JPS60221763A - Photoreceptible member - Google Patents

Abstract

PURPOSE:To apply the titled member to interferential light by distributing Ge of a conductive substance in a specified state to a photoreceptible layer constituted by providing an a-SiGe layer, an a-Si photoconductive layer and a reflection preventing surface layer in order on a supporting body, and also forming said layer to a specified layer structure. CONSTITUTION:The titled member has a multi-layer constitution photoreceptible layer 1000 provided with the first layer 1002 consisting of a-SiGe, the second layer 1003 consisting of a-Si and having photoconductivity, and a reflection preventive surface layer 1006 in order from a supporting body 1001 side, a distributing state of Ge in the layer 1002 is made ununiform in the layer thickness direction, also at least one of the layer 1002 and the layer 1003 contains a substance for controlling conductivity, and its contained layer area, the distributing state of its substance is made ununiform in the layer thickness direction, also the layer 1000 has a pair or more of non-parallel interfaces in a short range, and many non-parallel interfaces are arranged at least in one direction on the surface vertical to the layer thickness direction. In this way, by increasing the number of layers of the photoreceptible layer 1000, an interferential effect of an irradiated light is prevented. Also, an interference fringe generated in the minute part does not appear on a picture because its part is smaller than the irradiated light spot diameter.

Description

[Detailed description of the invention] [Industrial application field] The present invention is based on light (here, ultraviolet light in a broad sense).

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

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

[Prior art]

As a method for recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is developed. A well-known method is to record an image by performing processes such as transfer and fixing depending on the image.

Among these, in image forming methods using electrophotography, image recording is generally performed using a small and inexpensive He--Ne laser or semiconductor laser (usually having an emission wavelength of 650 to 820 nm).

In particular, as a light-receiving member for electrophotography that is suitable when using a semiconductor laser, Vickers For example, JP-A No. 54-86341 and JP-A-Sho 56-
A light-receiving member made of an amorphous material containing silicon atoms (hereinafter abbreviated as rA-siJ) disclosed in Japanese Patent No. 83746 is attracting attention.

Of course, if the photoreceptive layer is a single-layer A-91 layer, in order to maintain its high photosensitivity and ensure a dark resistance of 1012 Ωcm or more required for electrophotography, it is necessary to incorporate hydrogen atoms and halogen atoms. In addition to these, it is necessary to structurally contain poron atoms in a controlled manner in the layer in a specific star range, so it is necessary to strictly control the layer formation, etc. There are considerable limitations on tolerances in component design.

For example, Japanese Patent Laid-Open No. 54-121743 is an example of a system that can expand this design tolerance and make effective use of high light sensitivity even if the dark resistance is low to some extent.
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, or
No. 178, No. 52179, No. 52180, No. 581
59, No. 58160, and No. 58161, 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. , a light-receiving member with apparently increased dark resistance has been proposed.

Through such proposals, the A-5i-based light-receiving material has made dramatic progress in its commercialization design and actual tolerances, as well as in ease of manufacturing control 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, so the light-receiving layer is 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"). There is a possibility that each of the reflected lights may cause interference.

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

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

This point will be explained with reference to the drawings.

FIG. 1 shows light IQ incident on a certain layer constituting the light-receiving layer of a light-receiving member, reflected light R1 reflected at the upper interface 102,
The reflected light R2 reflected at the lower interface 101 is shown.

If the average layer thickness of the layer is d, the refractive index is n, and the wavelength of light is uneven due to the difference in layer thickness, the reflected lights R1 and R2 will be 2nd = m input (m
is an integer, and the amount of light absorbed and transmitted by a certain layer changes depending on which condition is met (reflected light strengthens and combined light weakens).

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, causing a defective image.

A method for solving this problem is to diamond-cut the surface of the support and provide unevenness of ±500 to ±100A to form a light-scattering surface (for example,
162975) 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. 57-165845), 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. 57-16554) etc. have been proposed.

Unfortunately, these conventional methods have not been able to completely eliminate the interference fringe pattern that appears on images.

In other words, in the first method, the surface of the support is simply provided with a large number of irregularities of a specific size, so although it does prevent the appearance of interference fringes due to the light scattering effect, it does not affect the light scattering. Since the specularly reflected light component still remains, in addition to the remaining interference fringe pattern due to the specularly reflected light, the irradiation spot spreads due to the light scattering effect on the support surface, resulting in a substantial This was a cause of a decrease in resolution.

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

In the case of the third method of irregularly roughening the surface of the support, as shown in FIG. teeth,
The light enters the inside of the light-receiving layer 302 and becomes transmitted light X1. A part of the transmitted light 11 is scattered on the surface of the support 302 and becomes diffused light Kl, 2, 3, etc., and the rest is specularly reflected and becomes reflected light R2; becomes the emitted light R3 and goes outside. Therefore, since the emitted light R3, which is a component that interferes with the reflected light R1, remains, the interference fringe pattern cannot be completely erased.

Furthermore, if the diffusivity of the surface of the support 301 is increased in order to prevent interference and multiple reflections 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 multilayered light-receiving member, even if the surface of the support 401 is irregularly roughened, as shown in FIG.
Reflected light R2 on the surface of layer 402, reflected light R on the second layer
1. Each of the specularly reflected lights R3 on the surface of the support 401 interferes, and an interference fringe pattern is produced according to the thickness of each layer of the light-receiving member. Therefore, in a light-receiving member having a multilayer structure, the support 4
It was impossible to completely prevent interference fringes by irregularly roughening the 01 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, the incident light at that part is 2. ndl=mλ or 2ndl=(IIIL+extension) is established, resulting in a bright area or a dark area, respectively. In addition, in the entire photoreceptive layer, the layer thickness of the photoreceptive layer is d1. d2. The maximum difference between d3 and d4 is 7
Since there is non-uniformity in the layer thickness, which is greater than 1, a light and dark striped pattern appears.

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

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

[Purpose of the invention]

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, high photosensitivity, and excellent electrophotographic properties.

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

Yet another object of the present invention is to provide a light-receiving member that can reduce light reflection on the surface of the light-receiving member and efficiently utilize incident light.

[Summary of the invention]

The light-receiving member of the present invention includes a first layer made of an amorphous material containing silicon atoms and germanium atoms, and a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. In a light-receiving member having a multilayer light-receiving layer in which a layer and a surface layer having an antireflection function are provided in order from the support side, the distribution state of germanium atoms in the first layer is The material is non-uniform in the thickness direction, and at least one of the first layer and the second layer contains a material that controls conductivity, and in the layer region containing the material, the material is nonuniform in the thickness direction. The distribution state is non-uniform in the layer thickness direction, and the photoreceptive layer has one or more pairs of non-parallel interfaces within a short range, and the non-parallel interfaces include at least one pair in a plane perpendicular to the layer thickness direction. It is characterized by being arranged in large numbers in the direction.

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

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

The present invention has a light-receiving layer having a multilayer structure along the slope of the unevenness on a support (not shown) having an uneven shape smaller than the required resolution of the device, and the light-receiving layer is shown in FIG. As shown in a partially enlarged view, since the layer thickness of the second layer 602 changes continuously from d5 to dB, the interface 603 and the interface 604 have a tendency toward each other. Therefore, the coherent light incident on this minute portion (short range) 31 causes interference in the minute portion, producing a minute interference fringe pattern.

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

Therefore, as shown in Figure 7 (C), the case where the pair of interfaces are non-parallel (r(B)J) is better than the case where the pair of interfaces are parallel (r(B)J).
r(A)J), even if there is interference, the difference in brightness of the interference fringe pattern is so small that it can be ignored. As a result, the amount of light incident on the minute portions is averaged.

This is true even if the thickness of the second layer 602 is macroscopically nonuniform (d7\ctB) as shown in FIG. 6, so the amount of incident light is uniform in the entire layer area. (See r(D)J in Figure 6).

Furthermore, to describe the effects of the present invention in the case where coherent light is transmitted from the irradiation side to the second layer when the light-receiving layer has a multilayer structure, as shown in FIG. Reflected lights R1, R2, R3, R4, and R5 exist for IO.

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

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

Further, interference fringes generated within the minute portion do not appear in the image because the size of the minute portion is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. Moreover, even if it appears in the image, it will not cause any substantial trouble because it is below the resolution of the eye.

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

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

Furthermore, in order to achieve the object of the present invention more effectively, the difference in layer thickness (d5-dB) in minute portions is assumed to be the wavelength of the irradiated light.

λ d5-d8≧Y〒1 (n: refractive index of second layer 602) It is desirable that

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

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

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. A phase method (PCVD method), optical CVD method, thermal CVD method, and sputtering method are employed.

The unevenness provided on the surface of the support can be achieved by fixing a cutting tool having a 7-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or lathe, and rotating the cylindrical support according to a program designed in advance as desired. However, by regularly moving in a predetermined direction, 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 chain line structure centered on the central axis of the cylindrical support. The chain line structure of the inverted ■-shaped protrusion may be a double or triple spiral structure, or a crossed spiral structure.

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

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. Preferably, it is an equilateral triangle. Of these shapes, isosceles triangles and right triangles are particularly desirable.

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

That is, firstly, the A-3i layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the layer quality changes greatly depending on the surface condition.

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

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

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

After considering the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, we found that:
The pitch of the recesses on the surface of the support is preferably 500 m~
Desirably, it is between 0.3 pLm and 1 pm, more preferably between 20'Om and 1 pm, optimally between 50 pLm and 5 gm.

Further, the maximum depth of the recess is preferably Ool-17t~
5 gm, more preferably 0.3 pm to 3 pm, optimally 0.6 gm to 2 μm. When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the slope of the recesses (or linear protrusions) is preferably 1
degrees to 20 degrees, more preferably 3 degrees to 15 degrees, optimally 4 degrees
It is desirable that the temperature be between 10 degrees and 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 pLm to 2 #Lm, more preferably 0.1 gm
, 5pm, optimally 0.2uLm-47zm.

The thickness of the surface layer with antireflection function is determined in a linear manner.

When the refractive index of the material of the surface layer is n and the wavelength of the irradiated light is d, the thickness d of the surface layer having an antireflection function is preferably as follows.

n=fT; A material with a refractive index of .

Considering such optical conditions, the thickness of the antireflection layer is preferably 0.05 to 21 Lm, assuming that the wavelength of the exposure light is in the wavelength range from near infrared to visible light. be.

In the present invention, materials that can be effectively used as the material for the surface layer having an antireflection function include, for example, MgF2.
Al2O3°ZrO2, TiO2, ZnS, CeO2°CeF2, 5i02. SiO, Ta205°AlF2,
Examples include inorganic fluorides, inorganic oxides, and inorganic nitrides such as NaF and Si3N4, and organic compounds such as polyvinyl chloride, polyamide resin, polyimide resin, vinylidene fluoride, melamine resin, epoxy resin, phenol resin, and cellulose acetate. It will be done.

In order to achieve the purpose of the present invention more effectively and easily, these materials can be used by vapor deposition, sputtering, or plasma vapor deposition (PCVD) because the layer thickness can be precisely controlled at an optical level.

Optical CVD method, thermal CVD method, and coating method are adopted.

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 the second layer and the second layer are provided in order from the support side, and the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness direction, resulting in an extremely excellent Indicates electrical, optical, photoconductive properties, electrical voltage resistance, and use environment characteristics.

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

Furthermore, the light-receiving member of the present invention has high photosensitivity in the entire visible light range, and is particularly excellent in photosensitivity characteristics on the long wavelength side, so it is particularly excellent in matching with semiconductor lasers, and has excellent optical response. is fast.

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

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

A light-receiving member 1004 shown in FIG. 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 1005 on one end surface. .

The photoreceptive layer 1000 is a-5i (hereinafter ra-3iGe (H
, X) J) 10
a-3i (hereinafter referred to as ra-3i (H,
) J), a second layer (S) 1003 having photoconductivity and a surface layer 100 having an antireflection function.
It has a layer structure in which 6 and 6 are laminated in order.

The remaining germanium atoms in the first layer (CG) 1002 are continuous in the layer thickness direction of the first layer (G) 1002 and are provided with the support 1'001. The side opposite to the side (the surface 1005 side of the photoreceptive layer 1001)
It is contained in the first layer (G) 1002 so that it is more distributed on the support 1001 side than on the support body 1001 side.

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

In the present invention, the second layer provided on the first layer CG)
The layer (S) does not contain germanium atoms, and by forming a light-receiving layer in such a layer structure, it can be used for light from relatively short wavelengths to relatively short wavelengths, including the visible light region. A light-receiving member having excellent photosensitivity to light of all wavelengths is obtained.

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

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

11 to 19 show typical examples of the distribution state of germanium atoms contained in the first layer (G) of the light-receiving member in the present invention in the layer thickness direction.

11 to 19, the horizontal axis represents the distribution concentration C of germanium atoms, the vertical axis represents the layer thickness of the first layer (G), and tB represents the thickness of the first layer (G) on the support side. The position of the end face,
t7 indicates the position of the end surface of the layer (G) on the opposite side to the support side. That is, the first layer containing germanium atoms (G
), layers are formed from the tB side toward the t7 side.

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

In the example shown in FIG. 11, the surface on which the first layer CG containing germanium atoms is formed and the first layer CG
) from the interface position tB to the position tl where germanium atoms are formed in the first layer (
G), and from the position tl, the concentration is gradually and continuously reduced from the concentration C2 up to the interface position t7. The distribution concentration C of germanium atoms at the interface position t7 is assumed to be the concentration C2.

In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position tB to the position t7, and reaches the concentration C5 at the position t7. is formed.

In the case of FIG. 13, from position tB to position t2, the distribution concentration C of germanium atoms is kept constant at concentration C6, and gradually and continuously decreases between position t2 and position t7. At t7, the distribution concentration C is substantially zero (substantially zero here means less than the detection limit amount).

In the case of FIG. 14, the distribution concentration C of germanium atoms is continuously gradually decreased from the concentration C8 from the position tB to the position t7, and becomes substantially zero at the position tT.

In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a constant value of concentration C8 between position tB and position 13, and is set to the concentration CIO at position t7.

Between position t3 and position t7, the distribution density C is linearly decreased from position t3 to position t7.

In the example shown in FIG. 16, the distribution concentration C is at the position t
From position B to position t4, the concentration C1l takes a constant value, and from position t4 to position t7, the distribution state is such that the concentration decreases linearly from C12 to C13.

In the example shown in FIG. 17, from position tB to position tT, the distribution concentration C of germanium atoms decreases linearly from the concentration C14 to substantially zero.

In FIG. 18, from position tB to position t5, the distribution concentration C of germanium atoms decreases linearly from concentration C15 to concentration C1B, and from position t5 to position t7.
An example is shown in which the concentration CIEi is set to a constant value.

In the example shown in FIG. 19, the distribution concentration C of germanilam atoms is the concentration CI? at position tB? , and this concentration CI? until reaching position t8. At first, the concentration is decreased slowly, and around the 70 position, it is rapidly decreased to a concentration C18 at the position t6.

The distance between the position meter 6 and the position Mt7 is decreased rapidly at first, and then gradually decreased until the position t7 is reached.
The concentration becomes C19, and between position t7 and position t8,
very slowly and gradually decreased at position t8,
The concentration reaches C20. Between position meter 8 and position t7, the concentration is reduced from C20 to substantially zero according to a curve shaped as shown in the figure. - As described above with reference to FIGS. 11 to 19, some typical examples of the distribution state of germanium atoms contained in the first layer (G) in the Fe thickness direction, in the present invention, On the support side, there is a part where the distribution concentration C of germanium atoms is high, and on the interface tT side, the distribution state of germanium atoms has a part where the distribution concentration C is considerably lower than that on the support side. It is desirable that it be provided in layer (G).

The first layer CG constituting the photoreceptive layer constituting the photoreceptor member in the present invention is preferably a localized region (A ) is desirable.

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

In the present invention, the localized region (A) is located at the interface position tB.
It may be a full layer region (LT) up to 5p thick, or it may be a part of a layer region (LT).

Whether the localized region (A) is a part or all of the layer region (L7) is appropriately determined according to the characteristics required of the light-receiving layer to be formed.

In the localized region (A), as a distribution state of germanium atoms contained therein in the layer thickness direction, the maximum value Cmax of the distribution concentration of germanium atoms is preferably ioo with respect to silicon atoms.

Atomic ppm or more, more preferably 5000ato
micppm or more, optimally 1x104 atomiccp
It is desirable that the layers be formed in such a way that a distribution state of pm or more can be achieved.

That is, in the present invention, the first layer (G) containing germanium atoms has a maximum distribution concentration Cma in a layer region of 5 pL thickness from the support side (within a layer thickness of 5 pL from tB).
Preferably, it is formed so that x exists.

In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the amounts of hydrogen atoms and halogen atoms contained in the second layer (S) constituting the photoreceptive layer to be formed The sum (H+X) is preferably 1 to 40 a'tomfc%
, more preferably 5-30 atomic%, optimally 5-30 atomic%
It is desirable to set it to 25 atomic%.

In the present invention, the content of germanium atoms contained in the first layer (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9. ．． Desirably, it is 5X105 atomic ppm, more preferably 100 to 8X1O"' atomic ppm, optimally 500 to 7X10" atomic ppm.

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

In the present invention, the layer thickness TB of the first layer (G) is preferably 30 to 504, more preferably 40λ to 40I.
L is preferably set to 50λ to 3°p.

Further, the layer thickness T of the second layer (S) is preferably 0.5 to 9
0JL, more preferably 1-8oIL optimally 2-50
It is desirable that the

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

In the light-receiving member of the present invention, the above numerical range of (TB+T) is preferably 1-ioo=, more preferably 1-80, most preferably 2-50. It is desirable that this is done.

In a more preferred embodiment of the present invention, the above layer thickness TB and layer thickness T are preferably TB/'T≦1.
When satisfying the following relationship, it is desirable to select appropriate numerical values for each of them.

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

In the present invention, when the content of germanium atoms contained in the first layer (G) is 1X11X105atoPPm or more, the layer thickness TB of the first layer (G) is made considerably thinner. is desirable, preferably 30 tons or less,
More preferably 25. Hereinafter, the optimum value is preferably 20 l or less.

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

In the present invention, the first layer (G) composed of a-3iGe (H, done by law. For example, to form the first layer (G) composed of a-3iGe(H,X) using the glow discharge method, basically,
A raw material gas for Si supply that can supply silicon atoms (Si), a raw material gas for Ge supply that can supply germanium atoms (Ge), and a raw material gas for introducing hydrogen atoms (H) or/and halogen as necessary. A raw material gas for introducing atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, and a predetermined support installed at a predetermined position is used. A layer consisting of a-3iGe(H,X) may be formed while controlling the distribution of germanium atoms contained on the body surface according to a desired rate of change curve. In addition, when forming by sputtering method, a target made of St and a target made of Ge are formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases. When performing sputtering using two sheets of or using a mixture of Si and Ge, hydrogen atoms (H
) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4゜Si2He, Si3HB
, Si4Hlo, and other gaseous or gasifiable silicon hydrides (silanes) can be effectively used, especially in terms of ease of handling during layer creation work, good Si supply efficiency, etc. Preferred examples include SiH4 and Si2H6.

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

Ge4Hlg, Ge5H12, GeBH14, Ge7H
Germanium hydride in a gaseous state or which can be gasified, such as 1B, Ge8HIB, GegH20, etc., can be used effectively, and in particular, ease of handling during layer formation work,
In terms of Ge supply efficiency, etc., Ge, H4, Ge2HB
, Ge3HB are preferred.

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

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, and C1F.

ClF3, BrF5, BrF3, IF3.

IF7. Interhalogen compounds such as I0 and IBr can be mentioned.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4, Si2FB.

SiC! Preferable examples include silicon halides such as L4 and SiBr4.

When forming the characteristic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen is used as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. The first layer CG) made of a-5iGe containing halogen atoms can be formed on a desired support without using silicon oxide gas.

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

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

A first layer (G) made of a-3iGe (H,
), for example, in the case of a sputtering method, a target made of St and a target made of Ge, or a target made of Si and Ge, are used and sputtered in a desired gas plasma atmosphere. However, in the case of the ion blating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or single crystal germanium are housed in the evaporation port as evaporation sources, and these evaporation sources are heated by resistance heating or electron beam heating. This can be carried out by heating and evaporating the flying evaporated material using a beam method (FB method) or the like and passing the flying evaporated material through a desired gas plasma atmosphere.

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

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing halogen atoms, but HF is also used.

Hydrogen halides such as He, HBr, HI, SiH2F
2, SiH2I2. , SiH20 sentence 2°5fHCu3,
5iH2Br2. Halogen-substituted silicon hydride such as SiHBr3, and GeHF3゜GeH2F2, GeB3F, G
eHCu3.

GeH2C sentence 2, GeB3C1, GeHBr3゜GeH
2Br2, GeB3Br, GeHI3.

Halides containing hydrogen atoms as one of their constituent elements, such as hydrogenated germanium halides such as GeH2I2 and GeB3I, GeF4, and GeCJlj4.

GeBr4, GeI4, GeF2, GeCu2゜GeB
The first layer (G
) can be mentioned as a starting material for the formation.

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

To structurally introduce hydrogen atoms into the first layer (G),
In addition to the above, H2, or SiH4゜Si2H6, S'1
Silicon hydride such as 3HB, Si4H10, etc. with germanium or a germanium compound for supplying Ge, or
GeH4゜Ge2HB, Ge3HB, Ge4H1, Ge
5H12,Ge6H14=Ge? HI8. Ge8H1B
This can also be achieved by causing germanium hydride such as =Ge8H2θ and silicon or a silicon compound for supplying St to coexist in the deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the quantities (H+x) is preferable, and S< is 0.01 to 4.
0 atomic%, more preferably 0.05 to 30 atomic%
It is desirable that the content be mic%, most preferably 0.1 to 25 atomic%.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first 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, in order to form the second layer (S) composed of aSz (H*X), the first layer region CG)
The starting material (starting material (II) for forming the second layer (S)) excluding the starting material that becomes the raw material gas for supplying Ge from the starting material (I) for forming the second layer (S) is used to form the second layer (S). 1st layer (G)
It 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 layer (S) composed of a-3i(H,X), for example, a glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon such as a sputtering method or an ion blating method. For example, in order to form the second layer (S) composed of a-3i (H, Along with the source gas, a source gas for introducing hydrogen atoms (H) and/or halogen atoms (, , and a layer consisting of a-3i (H, In addition, when forming by sputtering, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering.

In the light receiving member 1004 of the present invention, at least the first layer (G) 1002 or -/ and the second layer (S) 10
03 contains a substance (C) that controls conduction characteristics, and the layer containing the substance (C) is given desired conduction characteristics.

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

However, in any case, in the layer region (PN) containing the substance CC).

The distribution state of the substance in the layer thickness direction is non-uniform. Clogged,
For example, if the substance (C) is to be contained in the entire layer area of the first layer (G), the substance (C) should be distributed more toward the support side of the first layer (G). is the first layer (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 (CG).
In the case where the substance (C) is contained in the layer region (PN), the layer region (PN) containing the substance (C) is provided as an end layer region of the first layer CG), and is determined as appropriate each time as desired. .

In the present invention, the substance (C) is contained in the second layer (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 substance (C) in the first layer (G) is not contained. layer area and the second layer area.
It is desirable that the layer region of the layer (S) containing the substance (C) be in contact with each other.

Further, the substance (C) contained in the first layer (G) and the second layer (S) is of the same type in the first layer (G) and the second layer (S). However, they may be of different types, and their content may be the same or different in each layer.

However, in the present invention, if the substance (C) contained in each layer is the same type in both layers, the content in the first layer (G) may be sufficiently increased. Alternatively, it is preferable that each desired layer contains substances (C) having different electrical characteristics. .

In the present invention, at least the first layer constituting the photoreceptive layer
By incorporating a substance (C) that controls the conductive properties into the layer (G) and/or the second layer (S), the substance (C)
Control the conductive properties of the layer region containing C) (which may be part or all of the first layer (G) and/or the second layer (S)) as desired. However, examples of such a substance (C) include so-called impurities in the semiconductor field, and in the present invention, a- 3
For t(H, X) or/and a-3iGe(H,

Specifically, p-type impurities include atoms belonging to Group Ⅰ of the periodic table (Group Ⅰ atoms), such as B (boron), AfL (
Aluminum 1. ), Ga (gallium), In (indium), Tl (thallium), etc., and B is particularly preferably used.

It is Ga.

Examples of n-type impurities include atoms belonging to Group V of the periodic table (Group V atoms), such as P (phosphorus), As (arsenic), and sb (
antimore), Bi (bismuth), etc., and 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 appropriately selected depending on the organic relationship, such as the 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 wood IJJ, the content of the substance (C) that controls conduction characteristics contained in the single layer region (PN) is preferably 0. It is desirable that the amount is O1 to 5X104 atomic ppm, more preferably 0.5 to IX11X104 atomic ppm, and optimally 1-51-5X103 atomic ppm.

In the present invention, the content of the substance (C) that governs the conduction characteristics in the layer region (PN) containing the substance (C) is preferably set to 30 atomic ppm or more, more preferably 50 atomic ppm or more, to an optimum level. 100100 for
atoppm or more, for example, when the substance (C) to be contained is the above p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the photoreceptor layer from the support side is Injection of electrons into the photoreceptor layer can be effectively prevented, and when the substance (C) to be contained is the n-type impurity, the free surface of the photoreceptive layer is charged to O polarity. In this case, injection of holes from the support side into the photoreceptive layer can be effectively prevented.

In the above case, as mentioned above, the layer region (PN
) in the layer region (Z) excluding the layer region (PN) contains a substance that controls the conduction characteristics of a conduction type polarity different from the conduction type polarity of the substance that governs the conduction characteristics contained in the layer region (PN). It may be contained, or it may be contained in an amount much smaller than the actual amount of a substance having the same polar conductivity type and controlling conduction characteristics 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 according to the polarity and content of the substance (C) contained in is 0
．． It is desirable that the content be 1 to 200' atomic ppm.

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 single 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 preferable to set it to 0 atomic ppm 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.

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

27 to 35 show typical examples of the distribution state of the material layer (C) contained in the layer region (PN) of the light-receiving member in the present invention in the layer thickness direction. In addition, in each figure, the layer thickness and concentration are shown in an extreme form because if the values are shown as they are, the differences between each figure will not be clear, and these figures should be understood to be schematic. I want to be

As for the actual distribution, the purpose of the present invention can be achieved,
Ti (1≦i
≦8) or Ci (1≦i≦17), or the entire distribution curve should be multiplied by an appropriate coefficient.

27 to 35, the horizontal axis shows the distribution concentration C of the substance (C), the vertical axis shows the layer thickness of the layer region (PN), and tB
indicates the position of the end surface of the layer region (PN) on the support side, and t7 indicates the position of the end surface of the layer region (PN) on the opposite side to the support side. That is, the layer region (PN) containing the substance (C) is tB
Layer formation is performed from the side toward the t7 side.

FIG. 27 shows the substance (PN, ) contained in the layer region (PN, ).
A first typical example of the distribution state of C) in the layer thickness direction is shown.

In the example shown in FIG. 27, from the interface position tB where the surface where the layer region (PN) containing the substance (C) is formed and the surface of the layer region (P'N) are in contact, to the position tl. , the substance (C) is contained in the formed layer (PN) while the distribution concentration C of the substance (C) takes a constant value of the concentration C1, and the substance (C) is contained in the formed layer (PN) from the position t1 to the concentration C2 until the interface position t7. It has been gradually and continuously reduced. At the interface position t7, the distribution concentration C of the substance (C) is substantially zero. (Here, "substantially zero" means that the amount is below the detection limit.) In the example shown in Figure 28, the contained substance (C)
The distribution concentration C is the concentration C from position tB to position tT.
3, the concentration C gradually decreases continuously at position t7.
A distribution state of 4 is formed.

In the case of FIG. 29, from position tB to position t2, the distribution concentration C of germanium atoms is kept constant at concentration C5, and gradually and continuously decreases between position t2 and position tT. At t7, the distribution concentration C is substantially zero.

In the case of FIG. 30, the distribution concentration C of substance (C) is at position t
From B to position t7, the concentration is gradually and continuously reduced starting from C6, and from position t3, it is rapidly and continuously reduced to substantially zero at position tT.

In the example shown in FIG. 31, the distributed concentration C of the substance (C) is a constant value of concentration C7 between the position tB and the position t4, and the distributed concentration C is zero at the position t7. Ru. Between the position t4 and the position t7, the distribution density C is linearly decreased from the position to the position t7.

In the example shown in FIG. 32, the distribution concentration C takes a constant value of concentration C8 from position tB to position t5, and decreases in a linear function from concentration C8 to concentration CIO from position t5 to position t7. It is said to be a state.

In the example shown in FIG. 33, from the position tB to the position tT, the distribution degree C of the substance (C) is continuously decreased in a linear function from the concentration C1l, and reaches zero.

In FIG. 34, from position tB to position t6, the distribution concentration C of substance (C) is lower than concentration C12 and concentration C13.
An example is shown in which the concentration C13 is decreased linearly to a constant value between the position t6 and the position tT.

In the example shown in FIG. 35, the distribution concentration C of the substance (C) is the concentration C14 at the position tB, and is slowly decreased from this concentration C14 until reaching the position t7, and at the point of penetration at the position tl. is rapidly decreased and the position f
At f1t7, the density is C15.

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

As described above with reference to FIGS. 27 to 35, some typical examples of the distribution state of the substance (C) contained in the layer region (PN) in the layer thickness direction, in the present invention, the support On the body side, there is a part with a high distribution concentration C of the substance (C),
On the interface tT side, it is desirable that the layer region (PN) be provided with a distribution state of the substance (C) having a portion where the distribution concentration C is considerably lower than that on the support side.

The layer region (PN) constituting the light-receiving member in the present invention preferably has a localized region (B) containing the substance (C) at a relatively high concentration on the support side as described above. desirable.

In the present invention, the localized region (B) is
Explaining using the symbols shown in FIG. 5, it is desirable to provide within 5JL from the interface position tB.

In the present invention, the localized region (B) is located at the interface position tB.
It may be the entire layer region (L) up to 5 μl thick, or it may be a part of the layer region (L).

Whether the localized region (B) is a part or all of the layer region (L) is appropriately determined according to the characteristics required of the photoreceptive layer to be formed.

A substance that controls conduction properties (
C) For example, in order to form a layer region (PN) containing the substance (C) by structurally introducing a group II atom or a group V atom, group The starting material for introducing atoms or the starting material for introducing Group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming each layer.

As the starting material for introduction of such Group (I) atoms, it is desirable to employ those that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. As a starting material for introducing such a group (III) atom, specifically for introducing a boron atom, B2) (e, B4H
lo.

B5B9・B5H11・Be) ('to・B8H12°B6H14, etc., boron hydride, BF3, BCsL3.

Examples include boron halides such as BBr3. In addition,
A10 sentence 3, Ga0 sentence 3. Ga(CH3)3, IncJ
You can also raise lj3, T10 sentence 3, etc.

In the present invention, the starting materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms include PH3,
Hydrogen ratios such as P2H4, PH4I, PF3, PF5, P
C sentence 3. PCC3IPBr3. PBr5. PI3 and other halogenated phosphorus ratios are listed. In addition, AsH3, AsF3.
AsCl3°AsBrAsF5. SbH3, SbF3.
SbF5゜3+ 5bCu3, Sb0 sentence 5. BiI3. BiC sentence 3゜Bi
Br3 and the like can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the support used may be electrically conductive or electrically insulating. As a conductive support,
For example, NiCr, stainless steel, AM, Cr, Mo, A
u, Nb, Ta.

Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof.

Polyester is used as the electrically insulating support.

Films or sheets of synthetic resins such as polyethylene, polycarbonate-1, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used.

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, NiCr, AM
, Cr, Mo, Au, Ir, Nb.

Ta, V, Ti, Pt, Pd, In203.

Conductivity can be imparted by providing a thin film made of Sn02, ITo (IB203+Sn02), etc., or if it is a synthetic resin film such as a polyester film, N
iCr, A.M.

Ag, Pb*Zn+N1+Au*CrrMO+Ir, N
b. Vacuum deposition of thin films of metals such as Ta, V, Ti, Pt, etc.
Provided on the surface by electron beam evaporation, sputtering, etc.
Alternatively, the surface is laminated with the metal to impart conductivity to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the light receiving member 1004 in FIG. 10 may be used as a light receiving member for electrophotography. In the case of continuous high-speed copying, it is desirable to use an endless belt or a cylindrical shape. The thickness of the support is determined appropriately so that a desired light-receiving member is formed, but if flexibility is required as a light-receiving member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, from the viewpoints of manufacturing and handling of the support, mechanical strength, etc., the OIL is preferably 1 OIL or more.

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

FIG. 20 shows an example of a light-receiving member manufacturing apparatus.

In the gas cylinders 2002 to 2006 in the figure, raw material gas for forming the light receiving member of the present invention is sealed, and as an example, 2002 is SiH4 gas (purity 99.999%).

Hereinafter, it will be abbreviated as SiH4. ) cylinder, 2003 is a GeH4 gas (purity 99.999%, hereinafter abbreviated as GeH4) cylinder, 2004 is a SiF4 gas (purity 99.99%, hereinafter S
iF4) cylinder, 2005 is B2mB gas (purity 99.999%, hereinafter B2H8/H) diluted with B2.
Abbreviated as 2. ) cylinder, 2006 is B2 gas (purity 99.
999%) cylinder.

In order to flow these gases into the reaction chamber 2001, valves 2022 to 2026 of gas pumps 2002 to 2006,
Make sure the leak valve 2035 is closed,
In addition, inflow / valve 2012-2016, outflow valve 20
17-2021, make sure that the auxiliary valves 2032 and 2033 are open, and first open the main/club valve 2034.
is opened to exhaust the reaction chamber 2001 and the inside of each gas pipe. Next, when the reading on the vacuum gauge 2036 reaches approximately 5X10 torr, the auxiliary knobs 2032 and 2033 and the outflow valves 2017 to 2021 are closed.

Next, to give an example of forming a light-receiving layer on the cylindrical substrate 2037, SiH
4 gas, GeH4 gas from Gas Pombe 2003, B2H6/H'2 gas from Gas Pombe 2005, B2 gas from 2006 Valve 2022, 2023, 2025.20
26 and outlet pressure gauge 2027.

2028.2030.203.1 pressure IKg/Cm2
Adjust the inflow valve 2,012,2013.2015
．． Gradually open 2016 and mass flow control a-720
07, 20'08, 2010, and 2011, respectively. Subsequently, the outflow valve 2017, 2018, 20
20° 2021, the auxiliary valves 2032 and 2033 are gradually tapped to allow each gas to flow into the reaction chamber 2001. At this time, SiH4 gas flow rate, GeH4 gas flow rate, B2H
Outflow valve 2017.2018, 2020.20 so that the ratio of e/H2B2 gas flow rate 2 gas flow rates becomes the desired value.
21 and also adjust the opening of the main valve 2034 while checking the reading on the vacuum gauge 2036 so that the pressure inside the reaction chamber 2001 reaches the desired value.

After confirming that the temperature of the substrate 2037 is set to a temperature in the range of 50 to 400'C by the heating heater 2038, the power source 2. It is formed by generating a discharge and at the same time gradually changing the flow rate of GeH4 gas and B2He gas according to a pre-designed rate of change curve manually or by using an externally driven motor or the like to gradually change the openings of the valves 2018 and 2020. The distribution concentration of germanium atoms and boron atoms contained in the layer is controlled.

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

In addition, each layer of the first layer (S) and the second layer (G) can be made to contain or not contain boron by appropriately opening and closing the outflow valve 2020, or a part of the layer region of each layer can be made to contain boron or not. It is also possible to contain boron only in .

A surface layer is formed by sputtering on the light-receiving member that has been formed up to the second layer (S).

Using the apparatus shown in FIG. 20, a surface layer material is applied all over the cathode electrode, and H2 gas is replaced with Ar gas.

Next, the light-receiving member formed up to the second layer (S) is placed inside the device, the inside of the device is sufficiently filled, and Ar gas is introduced to a predetermined internal pressure. Then, a predetermined high frequency power is introduced to sputter the material on the cathode electrode to form a second layer (S
) to form a surface layer on top.

During layer formation, the substrate 2037 is preferably rotated at a constant speed by a motor 2039 in order to ensure uniform layer formation.

Examples will be described below.

Example I AJJ support (length L) 357 mm', diameter (r) 80
mm) under the conditions shown in Table 2, Fig. 21 (P: pitch,
D: Depth) Four types of lathes were used as shown.

Next, under the conditions shown in Table 1, an a-3i electrophotographic light-receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures (sample No.

201-204). ′ Note that the first layer is made of GeH4 and SiH4.

The mass flow controller 2007 adjusts the flow rates of each B2He/H2 gas as shown in Figures 22 and 36.
．． 2008 and 2010 on computer (HP984
5B).

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

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 807 zm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in any of the images of sample Nos. 201 to 204, which were sufficient for practical use.0 Example 2 AM support (length L) 357 mm, diameter (r) 80 mm
) under the conditions shown in Table 3, Fig. 21 (P: pitch, D =
Four types of lathes were used as shown in (depth).

Next, under the conditions shown in Table 1, an a-3i electrophotographic light-receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures (Sample No.

301-304).

Note that the first layer is GeH4, SiH'4.

The mass flow controller 2007 adjusts the flow rates of each B2He/H2 gas as shown in Figures 23 and 37.
．． 2008 and 2010 on computer (HP984
5B).

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

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 80 pm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in any of the images of sample Nos. 301 to 304, which were sufficient for practical use @ Example 3 An support (length L) 357 mm, diameter (r) 80 mm
) under the conditions shown in Table 5 in Figure 21 (P: pitch, D:
Four types of lathes were used as shown in (depth).

Next, under the conditions shown in Table 4, an a-5i electrophotographic light-receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures (sample no.

501-504).

Note that the first layer is made of GeH4 and SiH4.

The mass flow controller 2007 adjusts the flow rates of each B2H6/H2 gas as shown in FIGS. 24 and 38.
．． 2008 and 2010 on computer (HP984
5B).

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

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 80 pm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in any of the images of sample Nos. 501 to 504, which were sufficient for practical use.

Example 4 Layer A, support (length L) 3'57 mm, diameter (r) 80
mm) under the conditions shown in Table 6, Fig. 21 (P: pitch,
As shown in D=depth), four types of lathes were used.

Next, under the conditions shown in Table 4, an a-3i electrophotographic light-receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures (sample no.

601-604).

Note that the first layer is made of GeH4 and SiH4.

The mass flow controller 2007 adjusts the flow rates of each B2H6/H2 gas as shown in Figures 25 and 39.
．． 2008 and 2010 on computer (HP984
5B).

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

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 80 μm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in any of the images of sample Nos. 601 to 604, which were sufficient for practical use.

Example 5 Ai support (length L) 357 mm, diameter (r) 80 mm
) under the conditions shown in Table 8 in Figure 21 (P: pitch, D:
Four types of lathes were used as shown in (depth).

Next, under the conditions shown in Table 7, electrophotographic light-receiving members were produced according to various operating procedures using the film deposition apparatus shown in FIG. 20 (Sample Nos. 801 to 804).

Note that the first layer and the A layer are GeH4 and Si'H4.

Mass flow controller 2007.2008.
2010 was controlled by a computer (HP9845B).

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

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 80 pm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in the image, which was sufficient for practical use.

Example 6 An support (length L) 357 mm, diameter (r) 80 mm
) under the conditions shown in Table 10, Fig. 21 (P: pitch, D
:Depth), four types of lathes were used.

Next, under the conditions shown in Table 9, electrophotographic light-receiving members were produced according to various operating procedures using the film deposition apparatus shown in FIG. 20 (Samples N (1,1001 to 1004)).

Note that the first layer and the A layer are GeH4 and SiH4.

Adjust the flow rate of each gas of B2H13/H2 as shown in Figure 22 using the mass flow controller 2007.2008.
．． 2010 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 microscope, the results shown in Table 10 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter β Opm), and then developed and transferred to obtain images.

No interference fringe pattern was observed in the image, which was sufficient for practical use.

Example 7 AM support (length L) 357 mm, diameter (r) 80 mm
) under the conditions shown in Table 12, Fig. 21 (P: pitch, D
= depth), four types of lathes were used.

Next, under the conditions shown in Table 11, electrophotographic light-receiving members were produced in accordance with various operating procedures using the stacking apparatus shown in FIG. 20 (Sample Nos. 1201 to 1204).

Note that the first layer and the A layer are GeH4 and SiH4.

Mass flow controllers 2007, 2008 and 201O were controlled by a computer (HP9845B) so that the flow rates of each gas of B2H6/H2 were as shown in FIG.

When the layer thickness of each layer of the light-receiving member thus produced was measured using an electron microscope, the results shown in Table 12 were obtained.

These electrophotographic light-receiving members were subjected to image exposure using an image exposure apparatus shown in FIG. 26 (laser light wavelength: 780 nm, spot diameter: 80 pm), and then developed and transferred to obtain an image.

No interference fringe pattern was observed in the image, which was sufficient for practical use.

Example 8 On the An support of Table 2 No. 201 of Example 1, the first
The second layer was formed under the conditions shown in the table, and the surface layer was formed as shown in Table 13 (
Condition No. 1301 to 1322).

When image evaluation was performed on the above sample in the same manner as in Example 1, no interference fringe pattern was observed, and electrophotographic characteristics with high sensitivity and sufficient for practical use were obtained.

[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. FIG. 6 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIG. 7 is an explanatory diagram of a comparison of reflected light intensity 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. FIG. 9 is an explanatory diagram of the surface condition of each typical support. 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 germanium atoms in the first layer. FIG. 20 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 21 is an explanatory diagram of the surface state of the An support used in the examples. FIG. 22 to FIG. 25 and FIG. 36 to FIG. 42 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 26 is an explanatory diagram of the image exposure apparatus used in the example. FIGS. 27 to 35 are explanatory diagrams for explaining the distribution state of the substance (C) in the layer region (PN). iooo・・・・・・・・・・・・・・・Photoreceptive layer 1001・・・・・・・・・・・・・・・AJ
lj support body 1002・・・・・・・・・・・・・
・Ml layer 1003・・・・・・・・・・・・・・・
...Second layer 1004......
...Light-receiving member 1005......
...Free surface 1006 of light-receiving member...
......Surface layer 2601...
.........Light receiving member 260 for electrophotography
2・・・・・・・・・・・・・・・・・・Semiconductor laser 2603・・・・・・・・・・・・・・・fθ
Lens 2604・・・・・・・・・・・・・・・
Polygon mirror 2605・・・・・・・・・・・・・・・
... Plan view of exposure device 2606 ......
・・・・・・・・・Side view of exposure device Applicant Canon Co., Ltd. '% (zu) Time C time ('w') 40th (2) 410th

Claims (1)

[Claims] i(1) 1. containing silicon atoms and germanium atoms;
a first layer made of an amorphous material; a second layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity;
In a light-receiving member having a pre-receiving tau layer with a multilayer structure in which a surface layer having an antireflection function is provided in order from the support side, the distribution state of germanium atoms in the first layer is in the layer thickness direction. is non-uniform, and at least one of the first layer and the second layer contains a substance that controls conductivity, and in the iM region containing the substance,
The distribution state of the substance is 31° in the layer thickness direction.
．． : *", *JEje=9mM!t is"-1; The trench has one or more pairs of non-parallel interfaces, and a large number of the non-parallel interfaces are arranged in at least one direction in a plane perpendicular to the layer thickness direction. A light-receiving member characterized by: (2) The light receiving member according to claim 1, wherein the arrangement is regular. (3) The light receiving member according to claim 1, wherein the arrangement is periodic. (4) The light receiving member according to claim 1, wherein the short range is 0.3 to 500 IL. (5) 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. (6) The light-receiving member according to claim 5, wherein the unevenness is formed by an inverted V-shaped linear protrusion. (7) The light-receiving member according to claim 6, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially an isosceles triangle. (8) The light-receiving member according to claim 6, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a right triangle. (8) The light-receiving member according to claim 6, wherein the vertical cross-sectional shape of the inverted V-shaped linear protrusion is substantially a scalene triangle. (10) Claim 1, wherein the support body is cylindrical.
The light-receiving member described in 2. (11) The light-receiving member according to claim 10, wherein the inverted V-shaped linear protrusion has a chain line structure within the plane of the support. (12) The light-receiving member according to claim 11, wherein the chain line structure is a multiple chain line structure. (13) The light-receiving member according to claim 6, wherein the inverted V-shaped linear protrusion is divided in the direction of its ridgeline. (14) The light-receiving member according to claim 10, wherein the ridgeline direction of the inverted V-shaped linear protrusion is along the central axis of the cylindrical support. (15) Claim 5, wherein the unevenness has an inclined surface.
The light-receiving member described in 2. (1B) The light-receiving member according to claim 15, wherein the inclined surface is mirror-finished. (17) The light-receiving member according to claim 5, 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.