.
Between the 0 position t8 and the density C20, the density is reduced to substantially zero from the density C20 according to a curve shaped as shown in the figure.

As described above, from FIG. 20 to FIG. 28, one layer area (0ON)
As explained in some typical examples where the distribution state of atoms (00%) contained in the layer thickness direction is non-uniform, in the present invention, the distribution concentration of atoms (OCN) on the support side is The layer region (OCN) is provided with a distribution state of atoms (OCN) having a portion where C is high and where the distribution concentration C is considerably lower on the interface LT side than on the support side. .

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

The localized region (8) is desirably provided within 5μ from the interface position t8, if explained using the symbols shown in FIGS. 20 to 28.' In the present invention, the localized region (8) B) is interface position 1
．． In some cases, it is considered as the entire area (LT) up to the thickness of 1'5, and in other cases, it is considered as part of the layer area (Lt).

The localized region (B) may be part of the layer region (LT).

Whether it is the whole or part is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed.

The localized region (1) is the distribution of atoms (OCN) contained therein in the layer thickness direction, and the state is the distribution concentration C of atoms (OCW).
The maximum value Cmat is preferably 500 atomic
pps or more, more preferably 800 atomic pps
It is desirable that the layers be formed in such a manner that a distribution state of at least 1000 atoi+ic pp■ can be achieved.

That is, in the present invention, the layer region (00%) containing atoms (OCN) has the maximum value of the distribution concentration C within 5 JL in layer thickness from the support side (layer region 5 final thickness from ts). C
It is desirable to form such that a wet ax 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 gently by 1 at the interface between the layer region (0M) and other layer regions.

By doing so, it is possible to prevent the light incident on the light-receiving 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 (OCN).

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 (OCN) 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 (OCN), a starting material for introducing atoms (OIJ) is selected from among the starting materials for forming the photoreceptive layer as described above. Most of the gaseous substances whose constituent atoms are at least atoms (OCN) or gasified substances that can be gasified are used.・Specifically 1 For example, oxygen (02), ozone (03) - nitrogen oxide 010), nitrogen dioxide (1102), -nitrogen dioxide (N2.0), nitrogen sesquioxide (8203),
Nitrogen tetroxide (N20&), Nitrogen sesquioxide ('N20s
), nitrogen trioxide (NO3), silicon atom (Si)
1 whose constituent atoms are an oxygen atom (0) and a hydrogen atom (H), for example, disiloxane (H3SiOSiH3),
) lower cycloxane (H35iOSiH20SiH3), methane (CH4), ethane (C2
Ha), propane (C3M@), n-butane (n-Ca
Ht(i), pentane (Cs H12), etc. with 1 carbon number
~5 saturated hydrocarbons, ethylene (C2H4), propylene ((4H6), butene:1 (Ca'Hs), butene-2 (CsHs), inbutylene (CaHs)-pentene (Cs H1o), etc. with a carbon number of 2 ~5 ethylene hydrocarbons, acetylene (C2H2), methylacetylene (C3H4), carbon atoms 2 to 4 (F) 7 acetylene hydrocarbons such as Ca H6, nitrogen (N2)
, ammonia (NH3), hydrazine (82NNH
2), hydrogen azide (HNs), ammonium azide (
NH4N3), nitrogen trifluoride (Fan), nitrogen tetrafluoride C
F4N), etc.

In the case of the sputtering method, as starting materials for introducing atoms and molecules (OCN), in addition to the above-mentioned gasifiable starting materials listed in the glow discharge method, as solidified starting materials, Examples include SiO□, Si3N4% carbon plastic, etc. These are used as sputtering targets together with targets such as Si.

In the present invention, when forming the photoreceptive layer, atoms (OGN
) is provided.

A layer region (00
%), 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 the 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 some commonly used method such as manually or by an externally driven motor. At this time, the rate of change in flow rate is It does not have to be linear; the rate of change curve can be designed in advance using a microcomputer, for example.

The flow rate can also be controlled according to the line to obtain the desired content curve.

When forming a layer region (0(:N) by a sputtering method, the distribution concentration C of atoms (0ON) in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state of atoms (OCN) in the layer thickness direction. In order to form (dep+, hprafile), firstly, as in the case of the glow discharge method, a starting material for introducing atoms is used in a gaseous state, and a gas is used when introducing the gas into the deposition chamber. This is accomplished by appropriately changing the flow rate as desired.Secondly, if a target for sputtering is used, for example a mixed target of Si and 5i02, the mixing ratio of Si and 5i02 is adjusted to suit the target. This is achieved by changing the layer thickness direction in advance.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include old Cr, stainless steel, M, Cr, No, and Au.
, Nb, Ta, V, Ti, Pt, Pd, or 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. These electrically insulating supports are: 1. Preferably, at least one surface thereof is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, the surface may include old Or, At,
Cr, No, Au, Ir; Nb, Ta, V,
Ti, Pt, Pd, In2O3, 5n02, IT
Conductivity is imparted by providing a thin film made of O(In203+5n02), etc., or if it is a synthetic resin film such as a polyester film, old Cr, jLt
, Ag, Pb, Zn, Xi, Au, Or,
A thin film of metal such as No, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. gender is given. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired.
For example, if the light-receiving member 1004 in FIG. 1O is used as a light-receiving member for electrophotography, it is desirable to use an endless belt-like or cylindrical shape for continuous high-speed copying.The thickness of the support is as follows: It is determined as appropriate so that the desired light-receiving member is formed, but if flexibility is required as a light-receiving member, it is possible as long as the function as a support is fully exhibited. It is made as thin as possible. However, in such a case, the support is preferably 10#L or more in terms of manufacturing, handling, and functional strength.

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

FIG. 29 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. As an example, 2002 is SiH4 gas (purity 91
1.99i3% (hereinafter abbreviated as SiH4) cylinder, 20
03 is a G e H gas (purity 119.99!3%, hereinafter abbreviated as G e H4) cylinder, 2004 is a He gas (purity 9111.8913%, hereinafter abbreviated as NO) cylinder, and 2005 is a He gas (purity 99) .f3B13%) cylinder, 2008 is a H2 gas (purity 913.9139%) cylinder.

In order to flow these gases into the reaction chamber 2001, valves 2022 to 2026 of gas cylinders 2002 to 2008,
Make sure the leak valve 2035 is closed,
In addition, inflow valves 2012 to 2016, outflow valve 201
7~2021° Confirm that the auxiliary valves 2032 and 2033 are open, and first open the main valve 2034 to exhaust the reaction chamber 2001 and each gas pipe. Next, the vacuum gauge 2036 reads approximately 5. When the temperature reaches ×10”6tOrr, 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, 5iH
a gas, G e from gas cylinder 2003, H4 gas, NO gas from gas cylinder 2004, and H2 gas from 2008 by opening valve 2022.2023.2024.202B.
03117) Adjust the pressure to 1 Kg/crn', gradually open the inlet valve 20!2.20!3,2014.2016, and open the mass flow controller 2007.2008.2
009 and 2011, respectively. Subsequently, the outflow valves 2017, 2018, 2019, and 2021 and the auxiliary valves 2032 and 2033 are gradually opened to allow the respective gases to flow into the reaction chamber 2001. SiH4 gas flow rate at this time.

Ge1. Outflow valve 2017.2018.2 so that the gas flow rate, the ratio of NO gas flow rate and NO gas flow rate is the desired value.
019, 2021, and the opening of the main valve 2034 while checking the reading on the vacuum gauge 203B so that the pressure in one reaction chamber 2001 reaches the desired value. After confirming that the temperature □ of the substrate 2037 is set to a temperature in the range of 50 to 40.0°C by the heating heater 2038, the power source 2040 is set to the desired power and glow discharge is caused in the reaction chamber 2001. is contained in the layer formed by temporarily changing the opening of the valve 2018 by manually or using an externally driven motor or the like to control the flow rate of GeHa gas according to a pre-designed rate of change curve. Control the distribution concentration of germanium atoms.

In the manner described above, the first calendar (G) is formed on the base 2037 to a desired layer thickness by maintaining the G-discharge for the desired time.

At the stage where the first layer (G) has been formed to the desired layer thickness, the discharge valve 2018 is completely closed and the discharge conditions are changed as necessary, but the same conditions and procedures are followed for the desired time. By maintaining the gross discharge, it is possible to form an ls2 calendar (S) substantially free of germanium atoms on the first calendar (G).

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, form the second layer (S), for example 200B
Replace the hydrogen (H2) gas cylinder with a methane (CH4) gas cylinder, and install the mass flow controller 2007 and 2.
By maintaining the glow discharge for the desired time according to the same conditions and procedures except that 011 is set at a predetermined flow rate, a surface formed mainly of silicon atoms and carbon atoms on the second layer (S) is obtained. layers can be formed.

When forming the surface layer □ mainly made of silicon atoms and carbon atoms by sputtering, for example, 20
The hydrogen (H2) gas cylinder in 06 was replaced with an argon (Ar) gas cylinder, the deposition apparatus was cleaned, and a sputtering target made of, for example, Si and a sputtering target made of graphite were placed on the cathode electrode.
Spread it on one side so that it has the desired area ratio. After that 1. The device formed up to WS2 calendar (S) is placed in the device, and after the pressure is reduced, argon gas is introduced to generate glow discharge and sputter the surface layer material to form the surface layer to a desired thickness.

[Example] □ Examples will be described below.

Example 1 'M support (length L) 357■■, outer diameter (r)
・80■) was processed by keying to the surface properties shown in FIG. 30 under the conditions shown in Table 1a CB) to (E). Note that the symbols B-E representing the surface condition of the □ support shown in the table 4 below correspond to (B) to (E) in Table 1a, respectively.
This is in accordance with the above. Next, under the conditions shown in Table 1, using the film deposition apparatus shown in FIG.・Sample N (1,201
~204).

In addition, the first layer is G1! The mass flow controllers 2007 and 2008 were installed on a copy computer (HP9
845B). Further, the surface layer formed mainly of silicon atoms and carbon atoms was deposited as follows. That is, after the second layer is deposited, as shown in Table 1, the flow rate ratio of CH4 gas to giH4 gas is adjusted to correspond to each gas such that S1)la/CHa = 1-/3G. Set up the mass flow controller,
A surface layer was formed by generating a glow discharge using a high frequency power of 300 W.

When the thickness of each layer of the light-receiving member thus produced was measured using an electron microscope, the results shown in Table 2 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 38 (laser light wavelength: 780 nm, spot diameter: 80 scales), and then developed and transferred to obtain images. No interference fringes were observed in any of the images of sample Nos. 201 to 204.

It was sufficient for practical use. ``Example 2 M support (length L) 357++us, diameter (r
) 80 mm) was machined using a lathe to give the surface properties as shown in Table 1a (B) to (E).

Next, in the same manner as in Example 1 except that the conditions shown in Table 3 were used, a-5i electrophotographic light-receiving members were fabricated using the film deposition apparatus shown in FIG. 29 according to various operating procedures (sample No. 401-404).

Note that the 5th 1M controls the mass 70 controllers 2007 and 2008 using a computer (HP8845
B).

When the thickness of each layer of the light-receiving member thus produced was measured using an electron microscope, the results shown in Table 4 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 39 (laser light wavelength: 780 na, spot diameter: aog), and then developed and transferred to obtain images. No interference fringe pattern was observed in any of the images of sample Nos. 401 to 404, which were sufficient for practical use.

Example 3 M support (length L) 357 mm, diameter (r)
80 mm) was machined using a lathe to obtain the surface properties shown in (B) to (E) in Table 1a.

Next, in the same manner as in Example 1 except that the conditions shown in Table 5 were used, a-Si based electrophotographic light-receiving members were produced according to various operating procedures using the film deposition apparatus shown in FIG. No. 801 N804).

For the first layer, mass and flow controllers 2007 and 2008 were connected to a computer (HP9845
B).

When the thickness of each layer of the light-receiving member thus produced was measured using an electron microscope, the results shown in Table 6 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus (laser light wavelength: 780 nm, spot diameter: SOG) shown in FIG. 38, and then developed and transferred to obtain images. No interference fringe pattern was observed in any of the images of sample Nos. 801 to 604, which were sufficient for practical use.

Example 4 M support (length L) 357 mm, diameter (r)
80 mm) was machined using a lathe to obtain the surface properties shown in (B) to (E) in Table 1a.

Next, in the same manner as in Example 1 except that the conditions shown in Table 7 were used, a-Si based electrophotographic light-receiving members were produced according to various operating procedures using the film deposition apparatus shown in FIG. No. 801-804).

For the first layer, the mass flow controllers 2007 and 2008 were controlled by a computer (HP984
5B).

When the thickness of each layer of the light-receiving member thus produced was measured using an electron microscope, the results shown in Table 8 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure device (laser light wavelength 780 nm, spot diameter 80 μs) shown in FIG.
An image was obtained by transfer. Sample No. 801-804,
No interference aha was observed in the images of the deviations, which were sufficient for practical use.

Example 5 A-Si was prepared using the same conditions and procedures as in Example 4, except that the NH and gas used in Example 4 were changed to No gas.
A light-receiving member for electrophotography was produced.

Regarding these electrophotographic light-receiving members, the image exposure apparatus shown in No. □3 [1 (laser light wavelength 78G+■).

When image exposure was performed with a spot diameter of 80 scales and an image was obtained by developing and transferring the image, no interference fringe pattern was observed in any of the images obtained, and the images were sufficient for practical use. .

Example 6 The same conditions and procedures as in Example 4 were followed except that the NH gas used in Example 4 was changed to CH4 gas.
A 9i'-based electrophotographic photoreceptor was fabricated.・
, 'When these electrophotographic light-receiving members were subjected to image exposure using the image exposure device shown in FIG. 39 (laser light wavelength: 780 nm, spot diameter: 80 mm), and an image was obtained by developing and transferring the exposed material, the obtained image was obtained. No interference fringe pattern was observed in any of the images obtained, and they were sufficient for practical use.

Example 7 M support (cylinder No.
, 202) Same as Example 1 except that the No gas ratio was changed with time according to the change rate curve of gas flow rate ratio shown in FIG. 35 under the conditions shown in Table 9 above. A light-receiving member for electrophotography was produced under the same conditions.

The light-receiving member for electrophotography obtained in this way was exposed to the image exposure apparatus shown in FIG.
Image exposure was carried out using a spot diameter of 80 Im), which was then developed and transferred to obtain an image. No interference fringe pattern was observed in the resulting image, and it was sufficient for practical use. Ta.゛Example 8 ・□No. 29
M support (cylinder No., 202
) Under the conditions shown in Table 10 above, the conditions were the same as in Example 1, except that the flow rate ratio of NH3 gas was changed with the layer formation time according to the change rate curve of the gas flow rate ratio shown in FIG. , produced a light-receiving member for electronic photography.
・ , -The electrophotographic light-receiving member thus obtained was subjected to image exposure as shown in FIG.
Equipment (laser light wavelength 780n''m, spot diameter s
When an image was obtained by carrying out image exposure using a photoreceptor og), developing and transferring the image, no interference fringe pattern was observed in the obtained image, and the image was sufficient for practical use.゛Example'9 No gas was deposited on the M support (cylinder No. 202) using the film deposition 1 apparatus shown in Figure 128 under the conditions shown in Table 11 and according to the rate of change curve of the gas flow rate ratio shown in Figure 37. An electrophotographic light-receiving member was produced under the same conditions as in Example □1 except that the flow rate ratio was changed with the layer formation time □...: Electrophotographic light-receiving member obtained in this way The image exposure device shown in Fig. 38 (laser light wavelength 780 nm, spot diameter 80 mm) is used to expose the image to the image exposure device shown in Fig. 38, and the seven parts are developed and transferred to form an image. As far as I can tell, no interference fringe pattern was observed in the obtained image, which is useful for practical use.

It was sufficient.

Example 10 The same conditions and procedures as in Example 9 were followed except that the No gas used in Example 9 was changed to NHf1 gas. A photo-receiving member for electrophotography thus prepared was prepared using an image exposure apparatus shown in FIG. m'L Spot diameter 80m
)', image exposure was carried out, the image was developed and transferred, and an image was obtained. fI! No interference fringes were observed, and the results were sufficient for practical use.

Example 11 The N0 gas used in Example 9 was...C)! 4ga 1
An a-Si'-based electrophotographic □ light-receiving member was produced according to the same conditions and procedures as in Example 9, except that the material was changed to a light-receiving member.

The photoreceptor Mr'tt for electrophotography thus obtained
Based on □, the image exposure device/equipment (・ray・・ray・
When image exposure was carried out using laser light with a wavelength of 780 nm and a spot diameter of 80 nm, the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the resulting image, and it was sufficient for practical use. It was something.

Example 12 A super support (cylinder No.
202) Under the conditions shown in Table 12 above, the electron A photographic light-receiving member was produced.

The electrophotographic light-receiving member obtained in this way was exposed to the image exposure apparatus (laser light wavelength 7) shown in FIG.
When image exposure was carried out using 80 nm, spot diameter 80 scales), it was developed and transferred to obtain an image, no interference fringe pattern was observed in the obtained image, which was sufficient for practical use. .

Example 13 Using M support (cylinder No. 202), 5i) 1. during surface layer formation. The a-Si-based electrons were prepared under the same conditions and procedures as in Example 1, except that the flow rate ratio of gas and CH4 gas was changed as shown in Table 13, and the content ratio of silicon atoms and carbon atoms in the surface layer was changed. Photographic light-receiving members were created (samples, 42701-270B).

Regarding these electrophotographic light-receiving members, an image exposure apparatus (laser light wavelength of 780 nm) shown in FIG. 39 was used.

After performing image exposure with a spot diameter of 80 scales and repeating the steps of image formation, development and cleaning 50,000 times, one image was evaluated and the results shown in Table 13 were obtained.

Example! Same as Example 13 except that 4M support (cylinder No. 202) was used, 5iHa gas, CH4 gas and SiF4 were used during surface layer formation, and the flow rate ratio of these gases was changed as shown in Table 14. a-5i according to the conditions and procedures of
A light-receiving member for electrophotography was created (sample m2801~
2808).

Regarding these electrophotographic light-receiving members, an image exposure apparatus (laser light wavelength of 780 nm) shown in FIG. 3S was used.

After performing image exposure with a spot diameter of 80 μm and repeating the steps of image formation, development, and cleaning 50,000 times, image evaluation was performed, and the results shown in Table 14 were obtained.

Example 15 An a-5i electrophotographic light-receiving member was prepared using the M support (cylinder No. 202) and following the same conditions and procedures as in Example 1, except that the surface layer was formed by sputtering. At that time, the content ratio of Si and C was changed by changing the area ratio of the Si target and C target as shown in Table 15 (Samples Makoto 2f901 to 29
07).

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
Take out the hydrogen (H2) from the deposition device shown in the θ diagram.
Replace the gas cylinder with an argon (At) gas cylinder,
Clean the inside of the apparatus, 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 so that their area ratios are as shown in Table 15. Spread it on one side. Thereafter, the support with the second layer formed thereon was placed in the apparatus, the pressure was reduced, argon gas was introduced, and the surface layer material on the cathode electrode was sputtered to form the surface layer.

Regarding these electrophotographic light receiving members, an image exposure apparatus (laser light wavelength of 780 nm) shown in FIG. 3S was used.

After performing image exposure with a spot diameter of eoJm and repeating the steps of image formation, development, and cleaning for 50,000 @, image evaluation was performed, and the results shown in Table 15 were obtained.

(Effects of the Invention) As described above in detail, the present invention is suitable for image formation using coherent monochromatic light, is easy to manage in production, and is capable of eliminating interference fringe patterns that appear during image formation. ``It is possible to simultaneously and completely eliminate the appearance of spots during reversal development, and to provide a light-receiving member that has excellent mechanical durability, particularly abrasion resistance, and light-receiving properties.

[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 multilayered 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. Figures 6 (Todoroki), CB), (C), and (D) are explanatory diagrams showing that no interference fringes appear when the interfaces of the respective layers of the light-receiving member are non-parallel. FIGS. 7(A), CB), 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. 10 is an explanatory diagram of the layer region of the light receiving member. FIGS. 11 to 13 are explanatory diagrams for explaining the distribution state of germanium atoms in the first layer. Figures 20 to 28 show atoms (
0, , N) is an explanatory diagram for explaining the distribution state. FIG. 23 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 30 is an explanatory diagram of the surface state of the M support used in Examples. FIG. 31 to FIG. 38 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 39 is an explanatory diagram of the image exposure apparatus used in the example. 100 (1-・・・・・・・・・・・・・・・Photoreceptive layer 1001・・・・・・・・・・・・・・・M
Support body 1002・・・・・・・・・・・・・・・
・First calendar 1003・・・・・・・・・・・・・・・
・・Second calendar jO04・・・・・・・・・・・・・・・
...Light receiving member 1005-......
...Free surface 21101 of light-receiving member...
・・・・・・・・・・・・Light receiving member 28 for electrophotography
02・・・・・・・・・・・・・・・Semiconductor laser 2803-・・・・・・・・・・・・・・・-fθ
Lens 21304・・・・・・・・・・・・・・・・・・
・Polygon mirror 2805・・・・・・・・・・・・
... Plan view of exposure device 2808 ...
・・・・・・・・・Side view of exposure device Patent applicant
Canon Co., Ltd. 1II Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 (A), B. (C) Figure 7 Figure 8 (A) (B). (C) , ' Figure 9 Figure 1O Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Figure 17 Figure 18 Figure 19 □C Figure 20 Figure 21 Figure 22 Fig. 23 Fig. 24 Fig. 25 Fig. 26 Fig. 27 □C Fig. 28 Fig. 31 Fig. 32 Fig. 33 Fig. 34 Quantity EL Fig. 38 ・ Fig. 39

Claims (19)

[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; The light-receiving layer has a multilayer structure in which a surface layer made of an amorphous material containing atoms and carbon atoms is provided in order from the support side, and the distribution state of germanium atoms in the first layer is is non-uniform in the layer thickness direction, and the photoreceptive layer contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and contains one or more atoms within a short range.
A light-receiving member characterized in that it has a pair or more of non-parallel interfaces, 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. (2) oxygen atoms and carbon atoms contained in the photoreceptive layer;
Claim 1, wherein the distribution state of at least one kind of atoms selected from nitrogen atoms is non-uniform in the layer thickness direction.
The light-receiving member described in 2. (3) oxygen atoms and carbon atoms contained in the photoreceptive layer;
The light-receiving member according to claim 1, wherein the distribution state of at least one kind of atoms selected from nitrogen atoms is uniform in the layer thickness direction. (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 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.