JPS60203963A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To make the titled member applicable to coherent light by forming a photoreceptive layer provided, successively from a base side, with the 1st layer consisting of a-SiGe and the 2nd layer consisting of photoconductive a-Si into specific layer structure and incorporating O, C or N therein. CONSTITUTION:Atoms of one kind among O, C and N are incorporated into a photoreceptive layer 1000 made into the multi-layered structure provided, successively from a base 1001 side, with the 1st layer 1002 contg. a-SiGe and the 2nd layer 1003 contg. a-Si having photoconductivity. Said layer has >=1 pairs of non- parallel boundaries in the very small part. Many of such boundaries are arranged in at least one direction within the plane perpendicular to the layer thickness direction. The distribution condition of the O, C or N to be incorporated into the layer 1000 may be nonuniform or uniform. The interference effect of irradiated light can be prevented by increasing the number of the layers constituting the layer 1000 in the above-mentioned way. The interference fringes generated in the very small part do not appear on the image as the size of the very small part is smaller than the spot diameter of the irradiated light, i.e., said size is smaller than the resolution threshold. The generation of the interference fringes is thus prevented and the member is used for laser light, etc.

Description

[Detailed description of the invention] 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.

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 and A well-known method is to record an image by performing processes such as transfer and fixing accordingly.

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, in addition to the fact that the consistency of the photosensitivity region is much better than that of other types of light-receiving members, 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-3iJ) disclosed in Japanese Patent No. 83746 is attracting attention.

Of course, if the photoreceptive layer is a single-layer A-3i layer, in order to maintain its high photosensitivity and ensure a dark resistance of 1012 Ωcm or more, which is required for electrophotography, hydrogen atoms and halogen atoms are required. In addition to these, it is necessary to structurally contain poron atoms in a specific amount range in a controlled manner in the layer, so layer formation must be strictly controlled. There are considerable limitations on tolerances in component design.

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. 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 an increased apparent dark resistance of 7 has been proposed.

Through such proposals, the A-9i light-receiving member has made dramatic progress in terms of commercialization design tolerances, ease of manufacturing management, and productivity, and is moving towards commercialization. The speed of development 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 half-tone image with high gradation, the image becomes noticeably unsightly.

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

This point will be explained with reference to the drawings.

Figure 81 shows light I'Q incident on a certain layer constituting the light-receiving layer of the light-receiving member and reflected light R1 reflected at the upper interface 102.
, 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 λ,
If the thickness of a certain layer is uneven with a gradual thickness difference of □ or more, the reflected lights R1 and R2 become 2nd
= m input (m is an integer, reflected light strengthens and combined light weakens each other), the amount of absorbed light and transmitted light of a certain layer changes depending on which condition is met.

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

To solve this problem, the surface of the support is diamond-cut to form a light-scattering surface by dividing the unevenness of ±500 to ±xooooX into d parts (for example, the special DH
No. 8-162975) The surface of the aluminum support is treated with black alumite, or carbon or carbon is added to the resin.
A method of providing a light absorption layer by dispersing color pigments or dyes (for example, Japanese Patent Application Laid-Open No. 57-165845), applying a satin-like alumite treatment to the surface of an aluminum support, or forming fine grain-like irregularities by sandblasting. A method has been proposed in which a light scattering and antireflection layer is provided on the surface of a support (for example, JP-A-57-16554).

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

That is, in the first method, only a number of irregularities of a specific size are provided on the surface of the support, so although it does prevent the appearance of interference fringes due to light scattering effects, Since the specularly reflected light component still remains, in addition to the 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 caused a significant 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-8i layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed light-receiving layer is significantly deteriorated. 5i
It is damaged by plasma during layer formation, reducing its original absorption function, and has disadvantages such as deterioration of the surface condition, which adversely affects the subsequent formation of the A-3i layer.

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 II. 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, reflected light R1
Since the emitted light R3, which is a component that interferes with the light, remains, the interference fringe pattern cannot be completely erased.

Furthermore, 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. It also has the disadvantage of doing so.

In particular, in a light-receiving member having a multilayer structure, even if the surface of the support 401 is irregularly illuminated, as shown in FIG.
Reflected light R2 on the surface of layer 402, reflected light R on the second layer
1. The specularly reflected lights R3 on the surface of the support 401 interfere with each other, producing an interference fringe pattern depending on 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 were often formed in the rantum, and such large protrusions caused local breakdown of the photoreceptor 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 enters two 2nd pixels or 2 n dl=(m+34) λ, resulting in a bright part or a dark part, respectively. In addition, in the entire photoreceptive layer, the layer thickness di, d2. d3, due to the non-uniformity of the layer thickness, 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 surface of the support as explained for the single-layered light-receiving member in FIG. In addition to the interference with the reflected light on the surface of the light-receiving layer, interference due to the reflected light at the interface between each layer is added, so that the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member with a single-layer structure.

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 is easy to manufacture and maintain.

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.

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 the light-receiving member, the light-receiving layer has a multi-layered light-receiving layer provided in order from the support side, and the light-receiving layer contains at least one type of atom selected from elementary atoms, carbon atoms, and nitrogen atoms. and has one or more pairs of non-parallel interfaces within a short range, and is characterized in that a large number of the non-parallel interfaces are arranged in at least one direction within a plane perpendicular to the layer thickness direction. .

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

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

The present invention has a light-receiving layer having a multilayer structure along the slope of the unevenness on a support (not shown) having an uneven shape smaller than the required resolution of the device, and the light-receiving layer is shown in FIG. As shown in a partially enlarged view, since the layer thickness of the second layer 602 changes continuously from d5 to d6, the interface 603 and the interface 604 have a tendency toward each other. Therefore, the coherent light incident on this minute (short range) sentence is
Interference occurs in the minute portions, 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 reflected light R1 and the emitted light R3 with respect to the light IQ have different traveling directions, when the interfaces 703 and 704 are parallel (r in FIG.
(B) The degree of interference is reduced compared to J).

Therefore, as shown in Figure 7 (C), when a pair of interfaces are non-parallel (r(A)'') than when they are parallel (r(B)J), there is no interference even if they interfere. The difference in brightness of the striped pattern becomes negligible. As a result, the amount of light incident on the minute portions is averaged.

This is true even if the thickness of the second layer 602 is macroscopically nonuniform (ci7\d8) 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. For IQ, there are reflected lights R1, R2, R3, R4, and R5.

Therefore, in each layer, the same effect as shown in FIG. 7 and explained above occurs.

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

Furthermore, interference fringes that occur within minute portions do not appear in the image because the size of the minute portion is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. 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 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.

In addition, in order to more effectively achieve the object of the present invention, the difference in layer thickness (d5'-dB) in a minute portion should be d5-dB≧71 (n: The refractive index of the second layer 602 is preferably as follows.

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, the layers forming parallel layer interfaces have a uniform layer thickness over the entire area so that the difference in layer thickness at any two positions is 1 base (n: refractive index of the layer) or less. preferably formed.

The first layer containing silicon atoms and germanium atoms and the second layer containing silicon atoms constituting the photoreceptive layer are formed by controlling the layer thickness to an optical value in order to more effectively and easily achieve the object of the present invention. Plasma vapor phase method (PCVD method), optical CVD method, and thermal CVD method are adopted because they can be controlled accurately at a target level.

The unevenness provided on the surface of the support can be achieved by fixing a cutting tool having a 7-shaped cutting edge in a predetermined position on a cutting machine such as a milling machine or lathe, and rotating the cylindrical support according to a program designed in advance as desired. 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 V-shaped protrusion may be a double or triple chain line 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-9i layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the quality of the layer 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 reduce the quality of the A-3i 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 four parts of the support surface is preferably 500 gm
-0,3 pm, more preferably 200 gm -1 pLm
, most preferably between 50 lm and 5gm.

The maximum depth of the recess is preferably 0.1 m to 5 km.
, more preferably 0.3 gm to 3 gm, optimally 0.6 lm to 2 pm. 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 four parts (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.

Also, based on the non-uniformity of the layer thickness of each layer deposited on such a support, the maximum difference in layer thickness is preferably 0 within the same pitch.
．． 17pm to 2gm, more preferably O,l pLm
-1.5 pLm, optimally 0.2 pm to lpm.

Furthermore, the photoreceptive layer in the photoreceptive member of the present invention is composed of a layer of ff1l made of an amorphous material containing silicon atoms and germanium atoms and an amorphous material containing silicon atoms, and has photoconductivity. Since it has a multilayer structure in which layers 2 and 2 are provided in order from the support side, it exhibits extremely excellent electrical, optical, photoconductive properties, electrical pressure resistance, and use environment properties.

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

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. Answers are quick.

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 fool for the light-receiving member, and the light-receiving layer 1000 has a free surface 1005 on one end surface. .

It has a layer structure in which the second layer (S) 1003 and the second layer (S) 1003 are laminated in order. The germanium atoms contained in the first layer (G) 1002 are continuous and uniform in the layer thickness direction of the first layer (G) 1002 and in the in-plane direction parallel to the surface of the support. The first layer (G) 100 so as to be distributed
Contained in 2.

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

In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed in the entire layer region, so when a semiconductor laser or the like is used, the second layer (G) The first layer (G) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed in 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, sufficient chemical stability is ensured at the laminated interface.

In the present invention, the content of germanium atoms contained in the first layer is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1.
It is desirable that the atomic content is ~9.5X105 atomic ppm, more preferably 100~axto5 atomic ppm, optimally 500~1.7X10'' atomic ppm.

In the present invention, the layer thickness of the first layer CG) 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 λ to 50 pL, more preferably 40 to 40 pL.
．． The number of participants is preferably between 50 and 30 people.

Further, the layer thickness T of the second layer (S) is preferably 0.5 to 9
0. , more preferably 1 to 80 animals, most preferably 2 to 50 microns.

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 determined by the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. N is appropriately determined as desired when designing the light-receiving member based on the organic relationship between the characteristics and the characteristics.

In the light receiving member of the present invention, the above (TB +T)
The numerical range of is preferably 1 to 100 g, more preferably 1 to 80 g, most preferably 2 to 50 g.

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 the selection of the numerical values of the layer thickness TB and the 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 T B /T≦0.8 is satisfied.

In the present invention, the content of germanium atoms contained in the first layer (G) is lX11X105ato PPm
In the above case, the layer thickness TB of the first layer (G) is
It is desirable that it be fairly thin, preferably less than 30 µl, more preferably less than 25 µl, and optimally less than 20 µl.

In the present invention, if necessary, the first
Specific examples of the halogen atoms (X) contained in the layer (G) and the second layer (S) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as such.

In the present invention, the first layer (G) composed of a-3i Ge (H, It is done by a deposition method. For example, by glow discharge method, a-3iGe(H,X)
To form the first layer (G), basically, a raw material gas for Si supply that can supply silicon atoms (St) and a raw material gas for Ge supply that can supply germanium atoms (Ge) are used. The raw material waste and, if necessary, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) are introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure. , a glow discharge is generated in the deposition chamber, and a-
A layer consisting of 3i Ge (H,X) may be formed. In addition, when forming by sputtering method, for example, A
Using two targets, one made of Si and the other made of Ge, in an atmosphere of an inert gas such as R, He, or a mixed gas based on these gases, or
When performing sputtering using a mixed target of i and Ge, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering as necessary.

Substances that can be used as raw material 4 for supplying Si used in the present invention include SiH4゜Si2H6,5i3H
B, 5i4H10i gaseous silicon hydride (silanes) which can be gasified is mentioned as one that 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, Ge2 H6, Ge3 HB.

Ge4 Hoo, Ge5 H12, Ge (3HH, Ge
7H1e, Ge8. Germanium hydride in a gaseous state or that can be gasified, such as H18, Ge9 H20, etc., can be effectively used. In particular, GeH4 , Ge
2 H6 and Ge3 HB are preferred.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, 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 which 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 CIF.

C sentence F3, BrF5, BrF3, IF3.

Examples include interhalogen compounds such as IF7, IC compound, and IBr.

As silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, specifically, for example, S
iF4, Si2F6.

SiC sentence 4. Silicon halides such as SiBr4 are preferred.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, hydrogen as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge is used. Even without using silicon gas,
A first layer (G) made of a-3iGe containing halogen atoms can be formed on a desired support.

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

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

In order to form the first layer region (G) made of a-8i Ge (H, In the case of the ion blasting method, sputtering is performed using two targets made of Si and Ge, or a target made of Si and Ge in a desired gas plasma atmosphere. Polycrystalline germanium or single crystal germanium is housed in a deposition boat as an evaporation source, and the evaporation source is heated and evaporated by a resistance heating method, an electron beam method (EB method), etc., and the flying evaporated material is evaporated into a desired gas plasma atmosphere. This can be done by passing it through.

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 /\ halogen compound described in 111 or the silicon compound containing the halogen atoms described above is deposited. It is sufficient to introduce the gas into the chamber 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/
A plasma atmosphere of the gases may be formed by introducing gases such as germanium hydride 7 into a deposition chamber for sputtering.

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, SiH2C sentence 2゜5jHCu3
．． Halogen-substituted silicon hydrides such as 5iH2Br2, 5iHBr3, and GeHF3゜GeB2 F2, GeB3
F, GeHCi3.

GeB2 Cn2, GeH3CM, GeHB r3°GeB2 Br2, GeB3 Br, GeHI3.

Hydrogenation of GeB2 I2, GeH'3 I, etc./Halides containing hydrogen atoms as one of their constituents, such as germanium chloride, GeF4, GeC 4゜GeBr4
, Ge I4 , GeF2 , GeC sentence 2°GeB r
Gaseous or gasifiable substances such as germanium halides such as 2, GeI2''J, etc. may also be mentioned as useful starting materials for the formation of the first layer (d).

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

In order to structurally introduce hydrogen atoms into the layer (G) of t51, in addition to the above, H2, SiH4゜Si2 H6, S
germanium or germanium compound for supplying Ge to silicon hydride such as i3 HB, Si4 HlO,
Or GeH4.

Ge2 H6, Ge3 HB, Ge4 Hlo, Ge
5H12, Ge6H14, Ge7 H16, Ge8 H
lB.

This can also be achieved by causing germanium hydride such as Ge5H12 and silicon or a silicon compound for supplying Si to coexist in a deposition chamber to generate a discharge.

In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 0.01 to 40
atom ic%, more preferably 0.05~
30 atom ic%, optimally 0.1-2
It is desirable to set it to 5 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, the second
To form the layer (S), starting materials [second It can be carried out using the starting material (II)) for forming the layer (S) in accordance with the same method and conditions as in the case of forming the first layer CG).

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-3t (H, Along with the raw material gas, a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as needed is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. The layer 1 consisting of a-3i(H, In addition, when forming by a sputtering method, for example, when sputtering Terkerato composed of St 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 halogen atoms CX) introduction gas may be introduced into the deposition chamber for sputtering.

In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the group of hydrogen atoms and halogen atoms contained in the second layer (S) constituting the photoreceptive layer to be formed is sum(
H+
It is desirable to set it to atomic%.

In the light-receiving member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the light-receiving layer, the light-receiving layer contains , oxygen atom, carbon atom,
It contains at least one type of nitrogen atom. Such atoms (OCN) are 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 region of the photoreceptive layer, or they may be contained in only some layer regions of the photoreceptive layer. It may be unevenly distributed.

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

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

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

In the present invention, a layer region (OCN
) The content of atoms (OCN) contained in the layer region (O
CN) itself or the layer region (OCN).
) 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, when another layer region is provided in direct contact with the layer region (OCN), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. is also taken into account,
The content of atoms (OCN) is selected appropriately.

The amount of atoms (OCN) contained in the layer region (OCN) is appropriately determined as desired depending on the characteristics required of the light receiving member to be formed, but is preferably 0.001-5.
0 atomic%, more preferably 0.002-40a
tomic%, optimally 0.003-30at o
It is desirable to set it to mic%.

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

In the case of the present invention, if the ratio of the layer thickness TQ of the layer region (OCN) to the layer thickness T of the photoreceptive layer is two-fifths or more, Atoms contained (
The upper limit of OCN) is preferably 30 atomic
% or less, more preferably 2C1 atomic% or less, optimally 10 atomic% or less.

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

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

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

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

In FIGS. 16 to 24, the horizontal axis represents atoms (0(:
The vertical axis indicates the layer thickness of the layer region (OCN), tB indicates the position of the end surface of the layer region (OCN) on the support side, and tT indicates the layer region on the opposite side to the support side. (OCN)
Indicates the position of the end face. That is, the layer region (OCN) containing atoms (OCN) is formed from the tB side toward the tT side.

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

In the example shown in FIG. 16, the surface where the layer region (OCN) containing atoms (OCN) is formed and the layer region (OCN)
From the interface position B E 33 where it contacts the surface of N) to the position tl, the distribution concentration C of atoms (OCN) takes a constant value of 02, while the layer region (O
CN)) is contained therein, and the concentration is gradually and continuously decreased from the position t1 to the concentration C2 up to the interface position t-1-. At the interface position tT, the distribution concentration C of atoms (OCN)
is assumed to be concentration C3.

In the example shown in FIG. 17, the contained atoms (O
CN) forms a distribution state in which the concentration C gradually and continuously decreases from the concentration C4 from the position TB to the position tT, and reaches the concentration C5 at the position t-1-.

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

In the case of FIG. 19, the distribution concentration C of atoms (OCN) is gradually and continuously reduced from the concentration C8 from the position TB to the position 1ξtT, and becomes substantially zero at the position tT.

In the example shown in FIG. 20, the distribution concentration C of atoms (OCN) is a constant value of concentration C9 between the position TB and the position t3, and the concentration is CIO at the position t7. Between position t3 and position t-1-, the In concentration C is linearly decreased from position t3 to position t7.

In the example shown in FIG. 21, 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 tT, the concentration decreases linearly from CI2 to C13. In the example shown in FIG. 22, from position 1 TB to position tT, the distribution concentration C of atoms (OCN) decreases linearly from the concentration C14 to substantially zero.

In FIG. 23, from position tB to position ff1t5, the distribution concentration C of atoms (OCN) decreases linearly from the concentration CI5 to C·16, and between position t5 and position tT. , an example in which the concentration Cl13 is set to a constant value is shown.

In the example shown in FIG. 24, the distribution concentration C of atoms (OCN) is the concentration CI? , and this concentration CI? until reaching position t6. At first, the concentration is gradually decreased, and near the position t6, the concentration is rapidly decreased to a concentration C18 at the position t6.

Between position t6 and position a t 7, the concentration is decreased rapidly at first, and then gradually decreased to reach C19 at position t7, and between position t7 and position t8, it is extremely slowly decreased. The concentration is gradually decreased to reach the concentration C20 at the position t8. Between position t8 and position tT, the concentration is reduced from C20 to substantially zero according to a curve shaped as shown in the figure.

As described above, from FIGS. 16 to 24, the layer region (OCN)
As explained in the description of some typical examples of the distribution state of atoms (OCN) contained in the layer thickness direction, in the present invention,
On the support side, there is a part where the distribution concentration C of atoms (OCN) is high, and on the interface tT side, there is a part where the distribution concentration C is considerably lower than on the support side.
A distribution state of OCN) is provided in the layer region (OCN).

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

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

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

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

The localized region (B) is the atom contained therein, (OCN)
Atomic (OCN) minutes as the distribution state in the layer thickness direction! The maximum value Cmax of the ri concentration C is preferably 500ato
mic ppm or more, more preferably 800 atomic
More than ppm.

Optimally, it is desirable to form a layer so that a distribution state of 1,001,000 ato ppm or more can be obtained.

That is, in the present invention, the layer region (OCN) containing atoms (OCN) has a layer thickness of 5 μm or less from the support side (
The maximum value Cm of the distribution concentration C in the layer region with a thickness of 5 to tB)
It is desirable that the structure be formed such that a x exists.

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

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

Further, it is preferable that the change line of the distribution concentration C of atoms (0, CN) in the one-layer region (OCN) is a continuous and gentle change in order to provide a smooth refractive index change.

From this point, atoms (O
CN) is preferably contained in the layer region (OCN).

In the present invention, in order to provide a layer region (OCN) containing atoms (OCN) in the photoreceptive layer, 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 (OCN) is added to the starting material selected as desired from among the starting materials for forming the photoreceptive layer described above. It will be done. As the starting material for such introduction of atoms (OCN), most of the gaseous substances or gasified substances whose constituent atoms are at least atoms (OCN) are used.

Specifically, for example, acid 1 (02), ozone (03), -
Nitrogen resistant (No), nitrogen dioxide (NO2), -nitrogen dioxide (N20), nitrogen sesquioxide (N203), nitrogen tetroxide (N204).

Nitrogen sesquioxide (N205), Nitrogen sesquioxide 03).

Silicon atom (Si), oxygen atom (0) and hydrogen atom (H
) as constituent atoms, for example, disiloxane (H3S
1O3iH3), trisiloxane (H3S i OS
Lower siloxanes such as i H20S i H3), methane (CH4), ethane (C2H6), propa7 (C3
HB), n-butane (n -C4H10), pentane (
Saturated hydrocarbons having 1 to 5 carbon atoms such as C5HI2), ethylene (C2H4), propylene (C3H5), butene-
1 (C4H8).

Butene-2 (C4HB), inbutylene (C4H8),
Ethylene hydrocarbons having 2 to 5 carbon atoms such as pentene (C5'110), acetylene (C2H2).

Acetylenic hydrocarbons with 2 to 4 carbon atoms such as methylacetylene (C3H4) and butyne (C4H5), nitrogen (N2)
, ammonia (NH3), hydrazine (H2NNH2
), hydrogen azide (HN3N) 3゜ammonium azide (
HH4N3), nitrogen trifluoride (F3N), nitrogen tetrafluoride (F
4 N) and so on.

In the case of the sputtering method, as starting materials for the introduction of atoms (OCN), in addition to the above-mentioned gasifiable starting materials listed for the glow discharge method, as national starting materials,
S i02. Examples include S i 3N4° carbon black. These are used as sputtering targets together with targets such as Si.

In the present invention, when forming the photoreceptive layer, atoms (OCN
), the distribution concentration C of atoms (OCN) contained in the layer region (OCN)
is changed in the layer thickness direction to obtain the desired distribution state in the layer thickness direction (d
When forming a layer region (OCN) with a profile), in the case of a glow discharge, the distribution concentration C
This is accomplished by introducing a starting material gas for introduction of atoms (OCN) to be changed into the deposition chamber while appropriately changing the gas flow rate according to a desired rate of change curve.

For example, the opening of a predetermined needle valve provided in the middle of the waste flow rate system may be temporarily changed by any commonly used method such as manually or using an externally driven motor. At this time, the rate of change of lA5 knee does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a predesigned rate of change curve to obtain a desired content rate curve.

When forming a layer region (OCN) by sputtering, the distribution concentration C of atoms (OCN) in the layer thickness direction is changed in the layer thickness direction to obtain a desired distribution state (OC,N) of atoms (OC,N) in the layer thickness direction. In the case of forming a depfh profile), 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 when introducing the residue into the deposited material is used. This is accomplished by appropriately changing the flow rate as desired. Second, if a sputtering target is used, for example, a target that is a mixture of Si and SiO2, the mixing ratio of Si and SiO2 should be adjusted in the direction of the layer thickness of the target.
This is done by changing it in advance.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AM, Cr, Mo, and Au.
, 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, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, 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 a crow, NiCr, A,
Q, Cr, Mo, Au, Ir, Nb.

T a , V , T i , P t , P d , I
n 203.

S n02 , I To (I n203+s n02
), etc., or if it is a synthetic resin film such as a polyester film, NiCr, AM.

Ag, Pb, Zn, Ni, Au, Cr, Mo.

A thin film of metal such as Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam deposition, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. will be granted. 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, it is preferable to use lo
It is considered to be more than μ.

Examples of the present invention will be described below.

Example 1 In this example, a semiconductor laser (wavelength: 780 nm) with a spot diameter of 80 gm was used. Therefore, the cylindrical AM support (length L) on which A-3i:H is deposited is 357 mm.
, pitch (P) 25gm with a lathe to diameter (r) 80mm)l
A spiral groove was made with a depth D) of 0.83. The shape of the groove at this time is shown in FIG.

A light-receiving layer consisting of a first layer and a second layer was deposited on this An support using the apparatus shown in FIG. 12 in the following manner.

First, the configuration of the device will be explained. 1201 is a high frequency power supply, 1
202 is a matching box, 1203 is a diffusion pump and a mechanical booster pump, 12-04 is a motor for rotating the An support, 1205 is an An support, 1206 is a heater for heating the An support, 1207 is a gas introduction pipe, 12
08 is a cathode electrode for high frequency introduction, 1209 is a shield plate, 121O is a power source for a heater, 1221 N1225.
1241-1245 are /help, 1231-1235 are mass flow controllers, 1251-1255 are regulators, 1261 are hydrogen (H2) cylinders, 1262 are silane (S i H4) cylinders, 1263 are ammonia (NH3) cylinders, 126) 4 1265 is a nitrogen oxide (NO) cylinder, and 1265 is a germane (GeH4) cylinder.

Next, the manufacturing procedure will be explained. All main valves of cylinders 1261 to 1265 were closed, all mass flow controllers and valves were opened, and the pressure inside the deposition apparatus was reduced to 10-7 Torr using a diffusion pump 1203. At the same time 1
Heater of 206 heats 1205 An support body to 2500
Heated to 0 and held constant at 25.0'C.

1221~122.5.1241~1245 after the temperature of the An support of 1205 becomes constant at 250' Ci.
．． 1251-1255/Close help, 1261-1
Open the main valve of the cylinder 265 and replace the diffusion pump 1203 with a mechanical booster pump. 1251-12
The secondary pressure of the 55 regulator I1 valve is 1.5k.
g/Cm2. Set the 1231 mass flow controller to: 300SCCM, and set the 1241 valve and 1
The valves 221 were sequentially opened to introduce H2 gas into the deposition apparatus.

Next, SiH4 gas in cylinder 1262 and G in 1265
e H4 gas, set the mass flow controllers of 1232 and 1235 to 11005CC and 50SC, respectively.
Set to CM and add SiH using the same operation as introducing H2 gas.
4 gas and GeH gas were introduced into the deposition apparatus.

Next, set the No gas flow rate of 1264 to the sum of the SiH4 gas flow rate and the GeH4 gas flow rate to an initial value of 3.4V.
The mass flow controller of 1234 was set so that o1%, and No gas was introduced into the deposition apparatus in the same manner as the introduction of H2 gas.

When the internal pressure in the deposition apparatus stabilizes at 0.2 Torr, turn on the high frequency power supply 1201 and adjust the matching box 1202 to generate a glow discharge between the An support 1205 and the cathode electrode 1208. High frequency power is 150W, 5 layers m thickness A-5iGe:H:
A 0 layer (to become an A-3i'Ge:H layer containing 0) was deposited (first layer). In this way, 5 lm thick A-3iGe
1224.1 without turning off the discharge after depositing :H:O
225's 7<lub was closed to stop the flow of GeH4.

And 20pm thick A-3i:H with high frequency power of 150W.
deposited (second layer)
layers). Thereafter, the high frequency power supply and gas valves were all closed, the deposition apparatus was evacuated, the temperature of the An support was lowered to room temperature, and the support on which the photoreceptive layer was formed was taken out.

Separately, the first layer and the second layer were formed under the same conditions and manufacturing procedure as in the case of ``2'' except that the high frequency power was 40 W on the same cylindrical An support with the same surface properties. When formed on a support, the surface of the photoreceptive layer was parallel to the plane of the support 1301, as shown in FIG. At this time, the difference in the total layer thickness between the center and both ends of the All holder is 1°.
Met.

Further, in the case where the high-frequency power was set to 160 W, the surface of the light-receiving layer and the surface of the 140-piece support were non-parallel as shown in FIG. In this case, the average MP layer thickness difference between the center and both ends of the AM support was 2 gm.

The above two types of electrophotographic light-receiving members (with wavelength 7
Spot an 80nm semiconductor laser.

Image yellowing was carried out using the apparatus shown in Fig. 15 with a diameter of 80 μm.
It was developed and transferred to obtain an image. With the high-frequency power of 40 W during fabrication, the surface light-receiving member shown in FIG.
An interference fringe pattern was observed.

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

Example 2 The surface of a cylindrical Al support was machined using a lathe as shown in Table 1. An electrophotographic light-receiving member was placed on these cylindrical A-shaped supports (No. 1 to 108) under the same conditions as in Example 1 (high frequency power: 160 W) under which the interference fringe pattern disappeared. were produced (No. 111-118). At this time, the difference in average layer thickness between the center and both ends of the A4Q electrophotographic light-receiving member and support was 2. It was 2gm.

When the cross sections of these electrophotographic light-receiving members were observed with an electron microscope and the difference in the pitch of the second layer was measured, the results shown in Table 2 were obtained.

Regarding these light receiving members, as in Example 1, the 15th
The device shown in the figure uses a semiconductor laser with a wavelength of 780 nm and a spot diameter of 80. When image exposure was carried out using m, the results shown in Table 2 were obtained.

Example 3 Light-receiving members were produced under the same conditions as in Example 2 except for the following points (No. 112 to 128).

At that time, the thickness of the first layer was 10 μm. At this time, the difference in average layer thickness between the center and both ends of the first layer is 1.2 pm.
, the average difference in the thickness of the second layer between the center and both ends is 2.3
It was pm. No.

When the thickness of each layer of Nos. 121 to 128 was measured using an electron microscope, the results shown in Table 3 were obtained. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and the results shown in Table 3 were obtained.

Example 4 A cylindrical Al support with the surface properties shown in Table 1 (No.
A light-receiving member in which a layer of 1 containing nitrogen was provided on 108) was prepared under the conditions shown in Table 4. (No,'
401-408) The cross section of the light receiving member produced under the above conditions was observed with an electron microscope. The average layer thickness of the first layer is
It was 0.09 gm at the center and both ends of the cylinder. Second
The average layer thickness at the center and both ends of the cylinder was 31 Lm.

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 5.

Each light-receiving member was image-wise exposed to laser light in the same manner as in Example 1, and the results are shown in Table 5. Example 5 A cylindrical Al support (No.
101-108) A light-receiving member having a first layer containing nitrogen provided thereon was produced under the conditions shown in Table 6 (Sample No.
501-508).

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

The layer thickness difference within the short range of the photosensitive layer of each light-receiving member was the value shown in Table 7.

Each light-receiving member was imagewise exposed to laser light in the same manner as in Example 1, and the results are shown in Table 7. Example 6 A light receiving member provided with a first layer containing carbon was prepared under the conditions shown in Table 8. (
Sample Nos. 901 to 908) The cross sections of the light receiving members produced under the above conditions were observed using an electron microscope. The average layer thickness of the first layer was 0.08 pLm at the center and at both ends of the cylinder. The average layer thickness of the second layer was 2.5 pLm in the center and at both ends of the cylinder.

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 9.

Each light-receiving member was image-exposed to laser light in the same manner as in Example 1, and the results are shown in Table 9. Example 7 A cylindrical A-shaped support (No.
A light-receiving member in which a first layer containing carbon was provided on O1-107) was prepared under the conditions shown in Table 10 (No.
1101-1108).

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

The layer thickness difference within the short range of the second layer of each light receiving member was the value shown in Table 11.

When each light-receiving member was subjected to imagewise exposure with laser light in the same manner as in Example 1, the results shown in Table 11 were obtained.

Example 8 When forming the first layer, the NO gas flow rate was changed with respect to the sum of the SiH4 gas flow rate and the GeH4 gas flow rate as shown in FIG. The high frequency power of Example 1 was set to 16, except that it was set to zero.
An electrophotographic light-receiving member was produced under the same conditions as in the case of 0W. Separately, when the first layer and the second layer were formed on the support under the same conditions and manufacturing procedure as in the above case except that the high frequency power was 40 W, a photoreceptive layer was formed as shown in FIG. The surface of was parallel to the plane of the support 1301. At this time, the difference in the total layer thickness between the center and both ends of the An support 1301 was Igm.

Further, when the high frequency power is set to 160 W, the surface of the photosensitive layer 1403 and the support 1401 are connected to each other as shown in FIG.
was non-parallel to the surface of In this case, the difference in average layer thickness between the center and both ends of the An support was 2 pm.

Regarding the above two types of electrophotographic light receiving members, wavelength 7
Image exposure was performed using an apparatus shown in FIG. 14 using an 80 nm semiconductor laser with a spot diameter of 80 pm, and the image was developed and transferred to obtain an image. At high frequency power of 40 W during layer production, the first
In the superficial light-receiving member shown in FIG. 4, an interference fringe pattern was observed.

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

Example 9 The surface of a cylindrical A-shaped support was machined using a lathe as shown in Table 1. These (Cylinder No.

Example 8 on the cylindrical An support of 101-108)
Electrophotographic light-receiving members were produced under the same conditions (high-frequency power 160 W) under which the interference fringe pattern disappeared (sample Nos. 1201 to 1208). At this time, the difference in average layer thickness between the center and both ends of the An support of the electrophotographic light-receiving member was 2.2 lm.

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

Example 10 A light-receiving member was produced under the same conditions as in Example 9 except for the following points (sample No. 1301"1308). At that time, the layer thickness of the first layer was set as lopLm. The difference in average layer thickness between the center and both ends of the first layer is 1.2 μm, and the second layer
The average difference in layer thickness between the center and both ends is 2. ．． 3gm
Met. When the thickness of each layer of sample Nos. 1301 to 1308 was measured using an electron microscope, the results shown in Table 3 were obtained. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and as a result, the 13th
Obtained the results in the table.

Example 11 A light-receiving member in which a first layer containing nitrogen was provided on a cylindrical An support (cylinder No. 101 to 108) having the surface properties shown in Table 1 was prepared under the conditions shown in Table 14. Except for this, it was produced according to the same conditions and procedures as in Example 9. (Sample No.

1'501 to 1508) The cross section of the light receiving member produced under the above conditions was observed with an electron microscope. The average layer thickness of the first layer was 0.09 ILm in the center and at both ends of the cylinder. The average layer thickness of the second layer was 3 m in the center and at both ends of the cylinder.

The second of each light-receiving member (sample No., 1501-1508)
The layer thickness differences within the short range of the layers were the values shown in Table 15.

When each light-receiving member (sample No. 151 to 158) was image-exposed with laser light in the same manner as in Example 1, the 15th
The results shown in the table were obtained.

Example 12 A light-receiving member in which a first layer containing nitrogen was provided on a cylindrical AM support (cylinder No. 101 to 10.8) having the surface properties shown in Table 1 was subjected to the conditions shown in Table 16. It was produced according to the same conditions and procedures as in Example 9 except for the following. (Sample No. 1701-1708).

A light-receiving member (sample No.) produced under the above conditions.

1701 to 1708) were observed using an electron microscope. The average layer thickness of the first layer is 0 at the center and both ends of the cylinder.
．． It was 3pm. The average layer thickness of the photosensitive layer was 0.3 gm at the center and both ends of the cylinder.

Each light receiving member (sample No. 1701-1708').

The layer thickness difference within the short range of the photosensitive layer was the value shown in Table 17.

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

Example 13 Example except that the light-receiving member in which a nitrogen-containing layer was provided on the surface cylindrical An support (cylinder No. 101-108) shown in Table 1 was made under the conditions shown in Table 18. It was produced according to the same conditions and procedures as No. 9. (Sample No.
1901-1908).

A light-receiving member (sample No.) produced under the above conditions.

1901-1908) were observed using an electron microscope. The average layer thickness of the first layer is 0 at the center and both ends of the cylinder.
．． It was 08 pLm.

The average layer thickness of the photosensitive layer is 2.5p at the center and both ends of the cylinder.
It was m.

The layer thickness difference within the short range of the second layer of each light receiving member (sample No. 901-908) was the value shown in Table 19.

When each light-receiving member (sample No. 1901-1902) was imagewise exposed to laser light in the same manner as in Example 1, the results shown in Table 9 were obtained.

Example 14 A cylindrical A pattern support with the surface properties shown in Table 1 (Sample N
A light-receiving member having a nitrogen-containing first layer provided thereon was prepared according to the same conditions and procedures as in Example 9, except that the conditions shown in Table 20 were changed. (Sample No.

2101-2108).

A light-receiving member (sample No.) produced under the above conditions.

2101 to 2108) were observed using an electron microscope. The average layer thickness of the first layer is 1 at the center and at both ends of the cylinder.
．． It was 171m. The average layer thickness of the second layer was 3.4 m at the center and at both ends of the cylinder.

The second of each light receiving member (sample No. 2101 to 2108)
The layer thickness differences within the short range of the layers were the values shown in Table 21.

When each light-receiving member (sample No. 2101 to 2108) was imagewise exposed to laser light in the same manner as in Example 1, the results shown in Table 21 were obtained.

Flow example 15 The production equipment shown in FIG.
Table 22 to 2 on the support (cylinder No. 150)
Under each condition shown in Table 5, the gas flow rate ratio of No and Si H4 was changed with the elapsed layer formation time according to the rate of change curve of the gas flow rate ratio shown in FIGS. 25 to 28, and layer formation was performed. (Sample No. 2201)
~2204) was obtained.

When the characteristics of each light-receiving member thus obtained were evaluated under the same conditions and procedures as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. Example 16 of the Invention Using the production apparatus shown in FIG. 12, N was applied onto the An support of the cylinder (cylinder No. 105) under the conditions shown in Table 26 according to the rate of change curve of the gas flow rate ratio shown in FIG.
A light-receiving member for electrophotography was obtained by forming layers while changing the gas flow rate ratio of O and SiH4 with the elapsed time of layer formation.

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

Example 17 Using the manufacturing apparatus shown in FIG.
The gas flow rate ratio of NH3 and SiH4 and the gas flow rate ratio of CH4 and SiH4 were measured on the sL support (cylinder No. 105) according to the change rate curve of the gas flow rate ratio shown in FIG. 27 under each condition shown in Tables 27 to 28. Layers were formed by changing the gas flow rate ratio with the elapsed time of layer formation to obtain electrophotographic light-receiving members (sample NO, g2oe-2207).

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

[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. 6A to 6D 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) to 7(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 when the interfaces of each layer are non-parallel. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIG. 11 is an explanatory diagram of the surface state of the A-pattern support used in Example 1. FIG. 12 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 13 and FIG. 14 are schematic explanatory diagrams showing the structures of the light receiving members produced in Examples 1 and 8, respectively. FIG. 15 is a schematic explanatory diagram for explaining the image exposure apparatus used in the example. FIGS. 16 to 24 are explanatory diagrams for explaining the distribution state of atoms (OCN) in the layer region (OCN), respectively, and FIGS. 25 to 28 are respectively gas flow rates in the embodiment of the present invention. FIG. 3 is an explanatory diagram showing a ratio change rate curve. 1000......Photoreceptive layer 1001.1301.1401...A support 10
02.130:2,1402...First layer 10
03.1303.1403... Second layer 100
5・・・・・・・・・・・・・・・・Light receiving member 1
501...Eye...Old...Light receiving member for electrophotography 1502......
Semiconductor laser 1503・・・・・・・・・・・・・・・
...ftheta lens 1504...kawa...
...Polygon Mirae 505...
...... Exposure device plane 1Δ1506...
・・・・・・Old・・・・Side view of exposure device Applicant: Canon Co., Ltd. IJ No. 30 No. 4

Claims (1)

[Scope of Claims] (1) 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 photoreceptive member having a multilayered photoreceptive layer in which layers are provided in order from the support side, the photoreceptor layer includes oxygen atoms, carbon atoms,
Contains at least one type of atom selected from nitrogen atoms, and has one or more pairs of non-parallel interfaces within a short range, and the non-parallel interfaces are in at least one direction in a plane perpendicular to the layer thickness direction. A light-receiving member characterized in that a large number of light-receiving members are arranged. (2) In the photoreceptive layer containing at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms, the distribution state of the atoms contained in the precursor layer is nonuniform in the layer thickness direction. A light-receiving member according to claim 1. (3) A patent claim in which, in a photoreceptive layer containing at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms, the distribution state of the contained atoms is uniform in the layer thickness direction. The light-receiving member according to item 1. (4) Claim 1, which is based on the nrj arrangement rule.
The light-receiving member described in 2. (5) The light receiving member according to claim 1, wherein the arrangement is periodic. (B) The light receiving member according to claim 1, wherein the short range is 0.3 to 500 l. (7) The light-receiving member according to claim 1, wherein the non-parallel interface is formed by regularly arranged irregularities provided on the surface of the support. (8) The light-receiving member according to claim 5, wherein the unevenness is formed by an inverted ■-shaped linear projection. (8) 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. (10) 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. (11) 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. (12) Claim 1, wherein the support body is cylindrical.
The light-receiving member described in 2. (13) The light-receiving member according to claim 1O, wherein the inverted V-shaped linear protrusion has a spiral pattern within the plane of the support. (14) The light-receiving member according to claim 11, wherein the spiral pattern has a multiple chain line structure. (15) The light-receiving member according to claim 6, wherein the inverted V-shaped linear protrusion is divided in the direction of its ridgeline. (16) The light-receiving member according to claim 10, wherein the ridgeline direction of the inverted ■-shaped linear protrusion is along the central axis of the cylindrical support. (17) Claim 5: The unevenness has an inclined surface.
The light-receiving member described in 2. (18) The light-receiving member according to claim 15, wherein the inclined surface is mirror-finished. (19) 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.