JPH0234384B2 - - 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, small and inexpensive He-Ne lasers or semiconductor lasers (usually with an emission wavelength of 650 to 820 nm) are used as lasers.
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 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 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 is a cause of image defects.Especially when forming a mid-tone image with high gradation, the image The unsightly appearance becomes noticeable. Furthermore, as the wavelength range of the semiconductor laser light used becomes longer, the absorption of the laser light in the photosensitive layer decreases, so the above-mentioned interference phenomenon becomes remarkable. This point will be explained with reference to the drawings. FIG. 1 shows light I ₀ incident on a certain layer constituting the light-receiving layer of a light-receiving member, reflected light R ₁ reflected at the upper interface 102, and reflected light R ₂ reflected at the lower interface 101.
It shows. The average layer thickness of the layer is d, the refractive index is n, and the wavelength of light is λ.
If the thickness of a certain layer is uneven with a gradual thickness difference of λ/2n or more, the reflected lights R ₁ and R ₂ will be 2nd =
mλ (m is an integer, reflected light strengthens each other) and 2nd = (m
+1/2) λ (m is an integer, reflected light weakens each other), the amount of absorbed light and transmitted light of a certain layer changes depending on which condition is met. In a light-receiving member with a multilayer structure, the interference effect shown in FIG. 1 occurs in each layer, and as shown in FIG.
A synergistic negative effect of each interference occurs. Therefore, interference fringes corresponding to the interference fringe pattern appear in the visible image transferred and fixed onto the transfer member, causing a defective image. To overcome this inconvenience, diamond cutting the surface of the support allows for
A method of forming a light-scattering surface by providing unevenness (for example, Japanese Patent Application Laid-Open No. 162975/1982), treating the surface of an aluminum support with black alumite, or dispersing carbon, color pigments, or dyes in a resin. (for example, Japanese Patent Application Laid-Open No. 57-165845), the surface of the aluminum support is treated with satin-like alumite, or the surface of the support is formed with fine roughness by sandblasting. A method of providing a light scattering and anti-reflection layer on the
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 exists, 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 layer quality of the formed light-receiving layer is significantly deteriorated. There are disadvantages such as being damaged by the plasma during Si formation, reducing the original absorption function, and having an adverse effect on the subsequent formation of an A-Si based photosensitive 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 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 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, the light-receiving layer 502 is usually deposited along the uneven shape of the surface of the support 501, as shown in FIG. Inclined surface and photoreceptive layer 5
The inclined surface of the unevenness of 02 becomes parallel. 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 , d ₄ of the photoreceptor 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, with high resolution, and with high quality. There is also. Yet another object of the present invention is high photosensitivity,
Another object of the present invention is to provide an electrophotographic light-receiving member having high signal-to-noise ratio characteristics and good electrical contact with a support. Another object of the present invention is to provide an electrophotographic light beam that has excellent durability, continuous repeatability, electrical pressure resistance, usage environment characteristics, mechanical durability, and light reception characteristics in addition to the above-mentioned excellent characteristics. It is also to provide a receiving member. [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 of 0.3 μm to 500 μm at a predetermined cutting position.
A support having a large number of convex portions formed on its surface, each having a convex shape in which sub-peaks are superimposed on a main peak having a maximum depth of 0.1 μm to 5 μm, and silicon atoms, germanium atoms, hydrogen atoms, and/or A first layer made of an amorphous material made of halogen atoms, a second layer made of an amorphous material made of silicon atoms and hydrogen 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 light-receiving layer having a surface layer made of an amorphous material containing atoms, and a distribution state of the germanium atoms contained in the first layer is non-uniform in the layer thickness direction. , the photoreceptive layer 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. In the present invention, on a support (not shown) having an uneven shape smaller than the required resolution of the device, a light-receiving layer with a multilayer structure is provided along the slope of the unevenness,
As shown enlarged in FIG. 6A, the second layer 60
Since the layer thickness of 2 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 R ₁ by the incident light I ₀ and the emitted light R ₃ 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 the pair of interfaces are parallel, the difference in brightness of the interference fringe pattern is smaller than B when they are non-parallel. Become. As a result, the amount of light incident on the minute portions is averaged. This means that the second layer 602, as shown in FIG.
The same can be said even if the layer thickness is macroscopically nonuniform (d ₇ ≠ d ₈ ), so the amount of incident light becomes uniform over the entire layer region (see "D" in FIG. 6). Furthermore, to describe the effect of the present invention in the case where the light-receiving layer has a multilayer structure and coherent light is transmitted from the irradiation side to the second layer, as shown in FIG. For I ₀ , the reflected lights R ₁ , R ₂ , R ₃ , R ₄ ,
_R5 exists. Therefore, in each layer what has been explained above with reference 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, it is preferable that the uneven inclined surface has a mirror finish 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 determined as follows: d ₅ − _{d 6} ≧, where λ is the wavelength of the irradiated light. It is desirable that it is λ/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 at 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) is used to form the layer, since the layer thickness can be precisely controlled at the optical level.
method), optical CVD method, and thermal CVD method. 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 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 to obtain the desired shape. The surface of the support can be precisely cut by fixing it in a predetermined position on a cutting machine and moving it regularly in a predetermined direction while rotating the cylindrical support according to a program designed in advance as desired. By processing, the desired uneven shape, pitch, and depth can be formed. The linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The 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. Further, it is preferable that the convex portion has a plurality of sub-peaks in order to further enhance the effect of the present invention and improve the adhesion between the light-receiving layer and the support. In addition to each of these, in order to efficiently scatter incident light in one direction, the convex portion may be symmetrical (FIG. 9A) or asymmetrical (FIG. 9B) around the main peak.
It is preferable that they be unified. However, in order to increase the degree of freedom in processing control 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 so as to effectively achieve the object of the present invention, taking into consideration the following points. That is, firstly, the A-Si layer constituting the photoreceptive layer is structurally sensitive to the condition of the surface on which the layer is formed, and the layer quality changes greatly depending on the surface condition. Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause a deterioration in the 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 gets 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 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 1.5 μm, most preferably 0.2 μm to 1 μm. The photoreceptive layer in the photoreceptive member of the present invention includes a first layer made of an amorphous material containing silicon atoms and germanium atoms, and a first layer made of an amorphous material containing silicon atoms and exhibiting photoconductivity. Because it has a multilayer structure in which the layer No. 2 and the surface layer are provided in order from the support side, it has extremely excellent electrical, optical,
Shows photoconductive properties, electrical pressure resistance, and usage 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 region, 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 photoresponse. early. 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. The light-receiving layer 1000 includes, from the support 1001 side, a first layer G1002 composed of a-Si (H, It has a layer structure in which a second layer S1003 made of -Si(H,X) and having photoconductivity and a surface layer 1005 are laminated in this order (here, X represents a halogen atom). The germanium atoms contained in the first layer G1002 are continuous in the layer thickness direction of the first layer G1002 and on the side opposite to the side on which the support 1001 is provided (light receiving). Surface layer 1 of layer 1000
The first layer G is distributed so that it is more distributed on the support 1001 side than on the support 1001 side (005 side).
Contained in 1002. 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, the second layer S provided on the first layer G does not contain germanium atoms, and by forming the photoreceptive layer in such a layer structure, The present invention provides 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. 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. Since the change decreases toward the support side, the affinity between the first layer G and the second layer S is excellent, and as will be described later, the distribution concentration C of germanium atoms at the edge of the support can be reduced. By making it extremely large, when a semiconductor laser or the like is used, the first layer G can substantially completely absorb light on the long wavelength side that is almost completely absorbed by the second layer S. This makes it possible to prevent interference due to reflection from the support surface. Furthermore, in the light-receiving member of the present invention, since each of the amorphous materials constituting the first layer G and the second layer S has a common constituent element of silicon atoms, the laminated interface Chemical stability has been sufficiently ensured. 11 to 19 show typical examples of the distribution state of germanium atoms contained in the first layer G of the light-receiving member according to the present invention in the layer thickness direction. 11 to 19, the horizontal axis represents the distribution concentration C of germanium atoms, and the vertical axis represents the first layer G.
, t _B indicates the position of the end surface of the first layer G on the support side, and t _T indicates the position of the end surface of the layer G on the opposite side from the support side. That is, the first layer G containing germanium atoms is formed from the t _B side toward the t _T 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 t _B where the surface on which the first layer G containing germanium atoms is formed and the surface of the _first layer G contact, the germanium The distribution concentration C of atoms is C ₁
The germanium atoms are contained in the first layer G with a constant value, and the concentration is lower than the position _t1 .
It is gradually and continuously decreased from _C2 to the interface position _tT . At the interface position _tT , the distribution concentration C of germanium atoms is _C3 . In the example shown in FIG. 12, the distribution concentration C of the contained germanium atoms is from position t _B to
A distribution state is formed in which the concentration gradually and continuously decreases from C ₄ until reaching t _T and reaches C ₅ at position t _T. 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 the case where it is less than the detection limit amount). In the case of Fig. 14, the distribution concentration C of germanium atoms is gradually decreased continuously from the concentration C ₈ from position t _B to position t _T , and becomes substantially zero at position t _T. . In the example shown in FIG. 15, the distribution concentration C of germanium atoms is a constant value of _C9 between position _tB and position _t3 , and the concentration _C10 at position _tT . be done. Between the position t ₃ and the position t _T , the distribution concentration C is linearly decreased from the position t ₃ to the position t _T . In the example shown in FIG. 16, the distribution concentration C
takes a constant value of concentration C ₁₁ from position t _B to position t ₄ , and from position t ₄ to position t _T the concentration is C ₁₂ to C ₁₃
It is said that the distribution state decreases in a linear function until . In the example shown in Fig. 17, the _position
Up to _tT , the distribution concentration C of germanium atoms decreases linearly from the concentration _C14 to substantially zero. In FIG. 18, the distribution concentration C of germanium atoms from position t _B to position t ₅ is the concentration
The concentration decreases linearly from C ₁₅ to C ₁₆ , and the position
An example is shown in which the concentration C ₁₆ is kept at a constant value between t ₅ and the position t _T. In the example shown in FIG. 19, the distribution concentration C of germanium atoms is a concentration C ₁₇ at a position t _B , and is gradually decreased from this concentration C ₁₇ until reaching a position t ₆ , and then at t ₆ . Near the position, the concentration decreases rapidly to a concentration _C18 at position _t6 . Between position t ₆ and position t ₇ , the concentration is first rapidly decreased, and then gradually decreased to reach C ₁₉ at position t ₇ , and between position t ₇ and t ₈ , very slowly and gradually decreased to position t ₈
At , a concentration of C ₂₀ 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 with reference to FIGS. 11 to 19, some typical examples of the distribution state of germanium atoms contained in the first layer G in the layer thickness direction, in the present invention, on the support side , the first layer G has a portion where the distribution concentration C of germanium atoms is high, and the distribution state of germanium atoms has a portion where the distribution concentration C is considerably lower on the interface _tT side than on the support side. It is set in. The first layer G constituting the light-receiving layer constituting the receiving member in the present invention preferably has a localized region A containing germanium atoms at a relatively high concentration on the support side, as described above. is desirable. In the present invention, the localized region A is desirably provided within 5μ from the interface position _tT , as 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 L _T up to 5μ thick from t _B , or it may be a part of the layer region L _T. Whether the localized area A is a part or all of the layer area L _T is determined as appropriate depending on the characteristics required of the photoreceptive layer to be formed. 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. , optimally 1×
It is desirable to form a layer so that a distribution state of 10 ⁴ atomic ppm or more can be achieved. That is, in the present invention, the first layer containing germanium atoms has a layer thickness from the support side.
It is preferable to form the layer so that the maximum value Cmax of the distribution concentration exists within 5μ (a layer region of 5μ from t _B ). In the present invention, the amount of hydrogen atoms (H), the amount of halogen atoms (X), or the sum of the amounts of hydrogen atoms and halogen atoms contained in the second layer S constituting the photoreceptive layer to be formed (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 %. 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 adequately provided. 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 40 μ,
Optimally, the thickness is preferably 50 Å to 30 μ. Further, the layer thickness T of the second layer S is preferably 0.5 to
It is desirable that the thickness be 90μ, more preferably 1 to 80μ, most preferably 2 to 50μ. The sum of the layer thickness T _B of the first layer G and the layer thickness T of the second layer S (T _B +T) is based on the mutual relationship between the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. Based on the organic relationship between them, they are determined as desired when designing the layers 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
It is desirable that appropriate numerical values be selected for each so as to satisfy the relationship T _B /T≦1. In the selection of the 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, 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, chlorine, bromine, and iodine. Among them, fluorine and chlorine are particularly preferred. In the present invention, the first layer G composed of a-SiGe (H, It is accomplished by doing so. For example, by the glow discharge method, a
- To form the first layer G composed of SiGe (H, Possible raw material gas for supplying Ge and raw material gas for introducing hydrogen atoms (H) as necessary or/
and introducing a raw material gas for introducing halogen atoms (X) into a deposition chamber whose interior can be reduced in pressure at a desired gas pressure to generate a glow discharge within the deposition chamber;
While controlling the distribution concentration of germanium atoms contained on the surface of a predetermined support that has been placed at a predetermined position in advance according to a desired rate of change curve, a-SiGe
A layer consisting of (H,X) may be formed. or,
For example, when forming by sputtering method,
Using two targets, one made of Si and the other made of Ge, in an atmosphere of inert gas such as Ar, 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 sputtering deposition chamber as necessary. Substances that can be used as raw material gas for supplying Si used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Gaseous silicon hydride (silanes) such as Si ₄ H ₁₀ , which can be gasified or gasified, can be effectively used, especially because of its ease of handling during layer creation work, good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Substances that can be used as raw material gas for Ge supply include:
GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and other germanium hydrides in a gaseous state or that can be gasified are mentioned as those that can be effectively used, especially during layer formation work. GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred in terms of ease of handling, good Ge supply efficiency, and the like. Effective raw material gases for introducing halogen atoms used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into Furthermore, silicon hydride compounds containing halogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and halogen atoms as constituent elements, can also be mentioned as effective in the present invention. Specifically, halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine,
Iodine halogen gas, BrF, ClF, ClF ₃ ,
Examples include interhalogen compounds such as BrF ₅ , BrF ₃ , IF ₃ , IF ₅ , 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 a silicon compound containing such a halogen atom is used to form the characteristic light-receiving member of the present invention by a glow discharge method, the raw material gas that can supply Si together with the raw 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 silicon hydride gas. When creating the first layer G containing halogen atoms according to the glow discharge method, basically, for example, Si
Silicon halide and Ge as raw material gas for supply
germanium hydride, which is the raw material gas for supply;
Gases such as Ar, H ₂ , He, etc. are introduced into the deposition chamber where the first layer G is to be formed 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
In order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. Moreover, each gas may be used not only as a single species but also as a mixture of a plurality of them at a predetermined mixing ratio. To form the first layer G made of a-SiGe (H, In the case of ion plating, for example, polycrystalline silicon or monocrystalline silicon and polycrystalline germanium can be sputtered in a desired gas plasma atmosphere using two sheets or a target consisting of Si and Ge. Alternatively, 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 electron beam method (EB method), and the flying evaporates are passed through a desired gas plasma atmosphere. It can be done by letting it happen. 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 ,
Gaseous or gasifiable substances such as germanium halides such as GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be mentioned as useful starting materials for forming the first layer G. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the first layer G. 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), the amount of halogen atoms (X), or the amount of hydrogen atoms and halogen atoms contained in the first layer G constituting the photoreceptive layer to be formed is The sum (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),
Alternatively, the amount of the starting material used to contain the halogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer S composed of a-Si (H, It can be performed according to the same method and conditions as when forming the first layer G using the starting material [starting material for forming the second layer S] excluding the starting material that becomes a gas. . That is, in the present invention, to form the second layer S composed of a-Si(H, It is done by law. For example, in order to form the second layer S composed of a-Si (H, Along with raw material gas,
If necessary, a raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber. A layer made of a-Si(H,X) may be formed on the surface of a predetermined support placed at a predetermined position. In addition, when forming by sputtering, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. In the light receiving member 1004 shown in FIG. 10, the surface layer 1 formed on the second layer 1003 is
005 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeatability, electrical pressure resistance, use environment characteristics, mechanical durability, and light reception characteristics. The surface layer 1005 in the present invention is an amorphous material (hereinafter referred to as " a−(Si _x C ₁ − _x ) _y (H,X)
₁ − _y ”. However, 0<x<1 and 0<y≦
It consists of 1). The surface layer 1005 composed of a-(Si _x C _{1 - x} ) _y ( _H ,
This is done by CVD method, sputtering method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. A surface layer 1 in which carbon atoms and halogen atoms are formed together with silicon atoms, which makes it relatively easy to control the manufacturing conditions for manufacturing a light-receiving member having
The glow discharge method or the sputtering method is preferably employed because of the advantages that it can be easily introduced into the 005. Furthermore, in the present invention, the surface layer 1005 may be formed using a glow discharge method and a sputtering method in the same apparatus system. To form the surface layer 1005 by the glow discharge method, _the raw material gas for forming a-(Si _x C ₁ - _x ) _y ( _H , A layer is formed on the support by mixing the gas in a mixing ratio of Above a-(Si _x C ₁ - _x ) _y (H,
X) ₁ − _y should be deposited. In the present invention, a-(Si _x C ₁ - _x ) _y (H,X) ₁
- The raw material gas for forming _{the y-} shape is a gaseous substance whose constituent atoms are at least one of silicon atoms (Si), carbon atoms (C), hydrogen atoms (H), and halogen atoms (X), or Most gasified substances that can be gasified can be used. When using a raw material gas containing Si as one of Si, C, H, and X, for example, Si
A raw material gas containing C as a constituent atom, a raw material gas containing C as a constituent atom, and, if necessary, a raw material gas containing H as a constituent atom or/and a raw material gas containing X as a constituent atom, at a desired mixing ratio. Use a mixture or
A raw material gas containing Si as a constituent atom and a raw material gas containing C and H as constituent atoms or/and a raw material gas containing C and X as constituent atoms are mixed at a desired mixing ratio, or Alternatively, a raw material gas containing Si as a constituent atom and a raw material gas containing Si, C, and H as constituent atoms, or a raw material gas containing Si, C, and X as constituent atoms are mixed and used. can do. Alternatively, a raw material gas containing Si and H as constituent atoms may be mixed with a raw material gas containing C as constituent atoms, or a raw material gas containing Si and X as constituent atoms may be mixed with C. The raw material gases used as constituent atoms may be mixed and used. In the present invention, preferred halogen atoms (X) contained in the surface layer 1005 are F,
Cl, Br, and I, with F and Cl being particularly preferred. In the present invention, raw material gases that can be effectively used to form the surface layer 1005 include gaseous materials or substances that can be easily gasified at room temperature and pressure. . In the present invention, gases such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H, etc. whose constituent atoms are Si and H are effectively used as the raw material gas for forming the surface layer 1005. Silicon hydride gas such as silanes, saturated hydrocarbons containing C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms,
Examples include acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogens, hydrogen halides, interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ),
Propane (C ₃ H ₈ ), n-butane (n-C ₄ H), pentane (C ₅ H), ethylene hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H), acetylene hydrocarbons such as acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI,
HCl, HBr, interhalogen compounds include BrF,
ClF, ClF ₃ , ClF ₅ , BrF ₅ , BrF ₃ , IF ₇ , IF ₅ ,
ICl, IBr, silicon halides include SiF ₄ ,
Si ₂ F ₆ , SiCl ₃ Br, SiCl ₂ Br ₂ , SiClBr ₃ , SiCl ₃ I,
As SiBr ₄ , halogen-substituted silicon hydride,
SiH ₂ F ₂ , SiH ₂ Cl ₃ , SiH ₃ Cl, SiH ₃ Br, SiH ₃ Br,
SiH ₂ Br ₂ , SiHBr ₃ , as silicon hydride, SiH ₄ ,
Silanes such as Si ₂ H ₈ , Si ₃ H ₈ , Si ₄ H,
etc. can be mentioned. In addition to these, CF ₄ , CCl ₄ , CBr ₄ , CHF ₃ ,
CH ₂ F ₂ , CH ₃ F, CH ₃ Cl, CH ₃ Br, CH ₃ I,
Halogen-substituted paraffinic hydrocarbons such as C ₂ H ₅ Cl, fluorinated sulfur compounds such as SF ₄ and SF ₆ , Si
Alkyl silicides such as (CH ₃ ) ₄ , Si(C ₂ H ₅ ) ₄ , and SiCl
Silane derivatives such as halogen-containing alkyl silicides such as (CH ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ and SiCl ₃ CH ₃ can also be mentioned as effective. These surface layer 1005 forming substances are used to form the surface layer 1005 so that the formed surface layer 1005 contains silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. They are selected and used as desired during formation. For example, Si(CH ₃ ) ₄ can easily contain silicon atoms, carbon atoms, and hydrogen atoms and can form a layer with desired characteristics, and SiHCl ₃ can contain halogen atoms. _{A- ( Si _ x} C ₁ −
A surface layer 1005 consisting of _x )(Cl+H) ₁ - _y can be formed. To form the surface layer 1005 by the sputtering method, target a single-crystal or polycrystalline Si wafer, a C wafer, or a wafer containing a mixture of Si and C, and process these as necessary. This may be carried out by sputtering in various gas atmospheres containing halogen atoms and/or hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, raw material gases for introducing C, H and/or The Si wafer may be sputtered by forming plasma. Alternatively, a gas atmosphere containing hydrogen atoms and/or halogen atoms can be created as necessary by using Si and C as separate targets or by using a mixed target of Si and C. This is done by sputtering inside. As the material gas for introducing C, H, and X, the material for forming the surface layer 1005 shown in the glow discharge example described above can be used as an effective material also in the sputtering method. In the present invention, the diluent gas used when forming the surface layer 1005 by a glow discharge method or a sputtering method is a so-called rare gas, for example,
Preferred examples include He, Ne, Ar, and the like. The surface layer 1005 in the present invention is carefully formed to provide the desired properties. In other words, substances containing Si, C, and optionally H or/and In the present invention, it exhibits properties ranging from semiconducting to insulating, and from photoconductive to non-photoconductive.
a-(Si _x C ₁ − _x ) having desired properties depending on the purpose
The preparation conditions are strictly selected according to the desired conditions so that _y (H,X) ₁ - _y is formed. for example,
In order to provide the surface layer 1005 with the main purpose of improving electrical voltage resistance, a-(Si _x C ₁ - _x ) _y (H,X) ₁
- _y is made as an amorphous material with pronounced electrically insulating behavior in the environment of use. In addition, when the surface layer 1005 is provided with the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment, the above-mentioned degree of electrical insulation is relaxed to some extent, and the surface layer 1005 is made of a non-woven material having a certain degree of sensitivity to the irradiated light. As a crystalline material a-(Si _x C ₁ - _x ) _y (H,X)
₁ − _y is created. a-(Si _x C ₁ - _x ) _y (H,X) ₁ - _y on the surface of the second layer
When forming the surface layer 1005 consisting of a−(Si _x C ₁ − _x ) _y
It is desirable that the temperature of the support during layer formation be strictly controlled so that (H,X) ₁ - _y can be formed as desired. In the present invention, the formation of the surface layer 1005 is carried out by appropriately selecting the optimum range in accordance with the method of forming the surface layer 1005 in order to effectively achieve the desired purpose. Desirably, the temperature is 400°C, more preferably 50-350°C, optimally 100-300°C. For forming the surface layer 1005, glow discharge method and sputtering method are used because delicate control of the composition ratio of atoms constituting the layer and control of layer thickness are relatively easy compared to other methods. Adoption of the ring method is advantageous, but when forming the surface layer 1005 by these layer forming methods, the discharge power during layer formation is created in the same manner as the support temperature described above _. C ₁ − _x ) _y (H, X) is one of the important factors that influences the characteristics of ₁ − _y . As a discharge _power condition for effectively producing a-( _{Si x} C ₁ - _x ) _y (H, is preferably 10~1000W, more preferably 20~
It is desirable that the power be 750W, and optimally 50 to 650W. The gas pressure in the deposition chamber is preferably about 0.01 to 1 Torr, more preferably about 0.1 to 0.5 Torr. In the present invention, the above-mentioned values are listed as the preferable numerical ranges of the support temperature and discharge power for creating the surface layer 1005, but these layer creation factors are independently and separately It is not determined, but the desired characteristic a-(Si _x C ₁ − _x )
It is desirable that the optimum value of each layer formation factor be determined based on mutual organic relationship so that a surface layer 1005 consisting of y (H,X _{) 1} - _y is formed. The amount of carbon atoms contained in the surface layer 1005 in the light-receiving member of the present invention is the same as the conditions for forming the surface layer 1005, so that the surface layer 1005 can be formed to obtain the desired characteristics to achieve the object of the present invention. This is an important factor. The amount of carbon atoms contained in the surface layer 1005 in the present invention is determined as desired depending on the type and characteristics of the amorphous material constituting the surface layer 1005. That is, the general formula a-(Si _x C ₁ - _x ) _y (H,X) ₁
- The amorphous material indicated by _y can be broadly classified as an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C ₁ - _a ". However, 0<a <
1), an amorphous material composed of silicon atoms, carbon atoms, and hydrogen atoms (hereinafter referred to as "a-(Si _b C ₁ - _b ) _c H _1
−c ”. However, 0<b, c<1), an amorphous material (hereinafter referred to as "a-
(Si _d C ₁ − _d ) _e (H,X) ₁ − _e ”. However, 0<d,
e<1). In the present invention, the surface layer 1005 is a-Si _a C ₁
- _a , the amount of carbon atoms contained in the surface layer 1005 is preferably from 1×10 ⁻³ to
It is desirable that the content be 90 atomic %, more preferably 1 to 80 atomic %, most preferably 10 to 75 atomic %. That is, if expressed as a in a-Si _a C _1-a above, a is preferably 0.1 to 0.99999, more preferably 0.2 to 0.99, and optimally 0.25 to 0.9. In the present invention, the surface layer 1005 is a-(Si _b C ₁
- _b ) When composed of _c H ₁ - _c , the amount of carbon atoms contained in the surface layer 1005 is preferably 1 x 10 ^-3
~90 atomic%, more preferably 1~
It is desirable that it be 90 atomic %, optimally 10 to 80 atomic %. The content of hydrogen atoms is preferably 1 to 40 atomic%, more preferably 2 to 35 atomic%, and optimally 5 to 30 atomic%.
It is desirable that the hydrogen content be within these ranges, and the light-receiving member formed when the hydrogen content is in this range can be sufficiently applied as an excellent material in practice. That is, in the expression a-(Si _b C ₁ - _b ) _c H ₁ - _c , b is preferably 0.1 to 0.99999, more preferably 0.1 to 0.99, optimally 0.15 to 0.9, It is desirable that c is preferably 0.6 to 0.99, more preferably 0.65 to 0.98, optimally 0.7 to 0.95. The surface layer 1005 is a-(Si _d C ₁ - _d ) _e (H,X)
₁ - _e , the content of carbon atoms contained in the surface layer 1005 is preferably 1 x 10 ^-3 to 90 atomic%, more preferably 1
It is desirable that it be ~90 atomic%, optimally 10-80 atomic%. The content of halogen atoms is preferably 1 to 20 atomic%, and the light-receiving member produced when the halogen atom content is within this range can be sufficiently applied to practical applications. It is. The content of hydrogen atoms, which may be included as necessary, is preferably 19 atomic % or less, more preferably 13 atomic %. That is, d of the previous a-(Si _d C ₁ - _d ) _e (H,X) ₁ - _e ,
If expressed as e, d is preferably 0.1 to
0.99999, more preferably 0.1-0.99, optimally
0.15 to 0.9, preferably e is 0.8 to 0.99, more preferably 0.82 to 0.99, most preferably 0.85 to 0.98. The numerical range of the layer thickness of the surface layer 1005 in the present invention is one of the important factors for effectively achieving the object of the present invention. In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose. In addition, the layer thickness of the surface layer 1005 is determined based on the relationship between the amount of carbon atoms contained in the layer and the layer thicknesses of the first layer and the second layer, as required for each layer region. It needs to be appropriately determined as desired based on organic relationships depending on the characteristics. In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production. The thickness of the surface layer 1005 in the present invention is preferably 0.003 to 30μ, preferably 0.004 to 20μ, and optimally 0.005 to 10μ. The surface layer 1005 can mainly function as a protective layer for mechanical durability and as an optically antireflection layer. The surface layer 1005 is suitable to function as an antireflection layer when the following conditions are met. That is, if the refractive index of the surface layer 1005 is n, the layer thickness is d, and the wavelength of the incident light is λ, then when d=λ/4n or an odd multiple thereof, the surface layer is suitable as an antireflection layer. There is. Also, when the refractive index of the second layer is na, when the refractive index n of the surface layer satisfies n=√, and the layer thickness d of the surface layer is d=λ/4n or an odd multiple thereof, The surface layer is most suitable as an antireflection layer. When a-Si:H is used as the second layer, the refractive index of a-Si:H is about 3.3, so a material with a refractive index of 1.82 is suitable for the surface layer. a-Si:H can be made to have such a refractive index by adjusting the amount of C, and can also fully satisfy mechanical durability, interlayer adhesion, and electrical properties. Therefore, it is the most suitable material for the surface layer. In addition, when placing emphasis on the role of the surface layer 1005 as an antireflection layer, the layer thickness of the surface layer is as follows:
More preferably, the thickness is 0.05 to 2 μm. The support used in the present invention may be electrically conductive or electrically insulating. Examples of conductive supports include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the light-receiving member 1004 in FIG. If used as a receiving member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is appropriately determined so as to form a desired light-receiving member, 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 described. FIG. 20 shows an example of a light-receiving member manufacturing apparatus. In the diagram, gas cylinders from 2002 to 2006 have
The raw material gas for forming the light-receiving member of the present invention is sealed, for example, 2002
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 _H2 gas (99.999% purity) cylinder, 2045 is
It is a CH ₄ gas (99.999% purity) cylinder. To allow these gases to flow into the reaction chamber 2001, make sure that the valves 2022 to 2026, 2044 of the gas cylinders 2002 to 2006, 2045, and the leak valve 2035 are closed, and also close the inflow valves 2012 to 2016, 2043, and the outflow valve. After confirming that the auxiliary valves 2017 to 2021 and 2041 and the auxiliary valves 2032 and 2033 are open, the main valve 2034 is first opened 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 and 2041 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 2037, a gas cylinder 2037 is used.
SiH ₄ gas from 002, 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 027, 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 the 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 substrate 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 200 is heated.
1, and at the same time, the flow rate of GeH ₄ gas is gradually changed by manual or external drive motor, etc. to gradually change the opening of the valve 2018 according to a pre-designed gas change rate curve. The distribution concentration of germanium atoms contained in the formed layer is controlled. Glow discharge is maintained for a desired time in the manner described above to form the first layer G on the base 2037 to a desired layer thickness. At the stage where the first layer G has been formed to a desired layer thickness, the steps are performed except for completely closing the outflow valve 2018 and changing the discharge conditions as necessary.
By maintaining glow discharge for a desired time under similar conditions and procedures, it is possible to form a second layer S substantially free of germanium atoms on the first layer G. After forming the second layer S, the second layer S is formed by maintaining glow discharge for a desired time under the same conditions and procedures except for setting the mass flow controllers 2007 and 2042 to a predetermined flow rate ratio. layer S of
A surface layer mainly composed of silicon atoms and carbon atoms can be formed thereon to a desired thickness. During layer formation, it is desirable that the substrate 2037 be rotated at a constant speed by a motor 2039 in order to ensure uniform layer formation. Examples will be described below. Example 1 Al support (length (L) 357 mm, diameter (r) 80 mm)
was machined using a lathe to give the surface texture as shown in FIG. 21B. Next, using the deposition apparatus shown in FIG. 20 and following various operating procedures under the conditions shown in Table 5, A-Si was deposited.
An electrophotographic light-receiving member was deposited on the aforementioned Al support. Note that the first layer a-(Si:Ge):H layer is GeH ₄
GeH ₄ and SiH ₄ mass flow controllers 2007 and 2008 were controlled by a computer (HP9845B) so that the flow rates of GeH 4 and SiH ₄ were as shown in FIG. Incidentally, the surface layer was deposited as follows. After the second layer is deposited, as shown in Table 5, the flow rate ratio of CH ₄ gas flow rate to SiH ₄ gas flow rate is SiH ₄ /CH ₄
= 1/30, and set the mass flow controller corresponding to each gas to 0.5μm with high frequency power of 150W.
A thick a-SiC(H) was deposited. The surface condition of the A-Si:H electrophotographic light-receiving member thus produced was as shown in FIG. 21C. Regarding the light-receiving members for electrophotography as described above,
Image exposure device shown in Figure 26 (laser light wavelength
Perform image exposure at 780 nm, spot diameter 80 μm),
It was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 2 After depositing up to the second layer in the same manner as in Example 1,
The hydrogen (H ₂ ) cylinder was replaced with an argon (Ar) gas cylinder, the deposition apparatus was cleaned, and a sputtering target made of Si and a sputtering target made of graphite were placed on the cathode electrode so that the area ratio was the same as Sample No. 1 in Table 1. 101. The light-receiving member is installed, and the pressure inside the deposition apparatus is sufficiently reduced using a diffusion pump. After that, argon gas was introduced to 0.015torr and high frequency power was 150W.
The surface layer of Sample No. 101 in Table 1 was deposited on the support by sputtering the surface material by generating a glow discharge. In the same way, by changing the area ratio of Si and graphite targets, the surface layer was
A light-receiving member was produced in the same manner as above except that it was formed as shown in FIG. Each of the electrophotographic light-receiving members thus obtained was image-exposed with a laser in the same manner as in Example 1, and after repeating the process up to transfer approximately 50,000 times, image evaluation was performed. I got similar results. Example 3 The same method as Example 1 was used except that when forming the surface layer, the flow rate ratio of SiH ₄ gas and CH ₄ gas was changed to change the content ratio of silicon atoms and carbon atoms in the surface layer. Each of the light-receiving members for electrophotography was manufactured using the following methods. Each of the electrophotographic light-receiving members thus obtained was image-exposed with a laser in the same manner as in Example 1, and after repeating the process up to transfer approximately 50,000 times, image evaluation was performed. I got similar results. Example 4 When forming the surface layer, SiH ₄ gas, SiF ₄ gas, CH ₄
Each of the electrophotographic light-receiving members was produced in the same manner as in Example 1 except that the gas flow rate ratio was changed to change the content ratio of silicon atoms and carbon atoms in the surface layer. Each of the electrophotographic light-receiving members thus obtained was image-exposed with a laser in the same manner as in Example 1, and after repeating the process up to transfer approximately 50,000 times, image evaluation was performed. I got similar results. Example 5 Electrophotographic light-receiving members were produced in the same manner as in Example 1 except that the thickness of the surface layer was changed. For each of the electrophotographic light-receiving members thus obtained, the steps of image formation, development, and cleaning were repeated in the same manner as in Example 1, and the results shown in Table 4 were obtained. Example 6 An electrophotographic light-receiving member was prepared in the same manner as in Example 1 except that the discharge power during the preparation of the surface layer was 300 W and the average layer thickness was 2 μm. The average layer thickness difference between the surface layer of the electrophotographic light-receiving member thus obtained was 0.5 μm between the center and both ends.
Furthermore, the difference in layer thickness at minute portions was 0.1 μm. No interference fringes were observed in such an electrophotographic light-receiving member, and although the steps of image formation, development, and cleaning were repeated using the same apparatus as in Example 1, the result was sufficient for practical use. Example 7 An electrophotographic light-receiving member was formed on a cylindrical Al support having the surface properties shown in FIGS. 27, 28, and 29 in the same manner as in Example 1 under the conditions shown in Table 5. . Note that the first layer a-(Si:Ge):HB layer is
GeH ₄ and SiH ₄ mass flow controllers 2007 and 2008 were controlled by a computer (HP9845B) so that the flow rates of GeH ₄ and SiH ₄ were as shown in FIG. 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. This image forming process was repeated 100,000 times. No interference fringes were observed in any of the images obtained in this case, 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 8 A light-receiving member for electrophotography was prepared in the same manner as in Example 1 on a cylindrical Al support having the surface properties shown in FIGS. 27, 28, and 29, except that the conditions shown in Table 6 were used. was formed. Note that the first layer a-(Si:Ge):HB layer is
GeH ₄ and SiH ₄ mass flow controllers 2007 and 2008 were controlled by a computer (HP9845B) so that the flow rates of GeH ₄ and SiH ₄ were as shown in FIG. 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. This image forming process was repeated 100,000 times. No interference fringes were observed in any of the images obtained in this case, 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 9 A light-receiving member for electrophotography was prepared in the same manner as in Example 1, except that the conditions shown in Table 6 were used on a cylindrical Al support with the surface properties shown in FIGS. 27, 28, and 29. was formed. Note that the first layer a-(Si:Ge):HB layer is
GeH ₄ and SiH ₄ mass flow controllers 2007 and 2008 were controlled by a computer (HP9845B) so that the flow rates of GeH ₄ and SiH ₄ were as shown in FIG. 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. This image forming process was repeated 100,000 times. No interference fringes were observed in any of the images obtained in this case, 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.

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use ×〓Produces image defects

[Table] ◎〓Very good ○〓Good △〓Sufficient for practical use
× = Causes image defects

【table】

【table】

[Table] [Effects of the invention] As explained in detail above, 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. A light-receiving member having excellent mechanical durability, particularly abrasion resistance, and light-receiving properties can be provided.

[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 a typical support. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. Figures 11 to 19 are
FIG. 3 is an explanatory diagram for explaining the distribution state of germanium atoms in the layer. FIG. 20 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. Second
FIG. 1 is an explanatory diagram of the surface state of the Al support used in Examples. FIG. 22 to FIG. 25 are explanatory diagrams showing changes in gas flow rate in the example. FIG. 26 shows an image exposure apparatus used in the example. FIG. 27, FIG. 28, and FIG. 29 are explanatory diagrams of the surface state of the Al support used in the 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... Surface layer, 2601... Light for electrophotography receiving member, 260
2... Semiconductor laser, 2603... fθ lens,
2604... Polygon mirror, 2605... Plan view of exposure device, 2606... Side view of exposure device.

Claims (1)

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