JPH0234023B2 - - 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,
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 the dark resistance of 10 ¹² Ωcm or more 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 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"). 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 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 (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 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 surface of the support, causing a substantial This caused 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 layer quality of the formed light-receiving layer is significantly deteriorated. It is damaged by plasma during the formation of the Si layer, reducing its original absorption function, and has disadvantages such as deterioration of the surface condition, which adversely affects the subsequent formation of the A-Si layer. 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 and goes outside. Therefore, since the emitted light _R3 , which is a component that interferes with the reflected light _R1 , remains, the interference fringe pattern cannot be completely erased. Furthermore, if the diffusivity of the surface of the support 301 is increased in order to prevent interference and multiple reflections inside the light-receiving layer, the resolution 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 regularly reflected light R ₃ from the support 401 interfere with each other, and an interference fringe pattern is produced 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 photoreceptive 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 single-layered light-receiving member. 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, in which digital image recording using electrophotography, especially digital image recording with halftone information, can be performed with clearness, high resolution, and high quality. It's also something to do. Yet another object of the present invention is to provide high sensitivity, high
Another object of the present invention is to provide an electrophotographic light-receiving member having good signal-to-noise ratio characteristics and good electrical contact with a support. [Summary of the Invention] The electrophotographic light-receiving member 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 silicon atoms, germanium atoms, and hydrogen atoms and/or halogen atoms. 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 distribution state of germanium atoms contained in the first layer is non-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 (shown below) 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, 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. 6, so the amount of incident light becomes uniform over the entire layer area. (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 explained above with reference to FIG. 7 occurs. Moreover, each layer interface within a microscopic portion acts as a kind of slit, where a diffraction phenomenon occurs. Therefore, the 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. 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 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, mechanical processing methods such as a lathe are preferred. For example, when machining the support with a lathe, etc., as shown in Fig. 30, 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. For example, by fixing the cylindrical support in 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 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. 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, first, 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 dimension 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 photoreceptive 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 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 due to 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 within the same pitch.
It is desirable that the thickness be 0.2 μm to 1 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 the distribution state of germanium atoms in the first layer is non-uniform in the layer thickness direction. Indicates electrical, optical, photoconductive properties, electrical voltage resistance, and use environment characteristics. In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical 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 1000 on a support 1001 for the light-receiving member, and the light-receiving layer 1000 has a free surface 1005 on one end surface. . The photoreceptive layer 1000 is a 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 made of a-Si(H,X) and having photoconductivity are laminated in this order. The germanium atoms contained in the first layer (G) 1002 are continuous in the thickness direction of the first layer (G) 1002 and are different from the side on which the support 1001 is provided. The support 1001 on the opposite side (the surface 1005 side of the photoreceptive layer 1001)
It is contained in the first layer (G) 1002 so that it is distributed more toward the sides. In the light-receiving member of the present invention, the distribution state of germanium atoms contained in the first layer (G) is as described above in the layer thickness direction,
It is desirable that the particles be uniformly distributed in the in-plane direction parallel to the surface of the support. 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. In particular, it is possible to obtain a light-receiving member that has excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths, including the visible light region. In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed in the entire layer region, and the distribution concentration C of germanium atoms in the layer thickness direction increases from the support side to the second layer. (S), the affinity between the first layer (G) and the second layer (S) is excellent, and as will be described later, the support side By extremely increasing the distribution concentration C of germanium atoms at the edge, when a semiconductor laser or the like is used, light on the long wavelength side that is hardly absorbed by the second layer (S) can be absorbed by the first layer. Layer (G) can absorb substantially completely 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. 11 to 19 show typical examples of the distribution state of germanium atoms contained in the first layer (G) of the light-receiving member in the present invention in the layer thickness direction. In FIGS. 11 to 19, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer (G).
tB indicates the position of the end surface of the first layer (G) on the support side, and tT indicates the position of the end surface of the layer (G) on the opposite side to the support side. That is, the first layer (G) containing germanium atoms is formed from the TB side toward the tT side. FIG. 11 shows a first typical example of the distribution state of germanium atoms contained in the first layer (G) in the layer thickness direction. In the example shown in FIG. 11, from the interface position tB where the surface on which the first layer (G) containing germanium atoms is formed and the surface of the first layer (G) are in contact, to the position t1. , the distribution concentration C of germanium atoms is
Germanium atoms are contained in the formed first layer (G) while maintaining a constant value of C1, and from the position t1, the concentration C2 is gradually and continuously reduced from the concentration C2 to the interface position tT. At the interface position tT, the distribution concentration C of germanium atoms is C2. In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms gradually and continuously decreases from the concentration C4 from the position TB to the position tT, and reaches the concentration C5 at the position tT. is formed. In the case of FIG. 13, from position tB to position t2, the distribution concentration C of germanium atoms is a constant value of concentration C6, and between position t2 and position tT,
The distribution concentration C is gradually and continuously decreased, and at the position tT, the distribution concentration C is substantially zero (substantially zero here means that it is less than the detection limit amount). In the case of Fig. 14, the distribution concentration C of germanium atoms is C8 from position tB to position tT.
It is gradually decreased more continuously and becomes substantially zero at position tT. In the example shown in FIG. 15, the distribution concentration C of germanium atoms between position tB and position t3 is as follows:
Concentration C9 is a constant value, and at position tT the concentration is
Considered to be C10. Between position t3 and position tT, the distribution density C is linearly decreased from position t3 to position tT. In the example shown in FIG. 16, the distribution concentration C
takes a constant value of concentration C11 from position tB to position t4, and takes a constant value of concentration C11 from position t4 to position tT.
The distribution is said to decrease linearly up to C13. In the example shown in FIG. 17, from position tB to position tT, the distribution concentration C of germanium atoms is
decreases linearly to substantially zero from the concentration C14. In FIG. 18, from position tB to position t5, the distribution concentration C of germanium atoms is the concentration
An example is shown in which the concentration is linearly decreased from C15 to C16, and the concentration C16 is kept at a constant value between position t5 and position tT. In the example shown in FIG. 19, the distribution concentration C of germanium atoms is C17 at the position tB.
Until reaching position t6, the concentration is gradually decreased from this concentration C17, and near the position t6, it is rapidly decreased to the concentration C18 at position t6. Between position t6 and position t7, the concentration decreases rapidly at first, then gradually decreases to C19 at position t7, and between position t7 and position t8, it gradually decreases very slowly. The position has been reduced to
At t8, the concentration C20 is reached. Between position t8 and position tT, the concentration is reduced from C20 to substantially zero according to a curve shaped as shown in the figure. As described above, from FIGS. 11 to 19, the first layer
As described in some of the typical examples of the distribution state of the germanium atoms contained in (G) in the layer thickness direction, in the present invention, the support side has a portion with a high distribution concentration C of germanium atoms. On the interface tT side, the first layer (G) is provided with a distribution state of germanium atoms in which the distribution concentration C is considerably lower than on the support side. The first layer (G) constituting the light-receiving layer constituting the light-receiving member of the present invention preferably has a localized region (G) containing germanium atoms at a relatively high concentration on the support side, as described above. It is desirable to have A). In the present invention, the localized region (A) is desirably provided within 5 μm from the interface position tB, if explained using the symbols shown in FIGS. 11 to 19. In the present invention, the localized region (A) is located at the interface position.
It may be the entire layer region (LT) up to 5μ thick from tB, or it may be a part of the layer region (LT). Whether the localized region (A) is a part or all of the layer region (LT) is appropriately determined depending on the characteristics required of the photoreceptive layer to be formed. The localized region (A) has a distribution state of germanium atoms contained therein in the layer thickness direction, and the maximum distribution concentration Cmax of germanium atoms is preferably 1000 atomic ppm or more, more preferably 5000 atomic ppm or more relative to silicon atoms. ppm or more, optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be obtained. That is, in the present invention, the first layer containing germanium atoms has a layer thickness from the support side.
It is preferable that the layer be formed such that the maximum value Cmax of the distribution concentration exists in the layer region of 5μ or less (from tB to 5μ). The amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) contained in the layer (S) is preferably 1.
~40 atomic%, more preferably 5-30 atomic%,
The optimum range is preferably 5 to 25 atomic%. 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 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 TB 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 that the thickness be ~50μ. The sum (TB+T) of the layer thickness TB of the first layer (G) and the layer thickness T of the second layer (S) is based on the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired when designing the layers of the light-receiving member based on the organic relationship between them. In the light receiving member of the present invention, the above (TB
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-80μ
It is desirable to set it to 50μ. In a more preferred embodiment of the present invention,
The above layer thickness TB and layer thickness T are preferably
When satisfying the relationship TB/T≦1, it is desirable to select appropriate numerical values for each. In selecting the numerical values of layer thickness TB and layer thickness T in the above case, more preferably TB/T≦
It is desirable that the values of the layer thickness TB and the layer thickness T be determined such that the relationship TB/T≦0.9 is satisfied, and optimally TB/T≦0.8. 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, it is desirable that the layer thickness TB of the first layer (G) is made quite thin, preferably
30μ or less, more preferably 25μ or less, optimally 20μ
The following is desirable. In the present invention, specific examples of the halogen atoms (X) contained in the first layer (G) and 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, done by. 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. A glow discharge is generated in the deposition chamber by introducing the germanium atoms under gas pressure, and the distribution concentration of germanium atoms contained on the surface of a predetermined support, which has been set in advance at a predetermined position, is adjusted according to a desired rate of change curve. While controlling a-SiGe (H,
It is sufficient to form a layer consisting of X). In addition, when forming by sputtering method, for example, Ar, He
Using two targets, one made of Si and the other made of Ge, in an atmosphere of an inert gas such as or a mixed gas based on these gases,
Or, when sputtering using a mixed target of Si and Ge, hydrogen atoms (H) may be added as necessary.
Or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. Substances that can be used as raw material gas for supplying Si used in the present invention include 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 , SiGl 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, it is necessary to use a silicon compound containing a halogen atom as a raw material gas capable of supplying Si together with a raw material gas for supplying Ge. 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, for example, Si
Silicon halide, which will be the raw material gas for supply, 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 the desired support by forming a A desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with the gas 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 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 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 ,
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 the 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 among the starting materials () for forming the layer region (G),
Starting material excluding the starting material that becomes the raw material gas for supplying Ge [Starting material for forming the second layer (S) ()]
It 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.
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 a-Si(H, ) may be formed. 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. 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 Pb, 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. 20 shows an example of a light-receiving member manufacturing apparatus. In the gas cylinders 2002 to 2006 in the figure, raw material gas for forming the light receiving member of the present invention is sealed.
is SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ )
Cylinder, 2003 is GeH ₄ gas (99.999% purity,
2004 is _{a SiF 4 gas} (purity 99.99%, hereinafter abbreviated as SiF ₄ ) cylinder, 200
5 is He gas (99.999% purity) cylinder, 2006
is a _H2 gas (99.999% purity) 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, H ₂ gas from 2006 valve 202
2, 2023, 2026 open and outlet pressure gauge 2
Adjust the pressure of 927, 2028, 2031 to 1Kg/cm ² , and inflow valve 2012, 2013, 2016.
Gradually open the mass flow controller 200.
7, 2008, and 2011, respectively. Subsequently, the outflow valve 2017, 2018, 202
1. Gradually open the auxiliary valves 2032 and 2033 to allow each gas to flow into the reaction chamber 2001. At this time, the outflow valve 20 is adjusted so that the ratio of SiH ₄ gas flow rate, GeH ₄ gas flow rate and H ₂ gas flow rate becomes the desired value.
17, 2018, and 2021, and also check the reading of the vacuum gauge 2036 to make sure that the pressure inside the reaction chamber 2001 reaches the desired value.
Adjust the opening of 4. After confirming that the temperature of the base body 2037 is set to a temperature in the range of 50 to 400°C by the heating heater 2038,
The power supply 2040 is set to the desired power and the reaction chamber 20 is
01, and at the same time, the flow rate of GeH ₄ gas is gradually changed by a method such as manual operation or an externally driven motor, etc., to gradually change the opening of the valve 2018 according to a pre-designed rate of change curve. The distribution concentration of germanium atoms contained in the layer is controlled. Glow discharge is maintained for a desired time in the manner described above to form the first layer (G) on the substrate 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 under 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 2037 is preferably rotated at a constant speed by a motor 2039 in order to ensure uniform layer formation. Examples will be described below. Example 1 An Al support (length (L) 357 mm, diameter (r) 80 mm) was
It was machined using a lathe as shown in FIG. 21B. Next, under the conditions shown in Table 1, a-Si:H-based electrophotographic light-receiving members were produced using the deposition apparatus shown in FIG. 20 according to various operating procedures. In addition, for the first layer a-SiGe:H layer, the flow rates of GeH ₄ and SiH ₄ are adjusted as shown in Fig. 22.
GeH ₄ and SiH ₄ mass flow controller 12
36 and 1232 were controlled by a computer (HP9845B). Regarding this light-receiving member for electrophotography, the image exposure apparatus shown in FIG.
Image exposure was carried out using a spot diameter of 80 μm), which was then developed and transferred to obtain an image. No interference fringe pattern was observed in the image in this case, and the image 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. 27, 28, and 29 under the conditions shown in Table 1. In addition, for the first layer a-SiGe:H layer, the flow rates of GeH ₄ and SiH ₄ are adjusted as shown in Fig. 23.
GeH ₄ and SiH ₄ mass flow controller 12
36 and 1232 were controlled by a computer (HP9845B). 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. Example 3 An electrophotographic light-receiving member was formed on a cylindrical Al support having the surface properties shown in FIGS. 27, 28, and 29 under the conditions shown in Table 2. In addition, for the first layer a-SiGe:H layer, the flow rates of GeH ₄ and SiH ₄ are adjusted as shown in Fig. 24.
GeH ₄ and SiH ₄ mass flow controller 12
36 and 1232 were controlled by a computer (HP9845B). 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 this case, no interference fringes were observed in any of the images obtained, and the characteristics were sufficient for practical use. or,
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. 27, 28, and 29 under the conditions shown in Table 2. In addition, for the first layer a-SiGe:H layer, the flow rates of GeH ₄ and SiH ₄ are adjusted as shown in Fig. 25.
GeH ₄ and SiH ₄ mass flow controller 12
36 and 1232 were controlled by a computer (HP9845B). 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 explained in detail above, according to the present invention,
It is suitable for image formation using coherent monochromatic light, is easy to manage, and can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development. , high light sensitivity,
It is possible to provide a light-receiving member that has high signal-to-noise ratio characteristics and electrical contact with the support, and is suitable for digital image recording.

【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 due to scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. FIG. 5 is an explanatory diagram of interference fringes when the interfaces of each layer of the light receiving member are parallel. FIG. 6 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIG. 7 is an explanatory diagram of a comparison of reflected light intensity when the interfaces of each layer of the light-receiving member are parallel and non-parallel. FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. FIG. 9 is an explanatory diagram of the surface condition of each typical support. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIGS. 11 to 19 are explanatory diagrams for explaining the distribution state of germanium atoms in the first layer. FIG. 20 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples.
FIG. 21 is an explanatory diagram of the surface state of the Al support used in the examples. FIG. 22 to FIG. 25 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 26 is an explanatory diagram of the image exposure apparatus used in the example. Fig. 27, Fig. 28, Fig. 2
FIG. 9 is an explanatory diagram of the surface state of the Al support used in Examples. FIG. 30 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, 2601... Electrophotographic light-receiving member, 2602...Semiconductor laser, 2603
...fθ lens, 2604 ...polygon mirror, 2
605... Plan view of the exposure device, 2606... Side view of the exposure device.

Claims (1)

[Claims] 1. The cross-sectional shape at a predetermined cutting position is 0.3 μm to 500 μm.
A support having many convex portions formed on its surface with a convex shape in which sub peaks are superimposed on a main peak with a maximum depth of 0.1 μm to 5 μm, and silicon atoms, germanium atoms, and hydrogen atoms. and/or a halogen atom, and a second layer made of an amorphous material that includes silicon atoms and hydrogen atoms and/or halogen atoms. a photoreceptive layer consisting of a photoreceptor layer, the distribution state of germanium atoms contained in the first layer is non-uniform in the layer thickness direction, and the photoreceptor layer has at least one photoreceptor 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.