JPS6198357A - Photoreceptor - Google Patents

Abstract

PURPOSE:To prevent an interference fringe pattern by forming a structure composed of a substrate, the first amorphous layer contg. Si and Ge, and the second amorphous layer contg. Si. CONSTITUTION:The photoreceptive layer 1000 has a multilayer structure formed by laminating on the substrate 1001 the first layer (G) 1002 made of Si and Ge and contg. H or/and halogen (X), when needed, that is, made of a-Si{a-SiGe (H,X)}, the second photoconductive layer (S) 1003 made of a-Si{a-Si(H,V)} contg. H or/and X, and a surface layer 1006 made of amorphous material contg. Si and C in succession. At least one of the layer 1002 and the layer 1003 contains a conductivity-governing substance (C) in a distribution nonuniform thickness direction. The surface layer 1006 formed on the layer 1003 has a free surface in the photoreceptor, and mainly enhancing humidity resistance, repeating use characteristics, high voltage resistance, mechanical resistance, and photorecep tivity characteristics.

Description

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

[Prior art]
1. As a method of recording digital image information as an image, electrostatic WI is created by optically scanning a light-receiving member with a laser beam modulated according to the digital image information.
Form an image, then develop the latent image, transfer if necessary,
A method of recording an image by performing processing such as fixing is well known. Among these, in image forming methods using electrophotography, image recording is generally performed using a small and inexpensive He-Me laser or semiconductor laser (usually having an emission wavelength of 650 to 820 nm).

In particular, as a light-receiving material for electrophotography that is suitable when using a semiconductor laser, in addition to the fact that the consistency of its photosensitivity region is much worse than that of other types of light-receiving materials, it also has a Vickers hardness. For example, JP-A No. 54-88341 and JP-A No. 58-8
A light-receiving member made of an amorphous material containing silicon atoms (hereinafter abbreviated as "rh-3i") disclosed in Japanese Patent No. 3748 is attracting attention.

However, if the photoreceptive layer is a single-layer a-5i layer, in order to maintain its high photosensitivity and ensure a dark resistance of 10I20C or higher required for electrophotography, hydrogen atoms and halogens must be added. Since it is necessary to structurally contain atoms or boron atoms in addition to these atoms in a specific amount range in a controlled manner in the layer, it is necessary to strictly control layer formation.

There are considerable limitations on the tolerances in the design of light receiving members.

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 is 1, for example, Japanese Patent Application Laid-Open No. 54-121743.
No. 1, JP-A-57-4053, JP-A-57-4
As described in Japanese Patent Publication No. 172, the photoreceptive layer may have a layer structure of two or more layers having different conductivity characteristics, and a depletion layer may be formed inside the photoreceptive layer.
No. 178, No. 52179, No. 52180, No. 581
59, No. 58'180, and No. 58181, a multilayer structure in which a barrier layer is provided between the support and the photoreceptive layer or/and on the upper surface of the photoreceptive layer is used. Accordingly, light-receiving members with apparently increased dark resistance have been proposed.

Through such proposals, the a-9i-based light-receiving material has made dramatic advances in its commercialization design tolerances, ease of manufacturing management, and productivity, and is expected to be commercialized. The speed of development towards this goal is accelerating.

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

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

Furthermore, as the wavelength range 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 becomes remarkable.

This point will be explained with reference to the drawings.

Figure vK1 shows the light 10 incident on the layer constituting the light-receiving layer of the light-receiving member and the reflected light R+ reflected at the upper interface +02.
, shows reflected light R2 reflected at the lower interface 101.

The average layer thickness of the layer is d, the refractive index is n, and the wavelength of light is input,
If the layer thickness of a certain layer is uneven with a smooth layer thickness difference of 6 or more, 1 reflected light R,, R2 becomes 2nd = mλ (m is an integer 1 reflected lights strengthen each other) and 2nd = (m++) input ( m is an integer 1 (reflected light weakens each other) The amount of absorbed light and transmitted light of a certain layer changes depending on which of the following conditions is met.

In a multilayered light-receiving member, 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 i, causing a defective image.

A method for solving this problem is to diamond-cut the surface of the support and provide unevenness of ±500A to ±10,000A to form a light-scattering surface (for example, as disclosed in Japanese Patent Laid-Open No. 58
-182975 Publication) A method of providing a light absorption layer by subjecting the surface of an aluminum support to black alumite treatment, or dispersing carbon, colored pigments, or dyes in a resin (
For example, JP-A No. 57-185845), a method of providing a light-scattering anti-reflection layer on the surface of an aluminum support by subjecting the surface of the support to satin-like alumite treatment or by sandblasting to provide fine roughness in the form of grains. (For example, Japanese Unexamined Patent Publication No. 57-18554) etc. have been proposed.

However, with these conventional methods, it has not been possible to completely eliminate the interference fringe pattern appearing on the lj original image.

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 irradiated spot I spreads due to the light scattering effect on the support surface, and the This caused a decrease in resolution.

``The second method is 4 black alumite treatment.

Complete absorption is impossible, and the light reflected on the surface of the support remains. In addition, when providing an R color pigment dispersed resin layer, a-5i
When forming the layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed photoreceptive layer deteriorates significantly.The resin layer is damaged by the plasma during the formation of the a-S4 layer, and the original It has disadvantages such as reducing the absorption function of 1 and adversely affecting the formation of the a-Si calendar after 7 due to the deterioration of the surface condition.

In the case of the third method of irregularly roughening the surface of the support, as shown in FIG. The rest,
enters the inside of the light-receiving layer 302 and becomes transmitted light II;
A part of the transmitted light It is scattered on the surface of the support 302 and diffused into X, K+, l[2, 3...
・The rest is specularly reflected and becomes the reflected light R2, and a part of it becomes the emitted light R3 and goes outside. Therefore, the emitted light R3, which is the component that interferes with the reflected light R1, remains, so it is still 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 inside the light-receiving layer, the resolution decreases because light is diffused within the light-receiving layer and causes halation. There was also the drawback of doing so.

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

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

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

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

Therefore, in that part, the incident light holds 2ndl=mλ or 2ndl=(m+%), and becomes a bright part or a dark part, respectively. Also, inside the photoreceptive layer, the layer thickness of the photoreceptor layer (
11, d2, d3, and da are 61""'1 m""1
″<Nhn6° 1 Therefore, the support 5
Merely roughening the 01 surface regularly cannot completely prevent the occurrence of interference fringes.

Furthermore, even 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, there is also interference due to the reflected light at the interface between each layer, so that the degree of interference fringe pattern development becomes more complicated than that of a single-layered light-receiving member.

[Purpose of the invention]

It is an object of the present invention to provide a new light-sensitive light-receiving member which eliminates the above-mentioned drawbacks.

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

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

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

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

Another object of the present invention is to improve the mechanical durability of the surface of the light-receiving member, especially the resistance to 1! Another object of the present invention is to provide a light-receiving member with excellent wear resistance and light-receiving properties.

[Summary of the invention]

The light-receiving member of the present invention includes a support, a first layer made of an amorphous material containing silicon atoms and germanium atoms, and an amorphous material containing silicon atoms, and has photoconductivity. and a surface layer made of an amorphous material containing silicon atoms and carbon atoms. At least one of the layer and the second layer contains a substance that controls conductivity, and in the layer region containing the substance, the distribution state of the substance is uneven in the layer thickness direction. , the photoreceptive layer contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and has one or more pairs of non-parallel interfaces within a short range, and the non-parallel interfaces are It is characterized in that a large number of them are arranged in at least one direction within a plane perpendicular to the thickness direction.

The present invention will be specifically explained below with reference to the drawings.

Diagram NIj6 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 calendar 802 changes continuously from ds to ds, the interface 803 and the interface 604 have a tendency toward each other. Therefore, the coherent light incident on this minute portion (short range) 1 causes interference in the minute portion 1, producing a minute interference fringe pattern.

Also, as shown in FIG. 7, the interface 703 between the first calendar 701 and the second F702 and the second F! ! If the free surface 704 of '702 is non-parallel, the incident light 1o
Since the traveling directions of the reflected light R1 and the emitted light R3 are different from each other, when the interfaces 703 and 704 are parallel (the seventh
The degree of interference is reduced compared to r (B) J ) in the figure.

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 layer thickness of No. 25802 is macroscopically non-uniform (d7"eda) as shown in Figure 6, so the amount of incident light is uniform in the entire layer area. Naru 16
(See figure r (D)J).

In addition, when the light-receiving layer has a multilayer structure and coherent light is transmitted from the irradiation side to the second calendar,
To describe the effect of the present invention with respect to i, as shown in FIG.
a, R5 is present. Therefore, in each layer, the same thing as described above in FIG. 7 occurs.

Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer.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.

The size l (one cycle of the uneven shape) of the minute portion suitable for the present invention is lf, where L is the spot diameter of the irradiation light, and j≦L.

In addition, in order to achieve the object of the present invention more effectively, the difference in layer thickness (ds - da ) in the minute portion t is calculated as follows, where the wavelength of the irradiation light is input, ds - ds ≧ 1 (n : refractive index of second layer 802).

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. The layer thickness of each layer is MW within the microcolumn, and if this condition is satisfied, any two layer interfaces may be in a parallel relationship within the microcolumn.

However, the layers forming parallel layer interfaces are formed to have a uniform layer thickness over the entire area so that the difference in layer thickness at any two positions is λ T1 (n: refractive index of the layer) or less. It is desirable that

In order to more effectively and easily achieve the object of the present invention, plasma gas is used to form the first layer and second layer constituting the photoreceptive layer because the layer thickness can be controlled accurately at the optical level. The phase method (PC''/D method), photo-CVD method, and thermal CVD method are employed.

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

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

The vertical cross-sectional shape of the uneven convex portions provided on the surface of the support is determined by the controlled non-uniformity of the layer thickness within the microcolumns of each layer formed, and by the difference between the support and the layer directly provided on the support. In order to ensure good adhesion and desired electrical contact between the two, the inverted V-shape is used, but preferably the shape is substantially isosceles triangular, right-angled triangular, or not, as shown in FIG. It is preferable that the shape is an equilateral triangle, and particularly an isosceles triangle or a right triangle.

In the present invention, each dimension of the irregularities provided on the surface of the support in a controlled manner is set in such a way that one of the objects of the present invention can be achieved as a result, taking into account the following points.

That is, the first is a-9iWI which constitutes the photoreceptive layer.

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

Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause deterioration in the layer quality of the a-5i layer.

Secondly, if the free surface of the photoreceptive layer is extremely uneven, it will not be possible to clean it completely after one image is formed. I again. When cleaning the blade, there is a problem in that the blade gets damaged quickly.

After considering the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, we found that:
The pitch of the recesses on the surface of the support is preferably 500u −
0.3 g, more preferably 200 to 1 u, optimally 50 μs to 5 scales.

Further, the maximum depth of the recess is preferably fl, 1 μs to 5 μs.
-2 preferably 0.3-3μs, optimally 0.8
- If the pitch and maximum depth of the recesses on the surface of the support are within the above range, it is desirable that the pitch and maximum depth of the recesses be two scales, then the # of the slope of the recesses (or linear protrusions)! Kiha.

Preferably it is 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees, most preferably 4 degrees to 10 degrees.

Further, the maximum difference in layer thickness due to the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0 within the same pitch.
．． 1-2μs, more preferably 0.1u-1.5u,
The optimum range is preferably 0.2u to 1p.

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 calendar and a third calendar made of an amorphous material containing silicon atoms and carbon atoms are provided in order from the support side, and has excellent electrical, optical, and photoconductive properties. Characteristics, electrical voltage resistance, and usage environment characteristics are shown.

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

Furthermore, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side. is fast.

In the light-receiving member of the present invention, the surface layer made of an amorphous material containing silicon atoms and carbon atoms provided on the second layer functions as a protective layer for mechanical durability and for optical protection. wA as an anti-reflection layer! ! can be mainly loaded.

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

That is, if the refractive index of one surface layer is n, the thickness of the layer is d, and the wavelength of incident light is input.

When the input d=T1 or an odd multiple thereof, one surface layer is suitable as an antireflection layer.

Further, when the refractive index of the second layer is nt, the refractive index n of the surface layer is.

nIII layer and the layer thickness d of one surface layer satisfies d''4'n (
・Surface layer I*・Ideal as an anti-reflection layer ・When using j' a-9i:H as the second calendar, the refractive index of a-5i:)I is approximately 3.3, so One surface layer has a refractive index of 1.8.
2 materials are suitable.

a-SiC:H can have a refractive index of such a value by adjusting the amount of C, and also has sufficiently satisfactory mechanical durability, interfacial adhesion, and electrical properties. Therefore, it is the most suitable material for one surface layer.

In addition, if the surface layer is designed to function as an antireflection layer, it is more desirable that the thickness of the surface layer be 0.05 to 2.

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

FIG. 10 is a schematic structural diagram schematically shown to explain the layer structure of a light receiving member according to an embodiment of the present invention.

A light-receiving member 1004 shown in FIG. 10 has a light-receiving layer 1000 on a support 1001 for the light-receiving member, and the light-receiving layer 1000 has a free surface toos on one end surface. .

picture,. 10001, □1001, 9. =tsu41
a-1i (hereinafter referred to as ra-3iGe
a-3i (hereinafter referred to as ra) containing hydrogen atoms and/or halogen atoms (X) as necessary;
-9i (H, It has a stacked layer structure.

In the light receiving member 1004 shown in FIG.

The surface Mtooe formed on the second calendar 1003 has a free surface and mainly meets the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, mechanical durability, and light reception characteristics. It is established to achieve this.

Surface W in the present invention! too is a silicon atom (S
i), a carbon atom (C), and, if necessary, a hydrogen atom (I(
) and/or an amorphous material containing a halogen atom (X) (
Hereafter, 'a-(SIxCt-x)y(H,XL-y
Denoted as J, provided that Q<x, 1<1).

a-(SiIlC,-11)y (H-X) ty'
-t's t Sale 6 Surface N1006 is formed using a plasma vapor phase method (PCVO method) such as a glow discharge method.
Or optical CVO method, thermal CVN method.

This is accomplished by a sputtering method, an electron beam method, or the like. These manufacturing methods are manufacturing conditions.

It is selected and adopted as appropriate depending on factors such as the load of equipment capital investment, the manufacturing scale, and the desired characteristics of the photoconductive member to be manufactured. Control is relatively easy. 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 Wtooe to be produced.

Furthermore, in one aspect of the present invention, the surface layer 100B may be formed using a glow discharge method and a sputtering method in the same apparatus system.

To form the surface W too by glow discharge method, a-(St, C,-11)y (l(,X) I-
The raw material gas for forming y is mixed with a dilution gas at a predetermined mixing ratio if necessary, and introduced into a deposition chamber where a support is installed.

The introduced gas is turned into gas plasma by causing a glow discharge, and a-(Si, 14-0), (11,
It is sufficient to deposit xL−y.

In the present invention, a-(Si, c, -X)y (
) I, Most gaseous substances or gasified substances containing gaseous substances can be used.

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

In addition, separately, a raw material gas containing Si and ) 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 an Iq material gas containing C as a constituent atom.

In the present invention, preferred halogen atoms (X) contained in one surface layer 1006 are F and α.

B', ■, and F and α are particularly desirable.

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

One surface layer in the present invention! Raw material gas for Oo8 formation, □
□□, 6°1, 91. □Yowa Silicon hydride gas such as silanes such as SiH4, 5I2H6, 5i3H6, 514M 16, etc., with C and H as constituent atoms, for example, isotropic carbonization with 1 to 4 carbon atoms Hydrogen, ethylene hydrocarbon having 2 to 4 carbon atoms, degree 5I
Examples include a few acetylenic hydrocarbons, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides.

Specifically, as a saturated hydrocarbon, methane (CHa)
, z Tough (C2Ha), Propa7 (CaHa
).

n-butay (++-(:4Hl(1), penta7(
C5HI2), x Tyrenic hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-
1(CaHe)-butene-2(C:aHe),
Inbutylene (CaHo), pentene (CsH
+o), 7 Cetylenic hydrocarbons include acetylene (CzH2), methylacetylene (C3Ha), butyne (CaHt, ); simple halogens include halogen gases such as fluorine, chlorine, bromine, and iodine; and hydrogen halides include: FH, MI Ho, HBr, interhalogen compounds include BrF, αF, αF3. αF1,
BrF5°BrF3, IF7. IF5. rα, l[
]r, SiF as silicon halide, Si2F
6, Siα38r, Siα28 T2゜5iCIB
r3, Siα31stBr4. As the halogen-substituted silicon hydride, SiH2F2. SiH2α2. ,
SiHo3, SiH3α, 5iH3Br, S,
1H2Br2, 5iHBr3 silicon hydride and shite are S
Examples include silanes such as iH4, Si2H6, 5i3HB, and 5laH+o.

In addition to these, CF, Caa, CBr4, (:)
IF3, (:H2F2, C)13F, CH3Cl
, CH3Br, CH31, (halogen-substituted paraffinic hydrocarbons such as 4H5α, SF4.

Fluorinated sulfur compounds such as SF; 5i(CH3,)a
,” (C2H5)4 and other alkyl silicides and Siα(C
H3)3, Siα2(0M3)2, Siα3CH,
Silane derivatives such as halogen-containing alkyl silicides can also be mentioned as effective.

These surface layer 100B forming substances are formed on the surface!
Silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are selected and used as desired when forming the first surface layer 100B so that the silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are contained in the silicon atoms 1008 in a predetermined composition ratio.

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(CH3)a and SiHα3, SiH2α2,5id4 or, as a substance containing a halogen atom,
Surface layer 1 is formed in a gas state with SiH3α etc. at a predetermined mixing ratio.
a-(SixCI-x)y (α+H) by introducing it into a device for forming 006 and causing a glow discharge.
A surface layer 100B made of Y can be formed.

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

For example, using a Si wafer as a target1
Lead 1"・C2・"1"/also 1"6
? -'''・1 Raw material gases are diluted as necessary and introduced into a deposition chamber for sputtering, and a gas plasma of these gases is formed to form the Si wafer/\-
All you have to do is sputter.

Alternatively, Si and C may be used as separate targets, or a mixed target of Si and C may be used in a gas atmosphere containing hydrogen atoms and/or halogen atoms as required. This is done by sputtering inside. As a material serving as a raw material gas for introducing C, H, and X, the material for forming the surface 5100!1 shown in the glow discharge example described above can also be used as an effective material in the sputtering method.

In the present invention, the stacking gas used when forming the surface a tooe by a glow discharge method or a sputtering method includes so-called rare gases, such as He, Me, and rgf.
can be cited as suitable.

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

That is, Si, C, H or/and X as necessary
Depending on the conditions in which it is created, the substances that make up one constituent atom can have structural forms ranging from crystalline to amorphous, and electrical properties ranging from conductivity to semiconductivity to insulating properties, as well as photoconductive properties. Since each of them exhibits non-photoconductive properties, in the present invention, 6 a-(Six Ct -X )y (I
(,
When providing with the main purpose of improving electrical withstand voltage, a-(SL+ CI-x)y (H,X) t-
y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use.

In addition, when the surface layer 100B is provided with the main purpose of improving the characteristics of repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and the sensitivity to the irradiated light is reduced to some extent. As an amorphous material having a-
(si, cl -1+l)y (H,X) t-F
is created. a-(Si) on the surface of the second layer 1003
, C1-x)y (H,X)ty
When forming 00B, the temperature of the support during layer formation is one of the important factors that influences the structure and properties of the formed layer.
It is desirable that the temperature of the support during layer formation be strictly controlled so that (Stl, 1C1-x)y (H,X)ry can be formed as desired.

In the present invention. The formation of the first surface layer 10011 is carried out by selecting an appropriate range in accordance with the method of forming the surface layer 1008 in order to effectively achieve the desired purpose, but preferably at a temperature of 20 to 400°C. The temperature is preferably 50 to 350°C, optimally 100 to 300°C.The formation of the surface layer 1006 requires delicate control of the composition ratio of the atoms constituting l, which is relatively difficult compared to other methods. It is advantageous to adopt a glow discharge method or a sputtering method because of ease of use, but when forming the surface layer 1008 using these layer forming methods, the layer temperature is similar to the above-mentioned support temperature. The discharge power during formation is created a-(Si, c, -X
)y (H,X) is one of the important factors that influences the characteristics of ry.

a-(Six Ct -x)y (H,,X) having the characteristics to effectively achieve the purpose of the present invention
The discharge power conditions for effectively creating I-y with good productivity are preferably 10~tooow, more preferably 20~750W, and optimally 50~850W.
It is desirable that this is the case.

The gas pressure in the deposition chamber is preferably 0.01 to I
Tarr is preferably about Q, 1 to Q, 5 Tarr.

In the present invention, the values in the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and discharge power for creating the surface layer 1008, but these layer creation factors can be determined independently and separately. Desired characteristics 1 without any problems
7) The optimum value of each layer creation factor is determined based on mutual organic compatibility so that the surface layer 100B consisting of a-(SixC+-m)y(H,x),-y is formed. desirable.

The amount of carbon atoms contained in the surface layer tooes in the photoconductive member of the present invention is the same as the conditions for forming the surface *tooe. This is one of the important factors.

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

That is, the general formula a-(Six c, +ll)y
(HlX) The amorphous material represented by ry can be broadly classified as an amorphous material (hereinafter referred to as "amorphous material") composed of silicon atoms and carbon atoms.

ra-! 1tiac I-* J, however, 0<
a(+), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as ra-(SEbCr-
b") eHl-cJ, where O< b, c
<1), an amorphous material composed of silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as ra-(SLC+-a)e(H-X)l-@J
However, it is classified as O < d, e < +).

In the present invention, one surface F! 1008 is a-5ilC1
-@Te configuration, the amount of carbon atoms contained in the surface layer 1008 is preferably IX1G'~9
0 atomic%.

More preferably 1 to 80 atasic%, optimally 10 to 80 atasic%
It is desirable that it be 75 atomic%.

That is, 1. If expressed as a in the above a-9ilC1-1, a is preferably 0.1 to 0.11+19
99. More preferably 0.2~o,es, optimally 0.2
It is 5 to 0.9.

On the other hand, in one aspect of the present invention, the surface layer tooe is a, -(Si
, C1→)e Hl-1l, the surface layer t
The amount of carbon atoms contained in oos is preferably lXl
0°3 to 90 atomic%, more preferably 1
#90atasic%, optimally 10-8Qatas
It is preferable to set it as ic%. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 3 atomic%.
It is desirable that the hydrogen content be 0 atomic%, and the light-receiving member formed when the hydrogen content is within these ranges is as follows:
It can be fully applied as an excellent thing in practice.

That is, if it is expressed as a-(SEbCr-b)eHt-1.

b is preferably 0.1 to 0.11919911. More preferably 0.1~o, ss, optimally 0.15~G, 9,
C is preferably 0.8 to 0.99, more preferably 0.6
5-0.98. The optimum value is 0.7 to 0.95.

The surface Jlj1008 is a-(jiiC+-i)*(
H,X)i-m, 11 surface layer 10(
The content of carbon atoms contained in 18 is preferably 1×10°3 to 90 atom+c%, more preferably 1 to 90 atom+c%, optimally 10 to 80 atom+c%.
It is desirable to set it to om+c%. The content of halogen atoms is preferably 1 to 20 ata
It is preferable that the halogen atom content be sic%, and a light-receiving member prepared when the halogen atom content is within this range can be sufficiently applied in practice. The content of hydrogen atoms contained as necessary is preferably 19ata
It is desirable that the content be mic% or less, more preferably 13 atomic% or less.

That is, f)a-C5iaC1-45acH,X), -
a (F) When expressed as d and e, d is preferably 0.1 to 0.99999, more preferably 0.1 to O,S
S, optimally 0.15-0.9°e, preferably 0.8
Desirably, it is ~0.99, more preferably 0.82-0.es, optimally 0.85-0.98.

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

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

The thickness of the surface layer 100B is 5iIgF, which is the same as the amount of carbon atoms contained in the layer and the thickness of the first to second layers.

However, it is necessary to appropriately determine the desired characteristics based on the organic relationship depending on the characteristics required for each layer.

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

The layer thickness of the surface layer 1008 in the present invention is preferably 0.003 to 30 mm, more preferably 0.004 to 2 mm.
It is desirable that the value be 0 scale, optimally 0.005 to ioIIm.

In the light receiving member 1004 of the present invention, at least the first calendar (G) 1002 or/and the second M (S) 1
003 contains a substance (C) that controls conduction properties, and the material (C) containing the material is given desired conduction properties.

In the present invention, the substance (C) that controls the conductive properties contained in the first calendar (G) 1002 or / 2 C and the second calendar (S) 1003 is It may be contained in the entire layer region of the layer containing the substance fi (C), or it may be contained so as to be unevenly distributed in a part of the layer region in which the substance fi (C) is contained.

However, in any case, in the layer region (PN) containing the substance (C), the distribution state of the substance in the layer thickness direction is non-uniform. Clogging, e.g. first layer (
If the substance (C) is to be contained in the entire layer area of the first calendar (G), the substance (C) is distributed more toward the support side of the first calendar (G). contained within.

In this way, by making the distribution concentration of the substance (C) uneven in the layer thickness direction in the layer region (PN), good optical and electrical bonding can be achieved at the contact interface with other layers. You can.

In the present invention, the first layer (G) is made such that the substance (C) that controls the conduction characteristics is unevenly distributed in a part of the layer region of the first layer (G).
In the case of containing the substance (C) in the layer region (PN) in which the substance (C) is contained, the first F! F (G) laWrM
9A*k L? ! QL+'+J'L-+ry>m
.

The law may be prescribed as appropriate depending on the person's wishes.

In the present invention, the substance (C) is added during the second calendar (S).
When containing, preferably at least the first layer (
It is desirable to contain the substance (C) in the layer region including the contact interface with G).

When both the first layer (G) and the second layer (S) contain a substance (C) that controls conduction characteristics, the first 7! ! '
The layer region containing the substance (C) in (G) and the second 1! ? It is desirable that the layer region (S) and the layer region containing the substance (C) be in contact with each other.

Also, the substance jj (C) contained in 1Ml of the calendar (G) and the second calendar (S) is the first layer (G) and the second layer (S).
Same thing! It may be of class i or class R11, and
The content may be the same or different in each layer.

According to the present invention, when the substance (C) contained in each layer is the same in both layers, the first N
The content in (G) should be increased sufficiently, or 1! It is preferable that each desired layer contains a substance (C) having an interesting chemical property.

In the present invention, at least the first layer constituting the photoreceptive layer
f) M (G) or/and the second layer (S) contains a substance (C) that controls the conduction properties, so that the layer region containing the substance (C) [first calendar] (G) and/or a part or all of the layer region of the second layer (S)] can be arbitrarily controlled as desired. Examples of (C) include so-called impurities in the semiconductor field. In the present invention, a-5i (H,X) or/and a-5i (H, 5iGe(H
,

Specifically, p1M impurities include atoms belonging to group V of the periodic table (group m atoms), such as B (boron), AI (
aluminum), Ga (gallium), In (indium), Tj (thallium), etc.

Particularly preferably used are B and Ga.

nyJ, impurities include atoms belonging to group V of the periodic table (group V atoms) 1, for example, p (phosphorus), Ax (arsenic), 5
b (7inch7in), Bj (bismuth), etc.
Particularly preferably used are P and As.

In the present invention, the content in the layer region (PN) in which the substance (C) that controls conduction characteristics is contained is determined by the conductivity required for the layer region (PN) or (PN
) is provided in direct contact with the support, it can be selected as appropriate in terms of organic continuity, such as the 511 relationship with the properties at the contact interface with the support.

In addition, the relationship between other layer regions provided in direct contact with the layer region (PN) and the properties at the contact interface with the other layer regions is also taken into account, and the material ( The content of C) is selected as appropriate.

In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is preferably 0.01-5 x 10' atomic pps.
, more preferably 0.5-I XIO' atomic
ppj, optimally rob; j ′””〜゛”°°山“°°″”:lt
6 M91 t.

In the present invention, the content of the substance (C) in the layer region (PN) containing the substance (C) that controls conduction properties is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more. For example, when the substance (C) to be contained is the p-type impurity described above, the free surface of the photoreceptive layer is charged to zero polarity. It is possible to effectively prevent the injection of electrons from the support side into the photoreceptive layer during treatment, and when the substance (C) to be contained is the n-type impurity, When the free surface of the receptor layer is charged to e-polarity, injection of holes from the support side into the photoreceptor layer can be effectively prevented.

In the above case, as mentioned above, the layer region (PN
) in the layer area (Z) excluding the layer area (P N)
It is also possible to contain a substance that controls recessive conduction characteristics of a conduction type different from the polarity of the conduction type of the substance that governs the conduction characteristics contained in the material, or a conduction characteristic that has conduction characteristics with the same polarity. The controlling (□) substance may be contained in a much smaller amount than the actual amount contained in the layer region (PN).

In such a case, the content of the substance controlling the conductive properties contained in the layer region (Z) is
) is suitably determined as desired depending on the polarity and content of the substance (C) contained in the substance (C), but preferably o,oot to 1001000ato ppm, more preferably 0.05 to 500 ato ppm. as+1aPP@,
The optimum range is preferably 0.1 to 200 atomic PPII.

In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is 3
It is desirable to set it to 0 atomic ppm or less.

In the present invention, when the layer region (P N) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is , preferably 30 atomic pp· or less.

In the present invention, the photoreceptive layer includes a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing the layer region in direct contact with the contact region.

Clogging 1 For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other to form a so-called p-n junction. , a depletion layer can be provided.

11 to 13 show typical examples of the distribution state of the substance (C) controlling conductivity contained in the layer region (PM) of the light-receiving member in the present invention in the layer thickness direction. .

In FIGS. 11 to 19, the horizontal axis shows the distribution concentration C of the substance (C), and the vertical axis shows the layer thickness of the first layer (G).
= indicates the position of the end face of F(G) in ml on the support side, and D indicates the position of the end face of CG) on the opposite side to the support side, that is, the first substance containing *<C) In the calendar (G), layers are formed from the t8 side to the 1T side, and in Figure 11, the 1st
A first typical example of the distribution state of the substance (C) contained in the layer (G) in the layer thickness direction is shown.

In the example shown in FIG. 11, the position of Ll from the interface position Ht where the surface where the first layer (G) containing the substance (C) is formed and the surface of the layer (G) of Ml is in contact with each other. Up to the first point, the substance (C) is formed while the distribution concentration C of the substance (C) takes a constant value CI! CG), and is contained in position 1. In other words, the concentration is gradually and continuously reduced from the concentration 2 to the interface level FIL t t. At the interface position, the distribution concentration C of the substance (C) is reduced to zero.

In the example shown in FIG. 12, the contained substance (C
) minute 2v concentration C is place! ! A distribution state is formed in which the concentration gradually and continuously decreases from C1 from ta to M tr, and the concentration becomes .

(In the case of Fig. 13, from position fll Lm to Ll, the distribution concentration C of substance 1 (C) is a constant value of concentration C, and between position t2 and position !l!, The concentration is gradually and continuously decreased from C7 to the level Ht
At r, the 1-distribution source degree C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of Figure 14, the distribution concentration C of substance (C) is ! t
Position 1 from LB. The concentration gradually decreases continuously from C8 until reaching the concentration C8, and becomes substantially zero at the first place 21.

In the example shown in FIG. 15, the minute 66 degrees C of the object jt (C) is located at the 1st place 1 ta, and the concentration is constant at C9 between 3 and the concentration at the 1st place II t r. Between position t3, which is defined as C3°, and position M tr , the one-distribution source degree C is reduced from position 1 t3 to position It tr in terms of first-order rJIJ numbers.

In the example shown in the first fl1g, the 1 minute lrI concentration C
Ha place S! From Ls to position t4, the concentration C11 takes a constant value, and from position t4 to position 1, the distribution state decreases in a linear function from concentration C12 to concentration CI3.

In the example shown in FIG. 17, the position Hta is
The distribution concentration C of substance (C) up to 11 guns
decreases linearly from the concentration C14 to substantially zero.

In FIG. 18, 5 positions 1. Up to WL5, the distribution concentration C of substance (C) is 2 degrees CI5.
1 position 1[, and position 1,
An example is shown in which the concentration CI & is set to a constant value.

In the example shown in FIG. 13, the distribution concentration C of the substance CG) is at position ti! At ILB, the concentration is CI7, and this concentration CI? until it reaches the 1st position t6. At first, the concentration decreases slowly, and around the position t6, it decreases rapidly, and at t6, the concentration becomes C1fl.

Between position 1tLa and position 11ty, the decrease is rapid at first, and then it is gradually decreased to 1.
The concentration becomes CI9, and the position is t7! t's, it is gradually decreased very slowly and reaches the concentration C26 at position t8 between 0, 11ta and ! ! tr, the concentration is reduced from C20 to substantially zero according to a curve shaped as shown in the figure.

That’s it for part 1! As described in FIG. 19 for some typical examples of the distribution state of the substance (C) contained in the one layer region (ρ) in the layer thickness direction, in the present invention, on the support side, having a portion with a high distribution concentration C of the substance (C),
On the interface 1T side, the distribution state of the substance (C) having a portion where the molecular ri concentration C is considerably lower than that on the support side is set in the first calendar (G) or the second calendar (S). It is desirable that the

The first layer (G) or the second layer (S) constituting the light-receiving layer constituting the light-receiving member in the present invention preferably has a relatively high content of the substance (C) on the support side, as described above. It is desirable to have a localized region (A) containing a high concentration.

In the present invention, the localized region (A) is
Explaining using the symbols shown in FIG. 9, it is desirable to provide within 5 points from the interface position La.

In the present invention, the localized region (A) is located at the interface position 1.
It may be the entire layer region (Lr) up to a final thickness of 5, or it may be a part of the layer region (Lt).

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

In the present invention, the first! (G) a second provided above;
of! (S) does not contain germanium atoms, and by forming a light-receiving layer with such a layered structure, it can be used for all wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. It is obtained as a light-receiving member having excellent photosensitivity to light of different wavelengths.

In addition, the distribution state of germanium atoms in the first M CO is such that germanium atoms are continuously distributed in the entire layer region, so when a semiconductor laser or the like is used, the second M CO I can't absorb much of it.1
The light on the long wavelength side is transferred to the f″1 layer (G)″ – so that it is substantially 1
``1: Can be completely absorbed 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 a-layer interface is sufficiently acidified to ensure chemical stability.

In the present invention, the content of germanium atoms contained in the first ja (G) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1-9. .5X 10'ato logic ppm
, more preferably 100~8X10Satoaic 9
It is desirable that it be 12m.

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, and is therefore formed. Considerable care must be taken in the design of the light receiving member to ensure that the desired properties are fully imparted to the light receiving member.

In the present invention, the layer thickness T of the first calendar (G) is
(Preferably 30A to 5Q islands, more preferably 40A to 40, most preferably 50A to 3Q islands. °0.5～
It is desirable to have 80 pots, more preferably 1 to 80 hours, optimally 2 to 50 hours.

The layer thickness T of the first layer (G) and the layer thickness T of the second layer (G)
The sum (Tm+T) can be determined as desired when designing the photoreceptive member based on the organic relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. , to be determined accordingly.

In the light receiving member of the present invention, the above numerical range of (T@10T) is preferably 1#+00L, more preferably 1 to 80JL, and most preferably 2 to 50IL. is desirable.

In a more preferred embodiment of the present invention, the above-mentioned layer thickness T and layer thickness T preferably have appropriate numerical values for each when satisfying the relationship Tj/d≦1. is preferably selected.

In selecting the numerical values of the layer thickness Tl and the layer thickness T in the above case, it is more preferable that τa/T≦0.9. Optimally, it is desirable that the values of the layer thickness T1 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 (G) is I x 1G' ata@ic
ppm or more, it is desirable that the layer thickness T of the first layer (G) is made considerably thinner, preferably 30
Less than the final, preferably less than 25 wins, optimally 20 JL
The following is desirable.

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

In the present invention, to form the gt layer (G) composed of a-5iGe (H, For example, by glow discharge method, a-5iGs(H,
X) In order to form the first layer CG), basically, a source gas for Si supply that can supply silicon atoms (Si) and a Ge supply gas that can supply germanium atoms (Ge) are used. The raw material gas for hydrogen atoms (H) introduction and/or the raw material gas for halogen atoms (X) introduction as needed are introduced into the deposition chamber whose interior can be reduced in pressure at the desired gas pressure. 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 calendar consisting of (H, X), or when forming by sputtering method.

For example, using two targets, one made of SI and the other made of Ge, in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or a target made of St and Ge. When sputtering using mixed targets.

1 Hydrogen atom (H) or / as necessary
and halogen; 1 A gas for introducing atoms (X) may be introduced into a deposition chamber for sputtering.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4, Si□H6゜S:3H
Hydrogenated atoms (silane!51) which can be gasified into gases and states such as B, 5iaH+o, etc. are mentioned as those which can be effectively used, and in particular, F! 5iHa and 5i2Hs in terms of ease of handling during F creation work, good Si supply efficiency, etc.
.

are listed as preferred.

Substances that can be used as raw material gas for supplying Ge include Ge)
[,,Ge2H6,Gl! 3H8, Ge8H+e, G
e5H12.

Ge&)l 14 + GetH161Ge8H+e
, GegH2 (, etc.) are effective examples of germanium hydride in a gaseous state or that can be gasified, especially in terms of ease of handling during layer formation work, good Ge supply efficiency, etc.

Preferable examples include GeHa, GezH6, and Ge3H6.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogen chlorides, interhalogen compounds, and silane derivatives substituted with halogen. Or a halogen compound that can be gasified is preferably mentioned.

Furthermore, it can be in a gaseous state or gasified, which contains silicon atoms and halogen atoms as constituent elements. Silicon hydride compounds containing halogen atoms are also effective in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Iodine halogen gas, BrF, αF, αF3, B
rF5.

Examples include intergen compounds such as BrF3, IF3, IFy, 1α, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF, Si2F6, Siαa, SiBr4
It is possible to create a car that uses silicon halides such as halides as preferred.

When forming the characteristic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying SL together with a raw material gas for supplying Ge. The first layer (G) made of a-9iGe containing halogen atoms can be formed on a desired support without using silicon oxide gas.

According to the glow discharge method, the first calendar containing halogen atoms (
G), basically, silicon halide, which will be the raw material gas for 1fsi supply, germanium hydride, which will be the raw material gas for Ge supply, and gases such as Ar, H, He, etc. By introducing these gases into a deposition chamber forming a first calendar (G) with the mixing ratio and gas flow rate, a glow discharge is generated to form a plasma atmosphere of these gases.

Although the first calendar (G) can be formed on a desired support, in order to more easily control the introduction ratio of hydrogen atoms, hydrogen gas or hydrogen atoms may be added to these gases. A layer may also be formed by mixing a desired amount of a silicon compound gas containing .

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

To form the first calendar (G) made of a-5iGe (H, Using two targets or a target made of Si and Ge, this is sputtered in a desired gas plasma atmosphere.
Polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in the evaporation port as evaporation sources, respectively, and the evaporation sources are heated and evaporated by a resistance heating method, an electron beam method (EB method), etc. to perform flying evaporation. This can be done by passing an object through a desired gas plasma atmosphere.

At this time, in order to introduce l\\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 if a plasma atmosphere of the gas is formed by introducing the gas into the atmosphere.

, 1) When introducing 2 hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H2, or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. What is necessary is to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or silicon compounds containing /10 gen are effectively used as the raw material gas for introducing /\ halogen atoms, but in addition, HF, )lα, Her .

1 (hydrogen halides such as I, SiH2F2, Si
H212.

5iH2C12, 5IHC11, 5iH2Br2, 5
Halogen-substituted silicon hydride such as iHBr3, and Gs)i
F3+GeH2F2, GeI3F.

Ge1(G3, GeH2α21 GeO20, Ge
) Her3.

GeH2Br2, GsH3Br, GeHI3,
Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as GeH2I2 and GeH3I, GeF4゜Geα, , GeBra,
Ge14. GaF2. Geα2, G5Br2
.

Gaseous or gasifiable substances such as germanium halides such as GeI2 can also be mentioned as effective starting materials for forming the first layer (G).
1 Among these substances, halides containing hydrogen atoms are the first
Hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, are also introduced into the layer at the same time as halogen atoms are introduced into the layer during the formation of calendar CG), so in the present invention, it is used as a suitable raw material for halogen introduction. be done.

To structurally introduce hydrogen atoms into the first layer (G),
In addition to the above, H2, or 5i)I4.5iz)iG*5
Silicon hydride such as i3H6, 5iaH1o, etc. with germanium or germanium compound for supplying Ge, or GeHa, Gs2H6, Ge3H6, G54H
16, G55H12.

GebH+a, GetHIb, GeJ□s
*This can also be achieved by causing germanium hydride such as GegH20 and silicon or a silicon compound for supplying Si to coexist in the deposition chamber to generate a discharge.

In a preferred example of the present invention, hydrogen atoms (1()
The amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms ()I+X) is preferably O,Ql-
40 atomic%, more preferably 0.05-30 a
tomic%, f & suitably 0.1-25 atomic%
It is desirable that this is done.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer (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), starting materials [second The first! ! 'CG
) can be carried out according to the same method and conditions as in the case of forming.

That is, in the present invention, to form the second ya <s> composed of a-5i (H, 0 made by vacuum deposition method
For example, in order to form the second layer (S) composed of a-Si (H, Along with the raw material gas, if necessary, a raw material gas for introducing hydrogen atoms (I()) and/or for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow is generated in the deposition chamber. What is necessary is to generate an electric discharge and form a calendar consisting of a-3i (H,

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 for introducing hydrogen atoms (H) or/and halogen atoms (X) is used. It may be introduced into a deposition chamber for sputtering.

1 *”') '□ 9tp m ＃c
g°゛11ゝ17;j In order to increase the dark resistance and further improve the adhesion between the support and the light-receiving layer, the light-receiving layer contains W1 elementary atoms and carbon atoms. , at least one type of atom selected from nitrogen atoms is contained in a uniform or non-uniform distribution state in the layer thickness direction. Such atoms (OCN) contained in the photoreceptive layer may be contained in the entire layer area of the photoreceptive layer, or may be unevenly distributed by being contained only in a part of the layer area of the photoreceptive layer. You can let me.

As for the distribution state of atoms (OCN), it is desirable that the distribution concentration C (QC:N) is uniform in a plane parallel to the surface of the support of the photoreceptive layer.

In the present invention, atoms provided in the photoreceptive layer (0 to N)
When the main purpose is to improve photosensitivity and dark resistance, the layer area (OCN) containing OCN is provided so as to occupy the entire layer area of the photoreceptive layer, and the area between the support and the photoreceptive layer is When the main purpose is to strengthen the adhesion between the layers, it is provided so as to occupy the end layer region of the light-receiving layer on the side of the support.

In the former case, the atoms (O
The content of CN) was compared to maintain high photosensitivity.
In the latter case, it is desirable to increase the amount relatively in order to ensure enhanced IE adhesion to the support.

In the present invention, a layer region (OCN
) 'c The content of gold-containing atoms (QC:N) depends on the properties required for the layer region (0(:N) itself, or when the layer region (OCN) is provided in contact with a support. for,
It can be selected as appropriate based 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 (OGN), 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 atoms (Ocll) contained in the layer region (OCN) 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 0.003-30 ata
It is desirable to set it to mic%.

In the present invention, whether the layer region (OCN) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is equal to the layer thickness To of the layer area (OCN). When the proportion of atoms (0ON) contained in the layer region (OCN) is sufficiently large, the upper limit of the content of atoms (0ON) contained in the layer region (OCN) is desirably set to be sufficiently larger 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, F! ! The upper limit of atoms (OCN) contained in the region (OCN) is preferably 30 atoms.
ic% or less, more preferably 20ato ic% or less,
Optimally, it is desirable to set it to 10 at.ic% or less.

According to a preferred embodiment of the invention, atoms (in the OC) are preferably present at least in said first layer, which is provided directly on the support. By containing atoms (OCN) in the body side end layer region,
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 light-receiving part.

In addition, multiple types of these atoms (OCN) may be contained in the photoreceptive layer. For example, oxygen atoms may be contained in the first layer, or oxygen atoms may be contained in the same layer region. 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 (QC), tB indicates the position of the end surface of the layer region (OCN) on the support side, and 1 indicates the layer region on the opposite side from the support side. Indicates the position of the end face of (OCN), that is, the position of the end face of (OCN) is 1! In the layer region (OCN), layers are formed from the La side toward the 11 side.

Figure 20 shows atoms (
The first case where the distribution state of IX:N) 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 (Ol
The interface position where the surface of l:N) contacts! From tv to the position, the layer region (Oll:N) where atoms (Oll:N) are formed while the distribution concentration C of atoms (OCN) takes a constant value CI.
00%), and the concentration is gradually and continuously reduced from the 1st position 21L+ until it reaches the interfacial position 1tty.

At the interface position WLr, the distribution concentration C of atoms (OCN) is set to be small.

In the example shown in FIG. 21, the contained atoms (O
The distribution concentration C of CX) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C4 until the position MtT reaches 1T.

In the case of Figure 22, Ht, Yori! ! Until t2, the distribution concentration C of atoms (0(:N) is assumed to be a constant value based on the concentration C, and gradually and continuously (decreases at the 1st place Mt) between position t2 and position d). The 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 (0(:N)) gradually decreases continuously from the concentration C8 from the position Its to the position tr, and becomes substantially zero at the 1st position 11tt. ing.

In the example shown in FIG. 24, the distribution concentration C of atoms (OCN) is at position 1. The concentration C9 is a constant value between and position 13, and from position It3 to position 11tt, the concentration C
9, it decreases linearly to substantially zero.

In the example shown in FIG. 25, the distribution concentration C is at position 1.
．． The density C1l takes a constant value up to the position ML4, and from the position t4 to the position ML4, the density decreases linearly from CI2 to C13.

In the example shown in FIG.
Until □, the distribution concentration C of atoms (0ON) is the concentration Ct
It decreases linearly from a to substantially zero.

In FIG. 27, from position t8 to position t, the distribution concentration C of atoms (OCN) is 01 from the concentration CI5.
1 position that is gradually decreased continuously until 6! [5th place 11
An example is shown in which the concentration CI & is set to a constant value between Lr and Lr.

In the example shown in FIG. 28, the distribution concentration C of atoms (OCN) is in the first place W! In ltB, the concentration is CF, and up to the first place Mt6, this concentration is CI? Initially, the concentration is gradually decreased, and around the t position, it is rapidly decreased to a concentration CI8 at 1 ota.

Between position t and position NL7, the concentration is first rapidly decreased, and then gradually decreased to become the concentration CtS at position gtf, and between position 1th and position Mt8,
At L8, the concentration is gradually decreased very slowly, and between the 0th position MLta and the position MtT, which reaches the density C20, the density is decreased according to a curve shaped as shown in the figure so as to be substantially similar to the density C2°.

As described above, one layer area (OCN) is shown in FIGS. 20 to 28.
As explained in some of the typical examples where the distribution state of atoms (OCN) 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 (B) containing atoms (0ON) at a relatively high concentration on the support side as described above. Desirably, in this case, the adhesion between the support and the light-receiving layer can be further improved.

The localized region (B) can be explained using the symbols shown in FIGS. 20 to 28 at interface position 1. It is more preferable to set it within 5 trigrams.

In the present invention, the localized region (B) is located at the interface position t
It may be the entire region (LT) from l to 5 final thickness, or it may be a part of the one-layer region (LT).

Shin 11 Localized region CB) to layer region (
Whether L")-114 should be 6"' or all of it is determined as appropriate depending on the properties required of the light-receiving layer to be formed.

The localized region (B) has a distribution state of atoms (OCN) contained therein in the layer thickness direction such that the maximum value Cmaz of the atomic (OCN) distribution concentration C is preferably 500 atoms+c p
p- or more, more preferably 1100 atomic pp-
As described above, it is desirable that the layers be formed in such a way that a distribution state of 10QOatasic pp■ or more can be achieved optimally.

That is, in the present invention, the layer region (OCN) containing j Cs
It is desirable to form such that aw 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 (00%
) and other layer regions, it is desirable to form a distribution state of atoms (0ON) in the layer thickness direction so that the refractive index changes gradually.

By doing this, the light incident on the photoreceptive layer is prevented from being reflected at the contact interface, and interference fringes are formed.
1-like expression can be more effectively prevented.

Further, it is preferable that the change line of the distribution concentration C of atoms (OCN) in the one-layer region (OCX) continuously and gently change in order to provide a smooth change in the refractive index.

From this point, for example, Figures 20 to 231! Il! It is desirable that atoms (Oll:N) be contained in the layer region (0011) so as to have the distribution states shown in FIGS. 26 and 28.

In the present invention, in order to provide a layer region (OCN) containing atoms (OCN) in the photoreceptive layer, a starting material for introducing atoms (OCN) is added to the above-mentioned photoreceptor when forming the photoreceptor layer. It may be used together with the starting material for forming the layer, and may be incorporated in the formed layer in a controlled amount.

When a glow discharge method is used to form the layer region (OCN), a starting material for introducing atoms (011; As the material, most gaseous substances whose constituent atoms are at least atoms (OCS) or gasified substances that can be gasified are used.

Specifically, for example, oxygen (02), ozone (03) - nitrogen oxide (MO), nitrogen trioxide (NO2), -dioxide chamber 3K (820), sesquioxide ml (N203),
Trinitric oxide (NzQa), mini nitric oxide ([2O5)
, nitrogen trioxide (NO), 1 whose constituent atoms are a silicon atom (Si), an oxygen atom (0), and a hydrogen atom ()I)
For example, lower cycloxanes such as disiloxane (835iO5iH3), tricycloxane (H3SiO5iH□05iH3), methane CCHa>, ethane (C2H&)
, propane (CI Hl), n-butane (n-CaH
saturated hydrocarbons having 1 to 5 carbon atoms such as so)-pentane (C5H12), ethylene (C2H4), propylene (C3
Hs'), butene-1 (Ca Is ), butene-2 (
C4H*), inbutylene (Ca Hl), pentene (
Ethylene hydrocarbons having 2 to 5 carbon atoms such as Cs Hs・), acetylene (CzHz), methylacetylene (C3)
[4) Acetylenic hydrocarbons having 2 to 4 carbon atoms such as butyne (CaHa),! 1 element (N2), ammonia (
NH3), hydrazine (H2NNH2) - hydrogen azide (HNa), ammonium azide (NH4N3
), nitrogen trifluoride (F3N), nitrogen tetrafluoride CF4N), etc.

In the case of the sputtering method, the starting materials for introducing atoms (OCN) include, in addition to the above-mentioned gasifiable starting materials listed for the glow discharge method, solidified starting materials:
5i02. Examples include Si3Ha and carbon black. These are used as sputtering targets together with targets such as Si.

In the present invention, when forming the photoreceptive layer, atoms (0[:
When providing a layer region (ocN) containing N), the concentration Ct of molecules a of atoms (OCN) contained in the layer region (ocN) is changed in the thickness direction to obtain a desired distribution state ( layer region (O
CM) for 1 minute mW in the case of glow discharge.
Change the degree C! # Introducing the starting material gas for introducing atoms (OCN) into the deposition chamber while appropriately changing the gas flow rate according to the desired rate of change curve (1° 1
This can be done by temporarily changing the opening of a specified needle valve installed in the middle of the gas flow system using some conventional method, such as manually or using an externally driven motor. However, the rate of change in the flow rate does not have to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

When forming the Fj II region (0ON) by the sputtering method, the distribution concentration C of atoms (OCN) in the layer thickness direction
By changing in the layer thickness direction, the desired distribution of atoms (OCN) in the layer thickness direction can be obtained! To create a (depthprofile).

Firstly, as in the case of the glow discharge method, the starting material for introducing atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition atmosphere is changed as desired. . Second, if a sputtering target is used, for example, a mixed target of Sl and 5i02, the mixing ratio of Si and 5i02 should be changed in advance in the direction of the layer thickness of the target. Made by
1 The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1°C, No, Au, Wb, Ta,
Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof.

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

For example, if it is glass, old Cr, A1.
Cr, No, ^U, Ir, Nb, Ta, V,
Ti, Pt, Pd.

In2O3, 5n02. ITO (In203 151
Conductivity can be imparted by providing a thin film consisting of NiCr, A1. AH, Pb, Z
n, old, Au, Cr.

1ijl of metals such as No, rr, Nb, Ta, V, Ti, Pt, etc. Conductivity is imparted to the surface by providing I on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating the surface with the above-mentioned metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs.For example, the light receiving member 1004 in FIG. In the case of continuous high-speed copying, the thickness of the support is preferably endless belt-like or cylindrical.

It is determined as appropriate to form a desired light receiving member, but if flexibility is required as a light receiving member,
It is made as thin as possible within a range that allows it to fully function as a support. In such a case, from the viewpoint of manufacturing and handling of the support and functional strength, preferably 1.
It is considered to be G end or higher.

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

FIG. 28 shows an example of a light-receiving member manufacturing apparatus.

Gas cylinders 2002 to 200B in the figure are sealed with raw material gas for forming the light receiving member of the present invention.
．． 9119%, hereinafter abbreviated as 5i)Is) cylinder, 2
003 is GeH4 gas (purity 119JH%, hereinafter GeH
4) cylinder, 2004 is NO gas (purity 11L) cylinder.
999%, hereinafter abbreviated as NO) cylinder, 2005 is B diluted with H2, H6 gas (purity ss, sas%, hereinafter 82) Is / )! 2) cylinder, 2006 is a H2 gas (purity 9L11911%) cylinder.

In order to flow these gases into the reaction chamber 2001, valves 2022 to 202B of gas cylinders 2002 to 200B,
Make sure that leak valve 2035 is closed, and inlet valves 2012-2018. Outflow valve 2
017~2021° Check that the auxiliary valves 2032 and 2033 are open, and then open the main valve 2034.
Open the reaction chamber 2001 and exhaust the inside of each gas pipe.The reading of the vacuum gauge 2036 is approximately 5
When the temperature reaches rr, close the auxiliary valve 2G32.2033 and the outflow valves 2017 to 2021.

(Next, a photoreceptive layer is formed on the cylindrical substrate 2037.
t6**. 1 o a 3, 6 o, 9□yx:
2002.

SiH4 gas, Ge from gas tube 2003) 1. Gas, gas cylinder 2004 NO gas, gas pump <200
5 to 82 Hb/Hz gas, 2008J:SuH2
Gas /< Lupu2022.2o23.2024.20
Open 25.2028 and outlet pressure gauge 2o27.202
8. The pressure of 2029.2030.2031 is l Kg/c
Adjust y4 to tn', inflow valve 2012.2013.2
014, 2015.2 o16 gradually opened, mass flow controller 2007゜2008.2009.2010
．． 2011 respectively. Ite continues to be leaked /<
Lupu2o17.2G18.2019.2020゜202
1. Gradually open the auxiliary valves 2032 and 2033 to supply each gas to the reaction chamber 200! to flow into. At this time, Si
H4 gas flow rate Get (4 gas flow rate, NO gas flow rate ratio is 16 to the desired value: Outflow/<kb2o17.201
8.2019.2020.2021, and also adjust the vacuum gauge 2 so that the pressure inside the reaction chamber 2001 reaches the desired value.
Adjust the opening of the main valve 2034 while checking the reading of 036. Then, f1! indicates that the temperature of the base body 2o37 is set to a temperature in the range of 50 to 400°C by the heating heater 2038! Ll&, tl[2040tW′f
fO? 1JJC;4:ii! L-IE.

A glow discharge is generated in the reception room 2001.

The glow discharge is maintained for a desired time in the manner described above to form the first calendar (G) on the base 2037 to a desired layer thickness. At the stage where the first layer (G) has been formed to a desired layer thickness, glow discharge is performed for a desired time according to the same conditions and procedures, except for completely closing the outflow valve 2018 and changing the discharge conditions as necessary. By maintaining the second calendar (S) substantially free of germanium atoms on the first calendar (G)
can be formed.

In addition, in each layer of the first calendar (G) and the second calendar (S),
By appropriately opening and closing the outflow valve 2019 or 2020, oxygen atoms or boron atoms can be contained,
It is also possible to contain no elemental atoms or boron atoms, or to contain # elements or boron atoms only in some layer regions of each layer. Also, instead of an oxygen atom.

When nitrogen atoms or carbon atoms are contained in the layer, N formation may be performed by replacing the NO gas in the gas cylinder 2004 with, for example, H3 gas or CH4 gas.
Also, the amount of gas used! ! If you want to increase the number of layers, just add the desired gas cylinder and form the layers in the same way.During the formation of 6 layers, in order to make the layer formation uniform, the base 2
037 is preferably rotated at a constant speed by a motor 2039.

Finally, after forming the second calendar (S) above, 1 e.g. 200B
Replaced the hydrogen (H2) gas cylinder with a methane (CHa) gas phone, and installed mass flow controllers 2007 and 2.
By maintaining the glow discharge for the desired time according to the same conditions and procedures except for setting 011 to a predetermined flow rate, the second
A surface layer mainly composed of silicon atoms and carbon atoms can be formed on the calendar (S) of the present invention.

When the surface layer mainly formed from silicon atoms and carbon atoms is formed by sputtering.

For example, you can replace a 2006 hydrogen (H2) gas cylinder with argon (
A) Replace with a gas cylinder and clean the M1 equipment.

For example, a sputtering target made of Si and a sputtering target made of graphite are spread over the canned electrode so as to have a desired area ratio. After that, the device formed up to the second calendar (S) is placed in the device, and after the pressure is reduced, argon gas is introduced to generate a glow discharge and sputter the surface layer material to form the surface layer to the desired thickness. Form.

〔Example〕

Examples will be described below.

Example 1 Super support (length L) 357m5. Outer diameter (r)
80 Riho] was ground processed under the conditions shown in Table 1 (B) to have the surface properties shown in Figure 30.

Next, under the conditions shown in Table 2, ! in Figure 29! ! An a-5i electrophotographic light-receiving member was produced using a deposition apparatus and following a predetermined operating procedure. Further, the deposition of the surface layer mainly composed of silicon atoms and carbon atoms was carried out in a first-order manner.

That is, after depositing the second layer, C
H, the flow rate ratio of the gas flow rate to the SiH4 gas flow rate is S
A mass 70 controller (corresponding to each of these gases) is set so that the iHa/CH4 concentration is 1/30, and a glow discharge is generated with high frequency power of 300 liters to form one surface layer. Ta.

When the layer thickness distribution of the a-9i electrophotographic light-receiving member produced in this manner was measured using an electron microscope, the average layer thickness difference between the center and both ends of the first calendar was 0.1-1. It is 2u at the center and both ends of the calendar, and the difference in layer thickness in the minute part is the first
It was 0.02- in the first layer and 0.3- in the second layer.

Regarding the above electrophotographic light-receiving member, an image exposure apparatus shown in FIG. 31 (laser light wavelength: 780 nm) was used.

Perform image exposure with a spot diameter of 80μ), develop it,
An image was obtained by transfer. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use.

Example 2 Same as Example 1, super support [length L] 357■
, outer diameter (r) of 80 m-) was machined on the ground to the surface properties shown in Table 1 (C).

Next, in the same manner as in Example 1 except that the conditions shown in Table 3 were used, a-9i electrophotographic light-receiving members were prepared using the film deposition apparatus shown in FIG. 29 according to various operating procedures.
1 was created.

When the layer thickness distribution of the a-8i electrophotographic light-receiving member produced in this manner was measured using an electron microscope, the average layer thickness difference was 0.1μ between the center and both ends of the first calendar, The thickness at the center and both ends of the second calendar was 2 g, and the layer thickness of the minute portion was 0.03-μs in the first calendar and 0.3 μs in the second calendar.

Regarding the light-receiving member for electrophotography as described above.

Image exposure system M (laser light wavelength 7) shown in riS31 diagram
Image exposure was performed at a spot size of 80 ns and a spot diameter of 110 u), which was then developed and transferred to obtain an image. No fringe pattern was observed in the obtained image, which was sufficient for practical use.

Example 3 Similar to Example 1, at support [length L] 357
m5. The outer diameter (r) of 80 mm) was ground to the surface properties shown in Table 1 (D).

Next, a-5i electrophotographic light-receiving members were produced in the same manner as in Example 1 using the film deposition apparatus shown in FIG. 29 according to various operating procedures, except that the conditions shown in Table 4 were used.

When the layer thickness distribution of the thus produced a-9i electrophotographic light-receiving member was measured using an electron microscope, the average layer thickness difference was 0.8 scales between the center and both ends of the first calendar, and 0.8 scales at the second It is 2u at the center and both ends of the calendar, and.

The difference in layer thickness in the minute part was 0.01 μs in the first calendar and 0.3 scales in the second calendar.

Regarding the light-receiving member for electrophotography as described above.

Image exposure system shown in Figure 31! t (wavelength of laser light 78
Image exposure was performed with a spot size of 0 nm and a spot diameter of 80 scales.

It was developed and transferred to obtain an image. No fringe pattern was observed in the obtained image, which was sufficient for practical use.Example 4 Similar to Example 1, AI support [length L] 357
■The intestine (outer diameter (r) 80 mm) was ground processed to the surface properties shown in Table 1 (E).

Next, a-5i electrophotographic light-receiving members were prepared in the same manner as in Example 1, using the film deposition apparatus shown in FIG. 29, and following various operating procedures, except that the conditions shown in Table 5 were used. .

When the layer thickness distribution of the a-5i electrophotographic light-receiving member produced in this way was measured using an electron microscope, the average layer thickness difference was 0.8 scales between the center and both ends of the first calendar, and 0.8 scales at the second There are two scales at the center and both ends of the layer, and also.

The layer thickness difference in the minute part is the first calendar fo, 153 + a,
It was 0.3u in the second calendar.

Regarding the electrophotographic light-receiving member as described above, the wavelength of the image exposure Ilt'lC laser beam shown in FIG. 80n
Image exposure was performed with a spot diameter of 80 scales).

It was developed and transferred to obtain an image. The resulting image includes
No fringe pattern was observed, and the result was sufficient for practical use. Example 5 A-5i was prepared in the same manner as in Example 3, except that the CH and gas used in Example 3 were replaced with NH cogas. A light-receiving member for electrophotography was prepared.

Each of the light-receiving members thus produced was subjected to image exposure using an image exposure apparatus shown in FIG. An image was obtained by transfer. No interference fringe pattern was observed in any of the obtained images, and the images were sufficient for practical use.

Example 6 A-5i electrophotographic light-receiving members were produced in the same manner as in Example 4, except that the NO gas used in Example 4 was replaced with CH4 gas.

For each of the light-receiving members produced in this way, an image exposure apparatus (laser light wavelength 78
Image exposure was carried out at 0 rv, spot diameter 80 scales), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in any of the obtained images, which were sufficient for practical use.

Example 7 M support (length L) 357s, diameter (r)
80 m5) was processed at an inn to have the surface properties shown in Figure 1 CB) to (E).

Next, various operations were performed using the film deposition apparatus shown in FIG. 29 in the same manner as in Example 1 except that the conditions shown in Table 6 were used.
A-Si based electrophotographic light-receiving members were manufactured according to the manufacturing procedure (Sample Nos. 701 to 704).

Note that the boron-containing layer has a flow rate of 82[67H2]
Adjust the flow rate of NH to the 38th point as shown in the figure.
As shown in the figure, mass flow controllers 201O12009 for B2)167H2 and NH, respectively, were controlled by a computer ()IpH84511).

When the layer thickness of each layer of the light-receiving member thus produced was measured using an electron microscope I11 mirror photograph, the results shown in Table 7 were obtained.

Regarding these light-receiving members for electrophotography, an image exposure device shown in FIG. 31 is used! ! Image exposure was carried out using (laser light wavelength: 7 days 0 nm, spot diameter: 80 μm), which 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 8 Example 7 except that the MW and gas used in Example 7 were replaced with NO gas. A-9i-based electrophotographic light-receiving members were produced in the same manner as above (Sample Nos. 1101 to 804).
).

These electrophotographic light-receiving members were subjected to image exposure using an image exposure device M shown in FIG. 31 (laser light wavelength: 780 nm, spot diameter: 80 μm), developed, and printed to obtain images. No interference fringe pattern was observed in any of the images of sample N(!, 801 to 804), which was sufficient for practical use.

Example 9 'II) I3 gas used in Example 7 was changed to CH
a-S in the same manner as in Example 7 except that a gas was used.
An i-based electrophotographic light-receiving member was produced (sample No. 90
1-1304).

These electrophotographic light-receiving members were subjected to image exposure using the image exposure apparatus shown in FIG. 31 (laser light wavelength: 780 QIM, spot diameter: 80 scales), and then developed and transferred to obtain images. No interference fringe pattern was observed in any of the images of samples Nos. 901 to 804, which were sufficient for practical use.

Example 1 O M support (length L) 357 mm, diameter (r) 80 ■
m) was processed at an inn to give the surface properties as shown in Figures 1 (B) to (E).

Next, in the same manner as in Example 1 except that the conditions shown in Table 8 were used, a-5i electrophotographic light-receiving members were produced using the desalination transplantation apparatus shown in FIG. 29 according to various operating procedures (sample N
o, 1001-1004).

In addition, the boron-containing layer was formed so that the flow rate of 82 Is/Hz was as shown in FIG. 33, and the flow rate of CH was as shown in FIG. 37, respectively, at 82 Hb/H2.
and Cl44 mass flow controller 2010.20
It was controlled by a 011wo com viewer (HP9845B).

When the layer thickness of each layer of the light-receiving member thus produced was measured using an electron micrograph, the results shown in Table 9 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using the image exposure apparatus shown in FIG. 31 (laser light wavelength: 780 nm layer, spot diameter: 80 scales), and then developed and transferred to obtain images. The obtained image has no interference fringe pattern on the Il side, and is sufficient for practical use1.

to,! Example 11 A-9i electrophotographic light-receiving members were produced in the same manner as in Example 10, except that the CH4 gas used in Example 10 was replaced with NO gas (Sample Nos. 1101 to 1101).
1104).

Regarding the light receiving member for electrophotography produced in this way, the image exposure apparatus t shown in FIG.
Perform image exposure at 80 ms, spot diameter 80 u),
It was developed and transferred to obtain an image. Sample No. 1101
There is no interference fringe pattern in any of the -1104 images! ! It was not measured and was sufficient for practical use.

Example 12 An a-Si electrophotographic light-receiving member was produced in the same manner as in Example 1 (l) except that the CH4 gas used in Example 1O was replaced with NH3 gas (Sample No. 120).
1-1204).

These electrophotographic light-receiving members were subjected to image exposure using an image exposure device N shown in FIG. 31 (laser light wavelength: 780 mm, spot diameter: 80 g), and then developed and transferred to obtain images. Sample No. 1201~ (
Interference JI in any image of 1204! +8 was not observed, which was sufficient for practical use.

Example 13 Super support (length L) 357 m5, diameter (r)
80 am) was processed at an inn to have the surface properties shown in Figures 1 (B) to (E).

Next, in the same manner as in Example 1 except that the conditions shown in Table 10 were used, the sedimentation shown in FIG. 29 was carried out. An electrophotographic light-receiving member was prepared using an apparatus according to various operating procedures (sample No. 13).
G1-1304).

In addition, the boron-containing layer has a flow rate of 8286/H2
4. Adjust the NO flow rate as shown in Figure 38.
82 H6/H2 and N respectively as shown in the figure.
An O mass flow controller 2010.2o09 was controlled by a computer (HP9845B).

When the layer thickness of each layer of the light-receiving member thus produced was measured using an electron micrograph, the results shown in Table 11 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 31 (laser light wavelength: 7BOn, spot diameter: 80 m), developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use.

Example 14 Example! A-5i electrophotographic light-receiving members were produced in the same manner as in Example 13, except that the NO gas used in Example 3 was replaced with NH3 gas (Sample Nos. 1401 to 1).
404).

The electrophotographic light-receiving member produced in this way was exposed to the image exposure apparatus (laser light wavelength 78 cm) shown in FIG.
Image exposure was carried out at a spot diameter of 0 ns and a spot diameter of 8 degrees, and the image was developed and transferred to obtain an image. Sample No. 1401~
No interference fringe pattern was detected in any of the images of 1404,
It was sufficient for practical use.

Example 15 &-Si based electrophotographic light receiving members were produced in the same manner as in Example 13, except that the NO gas used in Example 13 was replaced with CH gas (Sample No. 1501-
1504).

Regarding these electrophotographic light receiving members, an image exposure device W! shown in FIG. 31 is used. 1 (laser light wavelength: 780 I, spot diameter: 80 mm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in any of the images of sample Nos. 1501 to 1504, which were sufficient for practical use.

Example 16 M support (length L) 357 mm, diameter (r)
80 mm) was machined using a lathe to obtain the surface properties shown in Figures 1 (, B) to (E).

Next, an electrophotographic light-receiving member was produced in the same manner as in Example 1, except that the conditions shown in Table 12 were used, using the deposition apparatus shown in FIG.
1-1804).

In addition, the boron-containing layer was formed by controlling the flow rate of B2H6/H as shown in Fig. 35 and the flow rate of NH3 as shown in Fig. 38, respectively.
3 mass flow controller 2010.200B was controlled by a computer (HP9845B).

5 The thickness of each layer of the light-receiving member thus produced was measured using an electron microscope photograph, and the results shown in Table 13 were obtained.

Regarding these light-receiving members for electrophotography, an image exposure device shown in FIG. 31 is used! Image exposure was carried out using (laser light wavelength 780 nm, spot diameter 80 nm), which 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 17 Same as Example 1B except that the NH3 gas used in Example 1B was replaced with No gas. An a-5i electrophotographic light-receiving member was prepared using the following methods (Sample! 1a, 1701
~+704).

These electrophotographic light-receiving members were subjected to image exposure using an image exposure device M shown in FIG. 31 (laser light wavelength: 780 nm, spot diameter: 80 scales), and then developed and transferred to obtain images. No interference fringe pattern was observed in any of the images of sample Nos. 1701 to 1704, which were sufficient for practical use.

Example 18 The NH3 gas used in Example IB was changed to CH, gas
An a-9i electrophotographic light-receiving member was produced in the same manner as in Example IB except for replacing with 1.
(Sample No. 1801-1804).

Regarding these electrophotographic light-receiving members, an image exposure apparatus shown in FIG. 31 is used! (Laser light wavelength 780■, spot,
Image exposure was performed with a cut diameter of 80 μ), and the image was developed and transferred to obtain an image. There is no interference fringe pattern on the sample in any of the images from 180L to 1804! ! It was not compromised and was sufficient for practical use.

Example 19 Regarding Example 1 to Example 18, 3000 in B2
B2) in contact with vol PPm water 1. B instead of gas
A light-receiving member for photographic use was prepared using PH3 gas diluted to 3000 ppm in 2 (Sample No.
1901-1950).

Note that other manufacturing conditions were the same as in Example 1 to Example 1B.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure device M (laser light wavelength: 780 nm, spot diameter: 80 u) shown in FIG. 31, and then developed and transferred to obtain images. No interference fringe pattern was observed in any of the images of samples No. 1+1+301 to 1950, which were sufficient for practical use.

Example 20 M support (length L) 357 am, diameter (r
) 5i) when forming one surface layer using 80ts)
A-5i electrophotographic photoreceptor was prepared under the same conditions and procedures as in Example 1, except that the flow rate ratio of ta gas and CH4 gas was changed as shown in Table 14 to form a surface layer. The members were produced (sample! 2701-2708
).

Each of the electrophotographic light-receiving members thus produced was image-exposed using the image exposure device shown in FIG. 31 (laser light wavelength 780n, spot diameter 80u).
After repeating the series of steps of image formation, development, transfer, and cleaning 50,000 times, image evaluation was performed, and the results shown in Table 14 were obtained.

Example 21 M support [length t,] 3571 feet, diameter (r
) 80 mm), the raw material gases used in forming the surface layer were SiH4 gas, CHa, and SiF4, and the flow rate ratios of these gases were changed as shown in Table 15, except that the surface layer was formed. , a −! according to the same conditions and procedures as in Example 20. 3i-based electrophotographic receiving members were produced (Samples Nos. 2801 to 2808).

For each of the light-receiving members produced in this way, an image exposure device M (laser light wavelength 7
80n++, spot diameter 80μs), and after repeating the series of steps of image formation, development, transfer, and cleaning 50,000 times, 7 image evaluations were performed, and the results shown in Table 15 were obtained. Ta.

Example 22 M support (length L) whose surface was machined with a lathe to give the surface properties as shown in FIG. 1 (8) 35? ■■, diameter (r
) 80 mm), and the surface layer was coated as shown below.
Except for changing the area ratio of the target and the C target as shown in Table 18,
According to the same conditions and procedures as in Example 1, a-Si based electrophotographic light-receiving members were produced (samples a2901 to 29
08) - That is, first, after forming the second layer, take out the support formed up to the second layer from the salt 8I apparatus shown in FIG. 29,
After replacing the hydrogen (H2) gas cylinder in the device with an argon (Ar) gas cylinder and cleaning the inside of the device, a sputtering target made of Si with a thickness of 5 mm and a thickness of 5 mm made of graphite was placed on the cathode electrode. sputtering targets were spread over one surface so that the area ratios were as shown in Table 16. After that, the support formed up to the second stage was installed in the device, the pressure was reduced, argon gas was introduced into the device, and the high frequency power was set to 300 W to generate glow discharge, and the material for forming the surface layer on the cathode electrode was was further sputtered onto the second N on the support to form a surface layer consisting of silicon atoms and carbon atoms at a predetermined mixing ratio.

For each of the electrophotographic light-receiving members thus produced, the image fRN optical device shown in FIG.
1 (laser light wavelength 780 nm, spot diameter aou), and after repeating the series of steps of image formation, development, transfer, and cleaning 50,000 times, one image evaluation was performed, and the results are shown in Table 16. The following results were obtained.

〔Effect of the invention〕

As described above in detail, according to the present invention.

It is suitable for image formation using coherent monochromatic light, has transparent manufacturing control, and can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development. Moreover, it is possible to provide a light-receiving member that is excellent in mechanical durability, particularly in abrasion resistance and light-receiving properties.

[Brief explanation of drawings]

FIG. 1 is a general explanatory diagram of interference fringes. FIG. 2 is an explanatory diagram of interference fringes in the case of a multilayer light receiving member. FIG. 3 is an explanatory diagram of interference fringes due to scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. FIG. 5 is an explanatory diagram of interference fringes when the interfaces of each layer of the light receiving member are parallel. FIGS. 6(A), (B), (G), and CD) are explanatory diagrams showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIGS. 7(A), (B), and (C) are explanatory diagrams for comparing the intensity of reflected light when the interfaces of each layer of the light-receiving member are parallel and non-parallel. FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. FIGS. 9(A), (B), and (C) are explanatory diagrams of the surface conditions of typical supports, respectively. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIGS. 11 to 19 are explanatory diagrams for explaining the distribution state of the substance (C) that controls conductivity contained in the layer region (PN), respectively. FIGS. 20 to 28 are explanatory diagrams for explaining the distribution state of atoms (O, C, X) in the layer region (OCN), respectively. FIG. 28 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 30 is an explanatory diagram 7 of the surface state exposure 1 of the M support used in the examples. FIG. 31 is an explanatory diagram of the image exposure apparatus used in the examples. FIG. 32 to FIG. 35 are 82 in each example.
There is a curve showing the rate of change of the flow rate of H67H2 gas. FIGS. 36 to 39 each show the rate of change curves of the gas flow rate ratio in the examples. 1000......Photoreceptive layer 1001...Super support +002...・・・・・・・・・・・・First layer 1003・・・・・・・・・・・・・・・・・・
Second calendar! 004・・・・・・・・・・・・・・・・・・
・Light receiving member 1005・・・・・・・・・・・・・・・
...Free surface 1008 of the light-receiving member...
......Surface layer 2601...
・・・・・・・・・Light receiving member for electrophotography 2602・
・・・・・・・・・・・・・・・・・・ Semiconductor laser 2
603・・・・・・・・・・・・・・・Fθ lens 2804・・・・・・・・・・・・・・・Polygon mirror 2805・・・・・・・・・・・・・・・・・・
... Plan view of exposure equipment 1
260B・・・・・・・・・・・・・・・Side view of exposure device No. 1m Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 (A) (8) Fig. 7 (A) (B) (C) 〒 Figure 9 Figure 10 □C 1st! Figure 12 Figure 13 Figure 14 Figure 15 Figure 18 Figure ti, Figure 18 Figure □C Figure 19 C- Figure 20 Figure 21 Figure 22 Figure 23 Figure 24 Figure 26 Figure 27 Figure 28 Figure 30 Figure 31 Time (minutes) Figure 32 0 20 40'/60 hours (minutes) Figure 33 Time (minutes) Figure 34 Time (minutes) *a5vA Fig. 36 (778 wash basin 1.1 Fig. 37 B, 1:, 11! Fig. 38

Claims (19)

[Claims] (1) A support, a first layer made of an amorphous material containing silicon atoms and germanium atoms, and a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. and a surface layer made of an amorphous material containing silicon atoms and carbon atoms. At least one of the two layers contains a substance that controls conductivity, and in the layer region containing the substance, the distribution state of the substance is uneven in the layer thickness direction, and the light-receiving layer contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and has one or more pairs of nonparallel interfaces within a short range, and the nonparallel interfaces are perpendicular to the layer thickness direction. A light-receiving member characterized in that a large number of light-receiving members are arranged in at least one direction within a plane. (2) Claim 1, wherein the photoreceptive layer contains at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform distribution in the layer thickness direction. photoreceptor member. (3) Claim 1, wherein the photoreceptive layer contains at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms in a non-uniform distribution in the layer thickness direction. The photoreceptive member described. (4) The light receiving member according to claim 1, wherein the arrangement is regular. (5) The light receiving member according to claim 1, wherein the arrangement is periodic. (6) The light receiving member according to claim 1, wherein the short range is 0.3 to 500μ. (7) The light-receiving member according to claim 1, wherein the non-parallel interface is formed based on regularly arranged irregularities provided on the surface of the support. (8) The light-receiving member according to claim 7, wherein the unevenness is formed by an inverted V-shaped linear protrusion. (9) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially an isosceles triangle. (10) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a right triangle. (11) The light-receiving member according to claim 8, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a scalene triangle. (12) Claim 1, wherein the support body is cylindrical.
The light-receiving member described in 2. (13) The light-receiving member according to claim 12, wherein the inverted V-shaped linear protrusion has a spiral structure within the plane of the support. (14) The light receiving member according to claim 13, wherein the helical structure is a multiple helical 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.