JPH0235298B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a light-receiving member for electrophotography that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, etc.). . More specifically, the present invention relates to an electrophotographic light receiving member suitable for using coherent light such as laser light. [Prior Art] As a method of recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is A well-known method is to develop the image, perform processes such as transfer and fixing as necessary, and then record the image. In particular, in image forming methods using electrophotography, the laser used is a small and inexpensive He-Ne laser or semiconductor laser (usually with an emission wavelength of 650 to 820 nm).
It is common to record images using . In particular, as a light-receiving material for electrophotography that is suitable when using a semiconductor laser, in addition to the fact that the consistency of the photosensitivity region is much better than that of other types of light-receiving materials, the Vickers hardness is is high,
For example, Japanese Patent Laid-Open No. 1983-1983-1 is non-polluting from a social point of view.
Amorphous materials containing silicon atoms (hereinafter referred to as "a
-Si) is attracting attention. However, when the photoreceptive layer is a single-layer a-Si layer, in order to maintain its high photosensitivity and ensure the dark resistance of 10 ¹² Ωcm or more required for electrophotography, hydrogen atoms and halogen atoms are required. In addition to these, it is necessary to structurally contain boron 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. Examples of methods that can expand this design tolerance and make effective use of high light sensitivity even if the dark resistance is low to some extent due to clogging include JP-A-54-121743 and JP-A-Sho. As described in Publication No. 57-4053 and Japanese Patent Application Laid-open No. 57-4172, the photoreceptive layer is formed into a layered structure of two or more layers having different conductivity characteristics, and a depletion layer is formed inside the photoreceptive layer. or JP-A No. 57-52178, No. 52179,
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 as described in the publications No. 52180, No. 58159, No. 58160, and No. 58161. Light-receiving members with increased apparent dark resistance have been proposed. Through such proposals, a-Si light-receiving members have made dramatic progress in terms of commercialization design tolerances, ease of manufacturing management, and productivity, and have become commercially viable. The speed of development towards this is accelerating. When laser recording is performed using a light-receiving member with such a multilayered light-receiving layer, the thickness of each layer is uneven, and the laser light is coherent monochromatic light, 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"). Each of the incoming reflected lights can cause interference. This interference phenomenon appears as a so-called interference fringe pattern in the formed visible image and becomes a cause of image defects. Particularly when forming a mid-tone image with high gradation, the image becomes noticeably difficult to see. 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 I ₀ incident on a certain layer constituting the light-receiving layer of a light-receiving member, reflected light R ₁ reflected at the upper interface 102, and reflected light R ₂ reflected at the lower interface 101.
It shows. 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 λ/2n or more, the reflected lights R ₁ and R ₂ will be 2nd =
mλ (m is an integer, reflected light strengthens each other) and 2nd = (m
+1/2)λ (m is an integer, reflected 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 with a multilayer structure, the interference effect shown in FIG. 1 occurs in each layer, and as shown in FIG.
A synergistic negative effect of each interference occurs. 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 overcome this inconvenience, diamond cutting the surface of the support allows for
A method of forming a light-scattering surface by providing unevenness (for example, Japanese Patent Application Laid-Open No. 162975/1983), the surface of the aluminum support is treated with black alumite, or carbon, color pigments, and dyes are dispersed in the resin. (for example, Japanese Patent Application Laid-Open No. 165845/1983), the surface of the aluminum support is treated with satin-like alumite, or the surface of the support is formed with fine roughness by sandblasting. A method of providing a light scattering and antireflection layer (for example, Japanese Patent Application Laid-Open No. 1986-
16554) etc. have been proposed. However, these conventional methods have not been able to completely eliminate interference fringe patterns appearing on images. In other words, in the first method, only a large number of irregularities of a specific size are provided on the surface of the support, so although it is true that the appearance of interference fringes due to light scattering effects is prevented, as for 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 factor in the resolution drop. The second method is at the level of black alumite treatment,
Complete absorption is impossible, and the light reflected 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. It has disadvantages such as being damaged by the plasma during the formation of the Si layer, reducing its original absorption function, and having an adverse effect on 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 .
The _remaining light enters the light receiving layer 302 and becomes transmitted light _I1 . The transmitted light I ₁ is transmitted through the support 30
On the surface of 2, part of the light is scattered and becomes diffused light K ₁ , K ₂ , K ₃ ..., the rest is specularly reflected and becomes reflected light R ₂ , and part of it becomes emitted light R ₃ . Get older and go 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 will decrease because light will diffuse within the light-receiving layer and cause halation. There was also the drawback of doing so. In particular, in a multilayered light receiving member, the fourth
As shown in the figure, even if the surface of the support 401 is irregularly roughened, the reflected light R ₂ on the surface of the first layer 402,
The reflected light R ₁ from the second layer and the specularly reflected light R ₃ from the surface of the support 401 interfere with each other, resulting in an interference fringe pattern depending on the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it has been impossible to completely prevent interference fringes by irregularly roughening the surface of the support 401. Furthermore, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies greatly between lots, and even within the same lot, the degree of roughness is uneven. , there was a problem with manufacturing management. In addition, relatively large protrusions are frequently formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer. Furthermore, if the surface of the support 501 is simply roughened regularly, as shown in FIG. The sloped surface 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 is 2nd ₁ = mλ
Or, 2nd ₁ = (m+1/2)λ holds true, resulting in a bright area or a dark area, respectively. In addition, in the entire photoreceptive layer, there is non-uniformity in the layer thickness such that the maximum difference between the layer thicknesses d ₁ , d ₂ , d ₃ , and d ₄ of the photoreceptive layer is λ/2n or more. A striped pattern appears. Therefore, simply 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. OBJECTS OF THE INVENTION It is an object of the present invention to provide a new light-sensitive electrophotographic light-receiving member which eliminates the above-mentioned drawbacks. Another object of the present invention is to provide an electrophotographic light-receiving member that is suitable for image formation using coherent monochromatic light and that is easy to manufacture and control. Still another object of the present invention is to provide an electrophotographic 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 for electrophotography that has high electrical pressure resistance and photosensitivity and excellent electrophotographic properties. Yet another object of the present invention is that the concentration is high;
Another object of the present invention is to provide a light-receiving member for electrophotography that is suitable for electrophotography and is capable of obtaining high-quality images with clear halftones and high resolution. [Summary of the Invention] The light-receiving member for electrophotography of the present invention (hereinafter referred to as "light-receiving member") has a cross-sectional shape at a predetermined cutting position with a pitch of 0.3 μm to 500 μm, and a maximum depth of 0.1 μm to 5 μm. An amorphous material consisting of a support having a large number of convex portions formed on its surface in which a sub-peak is superimposed on a main peak, and a silicon atom, a germanium atom, and a hydrogen atom and/or a halogen atom. A photoreceptive layer consisting of a first layer made of a material, a second layer made of an amorphous material made of silicon atoms, hydrogen atoms and/or halogen atoms, The photoreceptive layer also contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and the distribution state of germanium atoms contained in the first layer is uniform in the layer thickness direction, The photoreceptive layer is characterized by having at least one pair of non-parallel interfaces within the short range. The present invention will be specifically described below 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 the enlarged part of
Since the layer thickness of the second layer 602 changes continuously from _d5 to _d6 , the interface 603 and the interface 604 have an inclination to each other. Therefore, the coherent light incident on this minute portion (shot range) causes interference in the minute portion, producing a minute interference fringe pattern. In addition, as shown in FIG. 7, the first layer 701 and the second layer 7
02 interface 703 and the free surface 70 of the second layer 702
4 are non-parallel, as shown in A in FIG. 7, the traveling directions of the reflected light R ₁ and the emitted light R ₃ for the incident light I ₀ are different from each other, so that the interfaces 703 and 704 are parallel. The degree of interference is reduced compared to the case (“B” in FIG. 7). Therefore, as shown in C in Figure 7, when a pair of interfaces are non-parallel ("A") than when they are parallel ("B"), even if there is interference, the brightness of the interference fringe pattern will be lower. The difference becomes negligible. As a result, the amount of light incident on the minute portions is averaged. This is true even if the thickness of the second layer 602 is macroscopically non-uniform (d ₇ ≠ d ₈ ) as shown in FIG. becomes uniform (see "D" 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 I ₀ , the reflected lights R ₁ , R ₂ , R ₃ ,
R ₄ and R ₅ exist. Therefore, in each layer, what has been described above similar to FIG. 7 occurs. Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer, so according to the present invention, as the number of layers constituting the photoreceptive layer increases, the interference effect is further prevented. I can do it. Further, interference fringes generated within a 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 irradiated light. In addition, in order to more effectively achieve the object of the present invention, the difference in layer thickness (d ₅ − d ₆ ) in a minute portion is determined by the following formula, where d ₅ − ₆ d≧λ/, where λ is the wavelength of the irradiated light. 2n (n: refractive index of the second layer 602). In the present invention, within the layer thickness of a microscopic portion of a multilayer photoreceptive layer (hereinafter referred to as a "microcolumn"), each layer is formed so that at least any two layer interfaces are in a non-parallel relationship. The layer thickness is controlled within the microcolumn, but as long as this condition is satisfied, any two layer interfaces may be in a parallel relationship within the microcolumn. However, the layers forming the parallel layer interface can be any two layers.
It is desirable that the layer be formed to have a uniform layer thickness over the entire region so that the difference in layer thickness at two positions is λ/2n (n: refractive index of the layer) or less. 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. Phase method (PCVD method), light
CVD method and thermal CVD method are adopted. As methods for processing the support to achieve the objects of the present invention, chemical methods such as chemical etching and electroplating, physical methods such as vapor deposition and sputtering, and mechanical methods such as lathe processing can be used. However, in order to easily manage production, a mechanical processing method such as a lathe is preferred. For example, when processing the support with a lathe, etc., as shown in Fig. 29, a cutting tool 1 having a V-shaped cutting edge is rubbed with diamond powder and the cutting edge is shaped into the desired shape. The surface of the support is precisely cut by fixing it in a predetermined position on a processing machine and moving it regularly in a predetermined direction while rotating the cylindrical support according to a program designed in advance as desired. This allows the desired uneven shape, pitch, and depth to be formed. The linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The helical structure of the protrusion may be a double or triple helical structure, or a crossed helical structure. Alternatively, a linear structure along the central axis may be introduced in addition to the spiral structure. In order to enhance the effects of the present invention and to facilitate processing control, it is preferable that the convex portions within a predetermined cross section of the support of the present invention have the same shape in a linear approximation. Further, the convex portions are preferably arranged regularly or periodically in order to enhance the effects of the present invention. Further, it is preferable that the convex portion has a plurality of sub-peaks in order to further enhance the effect of the present invention and improve the adhesion between the light-receiving layer and the support. In addition to each of these, in order to efficiently scatter incident light in one direction, the convex portion may be symmetrical (FIG. 9A) or asymmetrical (FIG. 9B) around the main peak.
It is preferable that they be unified. However, in order to increase the degree of freedom in controlling the processing of the support, it is better to have both of them mixed together. The predetermined cutting position of the support in the present invention is
For example, in a support that has a cylindrical axis of symmetry and is provided with a convex portion with a spiral structure centered on the axis of symmetry, it refers to any plane that includes the axis of symmetry, and for example, In the case of a support having a planar shape such as a plate, the term refers to a plane that crosses at least two of the plurality of convex portions formed on the support. In the present invention, each dimension of the irregularities provided on the surface of the support in a controlled manner is set in such a way that the object of the present invention can be achieved as a result, taking into consideration the following points. That is, firstly, the a-Si layer constituting the photoreceptive layer is
The structure is 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 cause a deterioration in the layer quality of the a-Si 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. As a result of examining the above-mentioned problems in layer deposition, process problems in electrophotography, and conditions for preventing interference fringes, the pitch of the recesses on the surface of the support is preferably 500 μm to 0.3 μm, more preferably 200μm
~1 μm, optimally 50 μm to 5 μm. Also, the maximum depth of the recess is preferably 0.1 μm ~
5μm, more preferably 0.3μm to 3μm, optimally
It is desirable that the thickness be 0.6 μm 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 degree to 20 degrees, more preferably 3 degrees to 15 degrees
degree, optimally 4 degrees to 10 degrees. Further, the maximum difference in layer thickness based on the non-uniformity of the layer thickness of each layer deposited on such a support is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 2 μm within the same pitch.
It is desirable that the thickness be 0.1 μm to 1.5 μm, most preferably 0.2 μm to 1 μm. 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 has excellent electrical, optical, and photoconductive properties.
Indicates electrical voltage resistance and operating 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 properties are stable, it is highly sensitive, and it has high sensitivity.
It has a high signal-to-noise ratio, 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, 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 described in detail with reference 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 made of a-Si (hereinafter abbreviated as "a-SiGe (H, ) and a containing a hydrogen atom or/and a halogen atom (X) as necessary.
-A second layer (S) 100 composed of Si (hereinafter abbreviated as "a-Si(H,X)") and having photoconductivity
It has a layered structure in which 3 and 3 are laminated in order. The germanium atoms contained in the first layer (G) 1002 are continuous and uniform in the thickness direction of the first layer (G) 1002 and in the in-plane direction parallel to the surface of the support. It is contained in the first layer (G) 1002 so as to have a distribution state. In the present invention, germanium atoms are not contained in the second layer (S) provided on the first layer (G), and a photoreceptive layer is formed in such a layer structure. As a result, a light-receiving member having excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths including the visible light region can be obtained. In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed over the entire layer region, so when a semiconductor laser or the like is used, the second layer (S ) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed by the first layer (G), 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, chemical stability is sufficiently ensured at the laminated interface. In the present invention, the content of germanium atoms contained in the first layer (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 1. 9.5× ¹⁰⁵ atomic
ppm, more preferably 100 to 8×10 ⁵ atomic ppm
It is desirable that this is done. In the present invention, the layer thickness of the first layer (G) and the second layer (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the light-receiving member to ensure that the desired properties are fully imparted to the light-receiving member. In the present invention, the layer thickness T _B of the first layer (G) is
Preferably 30 Å to 50 μ, more preferably 40 Å to
It is desirable that the thickness be 40μ, optimally 50Å to 30μ. Further, the layer thickness T of the second layer (S) is preferably
0.5~90μ, more preferably 1~80μ, optimally 2~
It is desirable to set it to 50μ. The sum (T _B +T) of the layer thickness T _B 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. It is determined as desired when designing the layers of the light-receiving member based on the organic relationship between the properties of the light-receiving member. In the light receiving member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
When satisfying the relationship T _B /T≦1, it is desirable to select appropriate numerical values for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B 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 1×10 ⁵ atomic
In the case of ppm or more, the layer thickness T _B of the first layer (G)
It is desirable that the thickness be quite thin, preferably 30μ or less, more preferably 25μ or less, and optimally 20μ 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, Examples include chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. In the present invention, the first layer (G) composed of a-SiGe (H, It is done by law. For example, in order to form the first layer (G) composed of a-SiGe (H, A source gas for Ge supply that can supply germanium atoms (Ge) and a source gas for introducing hydrogen atoms (H) or/and a source gas for introducing halogen atoms (X) as necessary, The distribution of germanium atoms contained on the surface of a predetermined support that has been placed at a predetermined position in advance by introducing a gas at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. A layer of a-SiGe(H,X) may be formed while controlling the concentration according to a desired rate of change curve. In addition, when forming by sputtering method,
For example, in an atmosphere of an inert gas such as Ar, He, or a mixed gas based on these gases, a target composed of Si and a target composed of Ge may be used, or a target composed of Si and Ge may be used. When performing sputtering using a mixed target, a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) may be introduced into the deposition chamber for sputtering, if necessary. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous silicon hydride (silanes) such as Si ₄ H ₁₀ , which can be gasified or gasified, can be effectively used, especially because of its ease of handling during layer creation work, good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Further, a silicon hydride compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom and a halogen atom, can also be mentioned as an effective compound in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. 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, the material gas that can supply Si together with the material gas for supplying Ge may be used as a material gas. The first layer (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using silicon hydride gas. When creating the first layer (G) containing halogen atoms according to the glow discharge method, basically silicon halide, which is a raw material for supplying Si, and Ge
germanium hydride, which is the raw material gas for supply;
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber for forming the first layer (G) at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to remove these gases. The first layer (G) can be formed on the desired support by forming a plasma atmosphere, but in order to make it easier to control the ratio of hydrogen atoms introduced, A desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with the above gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. To form the first layer (G) made of a-SiGe (H, Using two targets or a target made of Si and Ge, this is sputtered in a desired gas plasma atmosphere, and in the case of the ion plating method, for example, polycrystalline silicon or single crystalline silicon and Crystalline 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 evaporates are brought 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 plating 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 introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides such as GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ ,
Germanium halides such as GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as useful starting materials for forming the first layer (G). Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the first layer (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer (G), in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
It is also possible to cause a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in the deposition chamber. I can do it. 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 Sum of quantities (H+X)
is preferably 0.01 to 40 atomic%, more preferably
It is desirable that the content be 0.05 to 30 atomic%, most preferably 0.1 to 25 atomic%. Hydrogen atoms (H) contained in the first layer (G)
Or/and to control the amount of halogen atoms (X), for example, the support temperature or/and hydrogen atoms (H),
Alternatively, the amount of the starting material used to contain the halogen atoms (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 a-Si (H,
From the starting materials (I) for forming the layer region (G), the starting materials excluding the starting materials that will become the raw material gas for supplying Ge [starting materials for forming the second layer (S)] The process can be carried out using the same method and conditions as in the case of forming the first layer (G). That is, in the present invention, to form the second layer (S) composed of a-Si(H,X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. It is made by vacuum deposition method. For example, a second layer (S) composed of a-Si(H,X) is formed by a glow discharge method.
Basically, in order to form the above-mentioned silicon atoms (Si), in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), if necessary, a gas for introducing hydrogen atoms (H) or/and
Then, a raw material gas for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber, so that the material gas is introduced onto the surface of a predetermined support that has been installed at a predetermined position in advance. a-Si(H,X)
What is necessary is to form a layer consisting of. In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the amount of hydrogen atoms and halogen atoms contained in the second layer (S) constituting the photoreceptive layer to be formed is determined. The sum (H+X) is preferably 1
~40 atomic%, more preferably 5-30 atomic%,
The optimum range is preferably 5 to 25 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 atoms, carbon atoms, and nitrogen atoms 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 area of the photoreceptive layer, or they may be unevenly distributed by being contained only in some layer areas of the photoreceptive layer. You can let me. The distribution state of atoms (OCN) is the distribution concentration C (OCN)
However, it is desirable that the photoreceptive layer be uniform in a plane parallel to the surface of the support. In the present invention, the layer region (OCN) containing atoms (OCN) provided in the photoreceptive layer is
When the main purpose is to improve photosensitivity and dark resistance, it is provided so as to occupy the entire layer area of the photoreceptive layer.
When the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, it is provided so as to occupy the end layer region of the photoreception layer on the support side. In the former case, the content of atoms (OCN) contained in the layer region (OCN) is kept relatively low in order to maintain high photosensitivity, while in the latter case, the content of atoms (OCN) contained in the layer region (OCN) is kept relatively low in order to maintain high photosensitivity; It is desirable to use a relatively large amount to ensure accuracy. In the present invention, the content of the layer region (OCN) provided in the photoreceptive layer depends on the characteristics required of the layer region (OCN) itself, or the content of the layer region (OCN) provided in contact with the support. If so, it can be appropriately selected based on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, when another layer region is provided in direct contact with the layer region (OCN), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of atoms (OCN) is selected appropriately, taking into consideration the following. Atoms contained in the layer region (OCN)
The amount can be determined as desired depending on the characteristics required of the light receiving member to be formed, but is preferably 0.001 to 50 atomic%, more preferably,
0.002-40atomic%, optimally 0.003-30atomic%
It is desirable that this is done. 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 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, the layer thickness To of the layer region (OCN)
In cases where the proportion of atomic percent (OCN) in the layer thickness T of the photoreceptive layer is two-fifths or more, the upper limit of the atoms (OCN) contained in the layer region (OCN) is preferably 30 atomic%. The following, more preferably
It is desirable that it be 20 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 end layer region of the support side of the photoreceptive layer, it is possible to strengthen the adhesion between the support and the photoreceptor layer. Furthermore, in the case of nitrogen atoms, for example, in the coexistence with boron atoms, it is possible to further improve dark resistance and ensure high photosensitivity, so it is desirable to contain a desired amount in the photoreceptive layer. Further, a plurality of types of these atoms (OCN) may be contained in the photoreceptive layer. That is, for example, oxygen atoms may be contained in the first layer, or oxygen atoms and nitrogen atoms may be contained coexisting in the same layer region. 16 to 24 show typical examples in which the distribution state of atoms (OCN) contained in the layer region (OCN) of the light-receiving member in the present invention in the layer thickness direction is non-uniform. . In Figures 16 to 24, the horizontal axis represents the distribution concentration C of atoms (OCN), and the vertical axis represents the layer region (OCN).
indicates the layer thickness, and t _B is the layer area on the support side (OCN)
t _T indicates the position of the end surface of the layer region (OCN) on the opposite side to the support side. In other words, the layer region (OCN) containing atoms (OCN) is from the t _B side.
t Layer formation occurs toward _{the T} side. FIG. 16 shows a first typical example where the distribution state of atoms (OCN) contained in the layer region (OCN) in the layer thickness direction is non-uniform. In the example shown in FIG. 16, the interface position t _B where the surface where the layer region (OCN) containing atoms (OCN) is formed and the surface of the layer region (OCN) are in contact with each other.
Up to the position t ₁ , the distribution concentration C of atoms (OCN) takes a constant value C ₁ and is contained in the layer region (OCN) where atoms ₍ OCN) are formed,
The concentration is gradually and continuously decreased from C ₂ to the interface position t _T . At the interface position _tT , the distribution concentration C of atoms (OCN) is assumed to be the concentration _C3 . In the example shown in FIG. 17, the distribution concentration C of the contained atoms (OCN) gradually and continuously decreases from the concentration _C4 from position _tB to _tT , and at position _tT the concentration _C5 decreases. The distribution state is formed as follows. In the case of Fig. 18, the distribution concentration C of atoms (OCN) from position t _B to position t ₂ is a constant value of concentration C ₆ , and gradually becomes continuous between position t ₂ and position t _T. The distributed concentration C is substantially reduced to zero at the position _tT (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 decreased from the concentration C ₈ from position t _B to position t _T , and at position t _T it becomes substantially zero. has been done. In the example shown in Figure 20, atoms (OCN)
The distribution concentration C is the concentration between position _tB and position _t3 .
_C9 is a constant value, and the concentration is _C10 at position _tT . Between position _t3 and position _tT , the distribution concentration C
decreases linearly from position _t3 to position _tT . In the example shown in FIG. 21, the distribution concentration C
takes a constant value of concentration C ₁₁ from position t _B to position t ₄ , and from position t ₄ to position t _T the concentration is C ₁₂ to C ₁₃
Until then, the distribution is said to decrease linearly. In the example shown in Fig. 22, the _position
Until _tT , the distributed concentration C of atoms (OCN) decreases linearly from the concentration _C14 to substantially zero. In FIG. 23, from position t _B to position t ₅ , the distribution concentration C of atoms (OCN) decreases linearly from the concentration C ₁₅ to C ₁₆ , and from position t ₅ to position t _T. An example is shown in which the concentration C ₁₆ is kept at a constant value. In the example shown in FIG. 24, the distribution concentration C of atoms (OCN) is the concentration C at position _tB .
The concentration C ₁₇ is at first gradually reduced until reaching the position _{t 6} , and around the position t ₆ it is rapidly reduced to the concentration C ₁₈ at the position t ₆ . Between position t ₆ and position t ₇ , the concentration is first rapidly decreased, and then gradually decreased to reach C ₁₉ at position t ₇ , and between position t ₇ and t ₈ , is gradually reduced very slowly to reach the concentration C ₂₀ at t ₈ . 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 with reference to FIGS. 16 to 24, some typical examples where the distribution state of atoms (OCN) contained in the layer region (OCN) in the layer thickness direction is non-uniform, this book is as follows. In the invention, the support side has a portion where the distribution concentration C of atoms (OCN) is high, and the interface _tT side has a portion where the distribution concentration C is considerably lower than that on the support side. A distribution state of OCN) is provided in the layer region (OCN). Layer region containing atoms (OCN)
As mentioned above, there are atoms (OCN) toward the support side.
Localized region containing relatively high concentration (B)
It is desirable that the support be provided as having the following properties, and in this case, the adhesion between the support and the light-receiving layer can be further improved. The above localized region (B) can be explained using the symbols shown in FIGS. 16 to 24, from the interface position _tB .
It is desirable that the distance be within 5μ. In the present invention, the localized region (B) may be the entire region (L _T ) up to 5μ thick from the interface position t _B , or it may be a part of the layer region (L _T ). In some cases. Whether the localized region (B) is a part or all of the layer region (L _T ) is appropriately determined depending on the characteristics required of the photoreceptive layer to be formed. The localized region (B) has a distribution state of atoms (OCN) contained therein in the layer thickness direction, such that the maximum value Cmax of the atomic (OCN) distribution concentration C is preferably 500 atomic ppm or more, more preferably 800 atomic ppm or more.
It is desirable that the layer be formed in such a way that a distribution state of at least 1000 atomic ppm can be obtained. That is, in the present invention, the layer region (OCN) containing atoms (OCN) has a distribution concentration C within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the maximum value Cmax 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, at the interface between the layer region (OCN) and another layer region.
Atomic (OCN) as refractive index and slowly change
It is desirable to form a distribution state in the layer thickness direction. By doing so, it is possible to prevent the light incident on the photoreceptive layer from being reflected at the layer contact interface, and to more effectively prevent the appearance of interference fringes. Further, it is preferable that the change line of the distribution concentration C of the atoms (OCN) in the layer region (OCN) continuously and gently change in order to provide a smooth change in the refractive index. From this point of view, it is desirable that the atoms (OCN) be contained in the layer region (OCN) so as to have the distribution states shown in FIGS. 16 to 19, 22, and 22, for example. 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 a material selected as desired from among the starting materials for forming the photoreceptive layer described above. As such, most gaseous substances whose constituent atoms are at least atoms (OCN) or gasified substances that can be gasified are used. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ )
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), tricycloxane (H Lower cycloxanes such as ₃ SiOSiH ₂ OSiH ₃ ), methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H Saturated hydrocarbons having 1 to 5 carbon atoms such as ₁₂ ), ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), etc. with 2 to 5 carbon atoms
Ethylene hydrocarbons, acetylene hydrocarbons with 2 to 4 carbon atoms such as acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N) etc. can be mentioned. In the case of sputtering method, atomic (OCN)
As starting materials for introduction, in addition to the gasifiable starting materials mentioned above for the glow discharge method, solid starting materials such as SiO ₂ , Si ₃ N ₄ , carbon black, etc. can be mentioned. These are used as targets for sputtering together with targets such as Si. In the present invention, when a layer region (OCN) containing atoms (OCN) is provided when forming a photoreceptive layer, the distribution concentration C of atoms (OCN) contained in the layer region (OCN) is In order to form a layer region (OCN) having a desired distribution state (depth profile) in the layer thickness direction by changing C in the layer thickness direction, in the case of a glow discharge, the distribution concentration C of the atoms (OCN) whose distribution should be changed is This is accomplished by introducing the starting material gas for introduction into the deposition chamber while appropriately varying 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 gas flow system may be temporarily changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When forming a layer region (OCN) by a sputtering method, the distribution concentration C of atoms (OCN) in the layer thickness direction is changed in the layer thickness direction.
In order to form the desired depth profile in the layer thickness direction, 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 is introduced into the deposition chamber. This is accomplished by appropriately changing the flow rate of the gas introduced into the interior as desired. Second, if a target for sputtering is used, for example a mixed target of Si and SiO ₂ , the mixing ratio of Si and SiO ₂ should be varied in advance in the layer thickness direction of the target. It is done by putting it in place. The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . 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,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted 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. If used as a receiving member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired light-receiving member is formed, but if flexibility is required as a light-receiving member, the thickness of the support may be determined appropriately. It is made as thin as possible within the range. However, in such a case, the thickness is preferably 10μ or more in terms of manufacturing and handling of the support and functional strength. Next, an outline of an example of the method for manufacturing the light receiving member of the present invention will be explained. FIG. 12 shows an example of a light-receiving member manufacturing apparatus. Gas cylinders 2002 to 2006 in the figure are sealed with raw material gas for forming the light-receiving member of the present invention.
SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ )
Cylinder, 2003 is GeH ₄ gas (99.999% purity,
₂₀₀₄ is NO gas (purity 99.999%, hereinafter abbreviated as NO) cylinder, 200
6 is a H ₂ gas (purity 99.999%) cylinder. In order to flow these gases into the reaction chamber 2001, valves 202 of gas cylinders 2002 to 2006 are used.
2-2026, check that the leak valve 2035 is closed, and also check that the inflow valve 2012-
2016, after confirming that the outflow valves 2017 to 2021 and the auxiliary valves 2032 and 2033 are open, first open the main valve 2034 to exhaust the reaction chamber 2001 and each gas pipe. Next, when the reading on the vacuum gauge 2036 reaches approximately 5×10 ⁻⁶ torr, the auxiliary valves 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, the gas cylinder 2037
SiH ₄ gas from 02, gas cylinder from 2003
GeH ₄ gas, NO gas from gas cylinder 2004,
From 2006, _H2 gas valve 2022, 202
3, 2024, 2026 open and outlet pressure gauge 2
The pressure of 027, 2028, 2029, 2031 is 1
Adjust to Kg/ ^cm2 , inlet valve 2012, 201
3, 2014, 2016 gradually opened, mass flow controller 2007, 2008, 2009,
2011 respectively. Subsequently, outflow valve 2017, 2018, 2019, 2021,
The auxiliary valves 2032 and 2033 are gradually opened to allow each gas to flow into the reaction chamber 2001. At this time, the outflow valve _{2017 , 2018} , 2019, 2021
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. Then, the temperature of the base 2037 is increased by the heating heater 2038.
After confirming that the temperature is set within the range of 50 to 400° C., the power source 2040 is set to the desired power to generate glow discharge in the reaction chamber 2001. The glow discharge is maintained for a desired time in the manner described above, and the first layer (G) is formed on the base 2037 to a desired layer thickness. At the stage where the first layer (G) has been formed to the desired layer thickness, the discharge valve 2018 is completely closed and the discharge conditions are changed as necessary for the desired time according to the same conditions and procedures. By maintaining glow discharge, it is possible to form a second layer (S) substantially free of germanium atoms on the first layer (G). In addition, by appropriately opening and closing the outflow valve 2019, each layer of the first layer (G) and the second layer (S) can contain or not contain oxygen atoms, or a part of each layer can be changed. It is also possible to contain oxygen atoms only in the region. Further, when nitrogen atoms or carbon atoms are contained in the layer instead of oxygen atoms, the layer may be formed by replacing the NO gas in the gas cylinder 2004 with, for example, NH ₃ gas or CH ₄ gas. Also, if you want to increase the types of gas you use, you can add the desired gas cylinders.
Layer formation may be performed in the same manner. 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 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 μm was used. Therefore a-
Cylindrical Al support shown in Figure 11B (length (L) 357 mm, diameter (r) 80 mm) on which Si:H is deposited
It was created. Next, under the conditions shown in Table 1a, using the film deposition apparatus shown in FIG. 12, an a-Si electrophotographic light-receiving member having a laminated surface layer was prepared according to a predetermined operating procedure. Note that the flow rate of NO gas is the same as that of SiH ₄ gas.
The initial value is 3.4 vol for the sum of the GeH ₄ gas flow rate.
A mass flow controller was set and introduced so that the In this case, the surface of the photoreceptive layer and the surface of the support were non-parallel as shown in FIGS. 11B and 11C. Regarding the above light-receiving members for electrophotography, the wavelength
The first 780mm semiconductor laser with a spot diameter of 80μm
Image exposure is carried out using the apparatus shown in Figure 5, and then it is developed and
An image was obtained by transfer. In this case, no interference fringe pattern was observed in the obtained image, which showed electrophotographic characteristics sufficient for practical use. Example 2 The surface of the cylindrical Al support was polished using a lathe.
It was processed as shown in FIGS. 3 and 14. An electrophotographic light-receiving member was produced on these cylindrical Al supports under the same conditions as in Example 1. When these light-receiving members were subjected to image exposure using a semiconductor laser with a wavelength of 780 nm and a spot diameter of 80 μm using the apparatus shown in FIG. 15 in the same manner as in Example 1, no interference fringe pattern was observed in the images. A product showing electrophotographic properties sufficient for practical use was obtained. Example 3 A light-receiving member was produced under the same conditions as in Example 2 except for the following points. At that time, the thickness of the first layer is
It was set to 10 μm. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and as a result,
No interference fringe pattern was observed in the image, and an image showing electrophotographic characteristics sufficient for practical use was obtained. Example 4 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 1. 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 0.09 μm at the center and at both ends of the cylinder. Second
The average layer thickness is 3 μm at the center and both ends of the cylinder.
It was hot. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and as a result,
No interference fringe pattern was observed in the image, and an image showing electrophotographic characteristics sufficient for practical use was obtained. Example 5 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 2. When each of these light-receiving members was subjected to imagewise exposure with laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image as a result of the imagewise exposure.
A product showing electrophotographic properties sufficient for practical use was obtained. Example 6 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 3. When each of these light-receiving members was subjected to imagewise exposure with laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image as a result of the imagewise exposure, indicating electrophotographic characteristics sufficient for practical use. was gotten. Example 7 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 4. When each of these light-receiving members was subjected to imagewise exposure with laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image as a result of the imagewise exposure, indicating electrophotographic characteristics sufficient for practical use. was gotten. Example 8 When forming the first layer, the NO gas flow rate was changed to the sum of the SiH ₄ gas flow rate and the GeH ₄ gas flow rate to the 22nd layer.
Change as shown in the figure, and at the end of layer production
An electrophotographic light-receiving member was produced under the same conditions as in Example 1 except that the NO gas flow rate was set to zero. Regarding the above light-receiving members for electrophotography, the wavelength
Image exposure was performed using a 780 nm semiconductor laser with a spot diameter of 80 μm using the apparatus shown in FIG. 15, and the image was developed and transferred to obtain an image. In this case, no interference fringe pattern was observed in the obtained image, and an image showing electrophotographic characteristics sufficient for practical use was obtained. Example 9 The surface of the cylindrical Al support was polished using a lathe.
It was processed as shown in FIGS. 3 and 14. An electrophotographic light-receiving member was produced on these cylindrical Al supports under the same conditions as in Example 8. When these light-receiving members were subjected to image exposure using a semiconductor laser with a wavelength of 780 nm and a spot diameter of 80 μm using the apparatus shown in FIG. 15 in the same manner as in Example 8, no interference fringe pattern was observed in the images. A product showing electrophotographic properties sufficient for practical use was obtained. Example 10 A light receiving member was produced under the same conditions as in Example 9 except for the following points. At that time, the thickness of the first layer is
It was set to 10 μm. These light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and as a result,
No interference fringe pattern was observed in the image, and an image showing electrophotographic characteristics sufficient for practical use was obtained. Example 11 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 5. When each light-receiving member was image-exposed to laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image, and the resulting image exhibited electrophotographic characteristics sufficient for practical use. Example 12 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 6. When each light-receiving member was image-exposed to laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image, and the resulting image exhibited electrophotographic characteristics sufficient for practical use. Example 13 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 7. When each light-receiving member was image-exposed to laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image, and the resulting image exhibited electrophotographic characteristics sufficient for practical use. Example 14 A light-receiving member was produced on a cylindrical Al support with the surface properties shown in FIGS. 13 and 14 under the conditions shown in Table 8. When each light-receiving member was image-exposed to laser light in the same manner as in Example 1, no interference fringe pattern was observed in the image, and the resulting image exhibited electrophotographic characteristics sufficient for practical use. Example 15 Using the manufacturing apparatus shown in FIG. 12, gas flow ratios shown in FIGS. 25 to 28 were prepared on a cylindrical Al support (cylinder B) under the conditions shown in Tables 9 to 2. Layers were formed by changing the gas flow rate ratio of NO and SiH ₄ with the elapsed layer formation time according to the rate of change curve to obtain each of the light receiving members for electrophotography. When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention. Example 16 Using the manufacturing apparatus shown in FIG. 12, NO and NO were deposited on a cylindrical Al support (cylinder B) under the conditions shown in Table 13 and 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 by changing the gas flow rate ratio with SiH ₄ with the elapsed time of layer formation. When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention. Example 17 Using the manufacturing apparatus shown in FIG.
Under each condition shown in the table, the gas flow rate ratio of NH ₃ to SiH ₄ and the gas flow rate ratio of CH ₄ to SiH ₄ were changed with the elapsed layer formation time according to the change rate curve of gas flow rate ratio shown in Figure 27. Layer formation was performed to obtain each light-receiving member for electrophotography. When the characteristics of each light-receiving member thus obtained were evaluated using the same conditions and means as in Example 1, no interference fringe pattern was observed with the naked eye, and the electrophotographic characteristics were sufficiently good. It was suitable for the purpose of the invention.

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【table】 [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, B, C, and D are explanatory diagrams showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIGS. 7A, B, and C are explanatory views for comparing the intensity of reflected light when the interfaces of each layer of the light-receiving member are parallel and non-parallel.
FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. Figure 9A,
B is an explanatory diagram of the surface state of each typical support. FIG. 10 is an explanatory diagram of layer regions of the light receiving member. Figures 11, 13 and 14 are
FIG. 2 is an explanatory diagram of the surface state of an Al support used in Examples. FIG. 12 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 15 is an explanatory diagram of the image exposure apparatus used in the example. Figures 16 to 24 show atoms (O, C,
FIG. 3 is an explanatory diagram for explaining the distribution state of N).
FIG. 25 to FIG. 28 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 29 is an explanatory diagram for explaining the processing of the support body. 1000...Photoreceptive layer, 1001...Al support,
1002...first layer, 1003...second layer, 10
04...Light receiving member, 1005...Free surface of light receiving member, 2601...Light receiving member for electrophotography, 260
2... Semiconductor laser, 2603... fθ lens, 26
04... Polygon mirror, 2605... Plan view of exposure device, 2606... Side view of exposure device.

Claims (1)

[Claims] 1. The cross-sectional shape at a predetermined cutting position is 0.3 μm or more.
A support that has many convex portions formed on its surface with a pitch of 500 μm and a main peak with sub-peaks superimposed on a main peak with a maximum depth of 0.1 μm to 5 μm, silicon atoms, germanium atoms, and hydrogen atoms. and/or a halogen atom, and a second layer made of an amorphous material consisting of silicon atoms, hydrogen atoms, and/or halogen atoms, It is composed of a photoreceptive layer consisting of
The photoreceptive layer also contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and the distribution state of germanium atoms contained in the first layer is uniform in the layer thickness direction. . A light-receiving member for electrophotography, wherein the light-receiving layer has at least one pair of non-parallel interfaces within the shot range. 2. The light-receiving member for electrophotography according to claim 1, wherein the convex portions are regularly arranged. 3. The light-receiving member for electrophotography according to claim 1, wherein the convex portions are arranged periodically. 4. The light-receiving member for electrophotography according to claim 1, wherein each of the convex portions has the same shape in a linear approximation. 5. The light-receiving member for electrophotography according to claim 1, wherein the convex portion has a plurality of sub-peaks. 6. The electrophotographic light-receiving member according to claim 1, wherein the cross-sectional shape of the convex portion is symmetrical about the main peak. 7. The electrophotographic light-receiving member according to claim 1, wherein the cross-sectional shape of the convex portion is asymmetrical with respect to the main peak. 8. The electrophotographic light-receiving member according to claim 1, wherein the convex portion is formed by mechanical processing. 9. The electrophotographic light according to claim 1, wherein the photoreceptive layer contains at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms in a uniform state in the layer thickness direction. Receptive member. 10 The photoreceptive layer contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms,
The electrophotographic light-receiving member according to claim 1, which contains the light-receiving member in a non-uniform state in the layer thickness direction.