JPH0238944B2 - - 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. Among these, in image forming methods using electrophotography, image recording is generally performed using a compact and inexpensive He--Ne laser or semiconductor laser (usually having an emission wavelength of 650 to 820 nm). In particular, as a light-receiving material for electrophotography that is suitable when using a semiconductor laser, in addition to the fact that the consistency of the photosensitivity region is much better than that of other types of light-receiving materials, the Vickers hardness is is high,
In terms of being non-polluting from a social perspective, for example,
Amorphous materials containing silicon atoms (hereinafter referred to as "A
-Si") is attracting attention. However, if the photoreceptive layer is a single-layer A-Si layer, in order to maintain its high photosensitivity and ensure a dark resistance of 10 ¹² Ωcm or more, which is required for electrophotography, hydrogen atoms and Since it is necessary to structurally contain halogen atoms or boron atoms in addition to these in a specific amount range in a controlled manner in the layer, it is necessary to strictly control layer formation, etc.
There are considerable limitations on the tolerances in the design of light receiving members. Examples of systems that can expand this design tolerance and make effective use of high light sensitivity even with clogging and a certain degree of low dark resistance include JP-A-54-121743 and JP-A-Sho. As described in Japanese Patent Application Laid-open No. 57-4053 and Japanese Patent Application Laid-open No. 57-4172, the photoreceptive layer is formed into a two or more layered structure in which layers with different conductivity characteristics are laminated to form a depletion layer inside the photoreceptive layer. or JP-A-57-52178, JP-A No. 52179, JP-A No. 57-52178,
A multilayer structure in which a barrier surface 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"). There is a possibility that each of the reflected lights may 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 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 becomes more significant. 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 (e.g., Japanese Patent Laid-Open No. 162975/1983). The surface of the aluminum support is treated with black alumite, or carbon, colored pigments, and dyes are dispersed in the resin. (for example, Japanese Patent Laid-Open No. 57-165845), the surface of the aluminum support is treated with satin-like alumite, or the surface of the support is provided with fine roughness in the form of grains by sandblasting. A method of providing a light scattering and anti-reflection layer (for example, Japanese Patent Application Laid-open No. 1983-1999)
16554) etc. have been proposed. . However, with these conventional methods, it has not been possible to completely eliminate the interference fringe pattern appearing on the image. 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 cause of a decrease in resolution. 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 quality of the formed light-receiving layer is significantly deteriorated. It has disadvantages such as being damaged by plasma during the formation of the Si layer, reducing its original absorption function, and adversely affecting the subsequent formation of the A-Si layer due to deterioration of the surface condition. In the case of the third method of irregularly roughening the surface of the support, as shown in _FIG .
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, there is non-uniformity in the layer thickness in the entire photoreceptive layer, such that the maximum difference among the respective layer thicknesses d ₁ , d ₂ , d ₃ , and d ₄ of the photoreceptive layer is λ/2n or more. A pattern of light and dark stripes 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 allows digital image recording using electrophotography, especially digital image recording with halftone information to be performed clearly and with high resolution and high quality. be. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide a light-receiving member for electrophotography that has high signal-to-noise ratio characteristics and good electrical contact with a support. [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 support consisting of a support having a large number of convex portions formed on its surface, each having a convex shape in which a sub-peak is superimposed on a main peak; and silicon atoms, germanium atoms, hydrogen atoms and/or halogen atoms. a first layer made of a crystalline material; a second layer made of an amorphous material made of silicon atoms, hydrogen atoms and/or halogen atoms; The distribution state of germanium atoms contained in the first layer is uniform in the layer thickness direction,
Further, the photoreceptive layer is characterized in that it has 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 d ₅ to d ₆ , the interface 603 and the interface 604 have a tendency toward each other. Therefore, the coherent light incident on this minute portion (short range) 1 causes interference in the minute portion 1, producing a minute interference fringe pattern. Moreover, 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, the reflected light _R1 and the emitted light _R3 for the incident light _I0 have different traveling directions, as shown in A in FIG. 7, so 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. Moreover, each layer interface within the micro-section acts as a kind of slit, where diffraction development occurs. Therefore, the effect of interference in each layer appears as a product of interference due to the difference in layer thickness and interference due to diffraction at the layer interface. 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 l (one period of the uneven shape) of the minute portion suitable for the present invention satisfies l≦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 the minute portion l is expressed as d ₅ - _{d 6} ≧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 l of a multilayered photoreceptive layer (hereinafter referred to as a "microcolumn"), at least any two layer interfaces are in a non-parallel relationship. The layer thickness of each layer is controlled within the microcolumn, but if 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 between two positions is λ/2n (n: refractive index of the layer) or less. A first layer containing silicon atoms and germanium atoms and a second layer containing silicon atoms constituting the photoreceptive layer.
In order to more effectively and easily achieve the purpose of the present invention, the plasma vapor phase method (PCVD method) is used to form the layer, since the layer thickness can be precisely controlled at the optical level.
Optical CVD method and thermal CVD method are used. As methods for processing the support to achieve the object 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 or the like, as shown in Fig. 17, a cutting tool 1 having a V-shaped cutting edge is rubbed with diamond powder to give the desired shape. For example, by fixing the cylindrical support at a predetermined position on a cutting machine and regularly moving it in a predetermined direction while rotating it according to a program designed in advance as desired, the surface of the support can be accurately cut. By doing so, the desired uneven shape, pitch, and depth are 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 spiral structure of the protrusion may be a double or triple spiral structure, or a crossed spiral structure. Alternatively, a linear structure along the central axis may be introduced in addition to the 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. Furthermore, 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 portions are unified into a symmetrical shape (FIG. 9A) or an asymmetrical shape (FIG. 9B) around the main peak. Preferably. 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. 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 account the following points. That is, the first 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-described 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
It is desirable that the thickness is ~1 μm, optimally 50 μm to 5 μm. Also, the maximum depth of the recess is preferably 0.1 μm to 5 μm.
m, more preferably 0.3μm to 3μm, optimally 0.6μm
It is desirable that the thickness is between m and 2 μm. When the pitch and maximum depth of the recesses on the support surface 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, preferably 4 degrees to 10 degrees. Further, the maximum difference in layer thickness due to the non-uniformity of the 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 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. Since it has a multilayer structure in which the second layer and the second layer 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 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 explained 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 1 on a support 1001 as a light receiving member.
000, and the photoreceptive layer 1000 has a free surface 1
005 on one end face. The photoreceptive layer 1000 has a first layer (G) composed of a-Si(H,X) (hereinafter abbreviated as "a-SiGe(H,X)") containing germanium atoms from the support 1001 side. 1002 and a second layer (S) 1003 composed of a-Si (H, X) and having photoconductivity are laminated in this order. First layer (G)1
The germanium atoms contained in the first layer (G) 1002 are distributed continuously and uniformly in the layer 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. 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 in the entire layer area, 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, the first layer
Since the amorphous materials constituting (G) and the second layer (S) each have a common constituent element of silicon atoms, chemical stability can be sufficiently ensured at the laminated interface. has been done. In the present invention, the content of germanium atoms contained in the first layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9.5×10 ⁵ atomic ppm,
More preferably, it is 100 to 8×10 ⁵ atomic ppm, most preferably 500 to 1.7×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer (G) and the second layer (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the light-receiving member to ensure that the desired properties are fully imparted to the light-receiving member. In the present invention, the layer thickness 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 that appropriate numerical values be selected for each. In the selection of 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 ppm.
In the above case, the layer thickness T _B of the first layer (G) is
It is desirable to make it fairly thin, preferably 30μ
Hereinafter, it is more preferably 25μ or less, most preferably 20μ or less. In the present invention, the halogen atoms (X) contained in the first layer (G) and the second layer (S) constituting the photoreceptive layer as necessary 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, by the glow discharge method, a
- To form the first layer (G) composed of SiGe (H, A raw material gas for supplying Ge that can supply a hydrogen atom (H) and/or a raw material gas for introducing a halogen atom (X) as needed are placed in a deposition chamber whose interior can be kept at a reduced pressure. It is sufficient to introduce the a-SiGe (H, . In addition, when forming by sputtering method,
For example, using two targets, one made of Si and the other made of Ge, in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, or a mixture of Si and Ge. When performing sputtering using the sputtering target, 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 the 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:
_GeH4 , _{Ge2H6 , Ge3H8 , Ge4H10 , Ge5H12 ,}
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 which can be gasified are mentioned as those which can be effectively used, especially in layer forming operations. 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. Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogen compounds, 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 photoconductive member of the present invention using 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 is used. The first layer (G) made of a-SiGe containing halogen atoms can be formed on a desired support without using hydrogen-silicon gas. When creating the first layer (G) containing halogen atoms according to the glow discharge method, basically, for example, Si
Silicon halide, which will be the raw material gas for supplying, germanium hydride, which will be the raw material gas for Ge supply, and Ar.
Gases such as H ₂ and He 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 create a plasma atmosphere of these gases. The first layer (G) can be formed on a desired support by forming a gas such as In addition, a desired amount of silicon compound gas containing hydrogen atoms may be mixed 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 region (G) made of a-SiGe (H, In the case of ion plating, for example, polycrystalline silicon or single crystal silicon is sputtered 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 or an electrobeam method (EB method) to create a desired gas plasma atmosphere of flying evaporates. 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 and 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 ,
_GeH2F2 , _GeH3F , _{GeHCl3 , GeH2Cl2 ,
GeH3Cl} , _GeHBr3 , _GeH2Br2 , _{GeH3Br ,}
Halides containing hydrogen atoms as one of their constituents, 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 the like, 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 and 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 ,
Generating 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 a deposition chamber. But it can be done. 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 atomic%, more preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms ( The amount of the starting material used to contain X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer (S) composed of a-Si (H,
From the starting materials (I) for forming the layer (G), the starting materials excluding the starting materials that will become the raw material gas for G supply [Second
Using the starting material ()] for forming the layer (S) of
It can be performed according to 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.
In order to form, basically, in addition to the above-mentioned raw material gas for supplying Si that can supply silicon atoms (Si), hydrogen atoms (H) and/or halogen atoms (X) are introduced as necessary. A raw material gas for use is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber to deposit a-Si (H, What is necessary is to form a layer consisting of. In addition, when forming by sputtering, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the 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 to
It is desirable that the content be 40 atomic %, more preferably 5 to 30 atomic %, most preferably 5 to 25 atomic %. 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, 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 support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, the thickness is preferably 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. Next, an outline of an example of the method for manufacturing the light receiving member of the present invention will be explained. FIG. 11 shows an example of an apparatus for manufacturing a light-receiving member. Gas cylinders 1102 to 1106 in the figure are sealed with raw material gas for forming the light-receiving member of the present invention.
is SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ )
Cylinder 1103 is GeH ₄ gas (99.999% purity,
1104 is _{a SiF 4 gas} (purity 99.99%, hereinafter abbreviated as SiF ₄ ) cylinder, 110
5 is He gas (99.999% purity) cylinder, 1106
is a _H2 gas (99.999% purity) cylinder. In order to flow these gases into the reaction chamber 1101, valves 112 of gas cylinders 1102 to 1106 are used.
2-1126, make sure the leak valve 1135 is closed, and also check that the inflow valve 1112
1116, confirm that the outflow valves 1117 to 1121 and the auxiliary valves 1132 and 1133 are open, and first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe.
Next, when the reading on the vacuum gauge 1136 reaches approximately 5×10 ^-6 torr, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 1137, the gas cylinder 11
SiH ₄ gas from 02, from gas cylinder 1103
Open the GeH ₄ gas valves 1122 and 1123 and set the pressure on the outlet pressure gauges 1127 and 1123 to 1Kg/cm ²
, gradually open the inflow valves 1112 and 1113, and open the mass flow controllers 1107 and 11.
08 respectively. Subsequently, the outflow valves 1117 and 1118 and the auxiliary valve 1132 are gradually opened to allow the respective gases to flow into the reaction chamber 1101. At this time, the outflow valve 111 is adjusted so that the ratio between the SiH ₄ gas flow rate and the GeH ₄ gas flow rate becomes the desired value.
7 and 1118, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure in the reaction chamber 1101 reaches the desired value. After confirming that the temperature of the base 1137 is set to a temperature in the range of 50 to 400°C by the heater 1138, the power supply 1140
is set to a desired power to generate a glow discharge in the reaction chamber 1101, thereby containing germanium atoms in the layer formed. The glow discharge is maintained for a desired time in the manner described above to form the first layer (G) on the base 1137 to a desired layer thickness. At the stage where the first layer (G) has been formed to the desired layer thickness, the discharge valve 1118 is completely closed and the discharge conditions are changed as necessary for the desired time according to the same conditions and procedures. By maintaining the glow discharge, it is possible to form a second layer (S) substantially free of germanium atoms on the first layer (G). During layer formation, the substrate 1137 is preferably rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation. Examples will be described below. Example 1 An Al support was machined using a lathe to have the surface properties shown in FIG. 12B. Next, using the deposition apparatus shown in FIG. 11 and following various operating procedures under the conditions shown in Table 1, A-Si was deposited.
An electrophotographic light-receiving member was deposited on the aforementioned Al support. The surface condition of the A-Si:H electrophotographic light-receiving member thus produced was as shown in FIG. 12C. Regarding the light-receiving member for electrophotography as described above, the apparatus shown in FIG.
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the image, which was sufficient for practical use. Example 2 An electrophotographic light-receiving member was formed on a cylindrical Al support having the surface properties shown in FIGS. 14, 15, and 16 under the conditions shown in Table 2. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and then developed, transferred, and fixed to obtain a visible image on plain paper. In the image obtained in this case, no interference fringes were observed, and the characteristics were sufficient for practical use. Example 3 An electrophotographic light-receiving member was formed on a cylindrical Al support having the surface properties shown in FIGS. 14, 15, and 16 under the conditions shown in Table 3. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and were developed, transferred, and fixed to obtain a visible image on plain paper. This image forming process was continuously repeated 100,000 times. In all of the images obtained in this case, no interference fringes were observed, and the characteristics were sufficient for practical use. Moreover, there was no difference between the initial image and the 100,000th image, and the images were of high quality. Example 4 An electrophotographic light-receiving member was formed on a cylindrical Al support having the surface properties shown in FIGS. 14, 15, and 16 under the conditions shown in Table 4. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and were developed, transferred, and fixed to obtain a visible image on plain paper. In this case, no interference fringes were observed in the obtained image, which had sufficient characteristics for practical use. [Effects of the Invention] As described above in detail, according to the present invention,
It is suitable for image formation using coherent monochromatic light, easy to manufacture, and can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development. has high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with the support, and can provide a light-receiving member suitable for digital image recording.

【table】

【table】

【table】

【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 caused by scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. Figure 5 shows
FIG. 3 is an explanatory diagram of interference fringes when the interfaces of each layer of the light-receiving member are parallel. FIG. 6 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIG. 7 is an explanatory diagram of a comparison of reflected light intensity when the interfaces of each layer of the light-receiving member are parallel and non-parallel. FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. FIG. 9 is an explanatory diagram of the surface condition of each typical support. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIG. 11 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 12 is an explanatory diagram of the surface state of the Al support used in the examples. FIG. 13 is an explanatory diagram of the image exposure apparatus used in the example. Figure 14,
FIG. 15 and FIG. 16 are explanatory diagrams of the surface state of the Al support used in the examples. FIG. 17 is an explanatory diagram for explaining the processing of the support. 1000... Light receiving layer, 1001... Al support, 1002... First layer, 1003... Second layer, 1004... Light receiving member, 1005... Free surface of light receiving member, 1301... Electrophotographic light-receiving member, 1302...Semiconductor laser, 1303
...fθ lens, 1304 ...polygon mirror, 1
305... A plan view of the exposure apparatus, 1306... A side view of the exposure apparatus.

Claims (1)

[Claims] 1. The cross-sectional shape at a predetermined cutting position is 0.3 μm to 500 μm.
m pitch, a support having many convex portions formed on its surface, each having a convex shape in which sub-peaks are superimposed on a main peak at a maximum depth of 0.1 μm to 5 μm, and silicon atoms, germanium atoms, and hydrogen atoms. A first layer made of an amorphous material made of atoms and/or halogen atoms, and a second layer made of an amorphous material made of silicon atoms and hydrogen atoms and/or halogen atoms. , a photoreceptive layer consisting of the following, the distribution state of germanium atoms contained in the first layer is uniform in the layer thickness direction, and the photoreceptive layer has at least one layer within the short range.
A light-receiving member for electrophotography, characterized by having at least a pair of non-parallel interfaces. 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.