JPH0235300B2 - - 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 for recording digital image information as an image, an electrostatic latent image is formed by optically scanning a light-receiving member with a laser beam modulated according to the digital image information, and then the latent image is A well-known method is to record an image by performing processing such as development, transfer and fixing as necessary. In particular, in image forming methods using electrophotography, the laser used is a small and inexpensive He-Ne laser or semiconductor laser (usually with an emission wavelength of 650 to 820 nm).
It is common to record images using . In particular, as a light-receiving material for electrophotography that is suitable when using a semiconductor laser, in addition to the fact that the consistency of the photosensitivity region is much better than that of other types of light-receiving materials, the Vickers hardness is is high,
For example, Japanese Patent Application Laid-Open No. 1983-1989 is non-polluting from a social perspective.
Amorphous materials containing silicon atoms (hereinafter referred to as "a
-Si) is attracting attention. Naturally, if the photoreceptive layer is a single-layer a- ^Si layer, 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. Reflected from the free surface of the laser beam irradiation side, each layer constituting the light-receiving layer, and the layer interface between the support and the light-receiving layer (hereinafter, both the free surface and the layer interface are collectively referred to as the "interface"). Each of the incoming reflected lights can cause interference. This interference phenomenon appears as a so-called interference fringe pattern in the formed visible image and becomes a cause of image defects. Particularly when forming a mid-tone image with high gradation, the image becomes noticeably difficult to see. Furthermore, as the wavelength region of the semiconductor laser light used becomes longer, the absorption of the laser light in the photoreceptive layer decreases, so the above-mentioned interference phenomenon is remarkable. This point will be explained with reference to the drawings. FIG. 1 shows light I _p 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, these conventional methods have not been able to completely eliminate interference fringe patterns appearing on images. In other words, in the first method, only a large number of irregularities of a specific size are provided on the surface of the support, so although it is true that the appearance of interference fringes due to light scattering effects is prevented, as for light scattering, Since the specularly reflected light component still remains, in addition to the remaining interference fringe pattern due to the specularly reflected light, the irradiation spot spreads due to the light scattering effect on the support surface, resulting in a substantial This was a 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. It has disadvantages such as being damaged by the plasma during the formation of the Si layer, reducing its original absorption function, and having an adverse effect on the subsequent formation of the a-Si layer due to deterioration of the surface condition. In the case of the third method of irregularly roughening the surface of the support, as shown in _FIG .
The _remaining light enters the light receiving layer 302 and becomes transmitted light _I1 . The transmitted light I ₁ is transmitted through the support 30
On the surface of 2, part of the light is scattered and becomes diffused light K ₁ , K ₂ , K ₃ ..., the rest is specularly reflected and becomes reflected light R ₂ , and part of it becomes emitted light R ₃ . Get older and go outside. Therefore, since the emitted light _R3 , which is a component that interferes with the reflected light _R1 , remains, the interference fringe pattern cannot be completely erased. Furthermore, if the diffusivity of the surface of the support 301 is increased in order to prevent interference and multiple reflections inside the light-receiving layer, the resolution will decrease because light will diffuse within the light-receiving layer and cause halation. There was also the drawback of doing so. In particular, in a multilayered light receiving member, the fourth
As shown in the figure, even if the surface of the support 401 is irregularly roughened, the reflected light R ₂ on the surface of the first layer 402,
The reflected light R ₁ from the second layer and the specularly reflected light R ₃ from the surface of the support 401 interfere with each other, resulting in an interference fringe pattern depending on the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it has been impossible to completely prevent interference fringes by irregularly roughening the surface of the support 401. Furthermore, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies greatly between lots, and even within the same lot, the degree of roughness is uneven. , there was a problem with manufacturing management. In addition, relatively large protrusions are frequently formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer. Furthermore, if the surface of the support 501 is simply roughened regularly, as shown in FIG. The sloped surface of the light-receiving layer 502 becomes parallel to the sloped surface of the unevenness of the light-receiving layer 502. Therefore, in that part, the incident light is 2nd ₁ = mλ
Or, 2nd ₁ = (m+1/2)λ holds true, resulting in a bright area or a dark area, respectively. In addition, there is non-uniformity in the layer thickness in the entire photoreceptive layer, such that the maximum difference among the respective layer thicknesses d ₁ , d ₂ , d ₃ , and d ₄ of the photoreceptive layer is λ/2n or more. A pattern of light and dark stripes appears. Therefore, simply by regularly roughening the surface of the support 501, it is not possible to completely prevent the occurrence of interference fringes. Furthermore, even when a multi-layered light-receiving layer is deposited on a support whose surface is regularly roughened, the specularly reflected light on the surface of the support as explained for the single-layered light-receiving member in FIG. In addition to the interference with the reflected light on the surface of the light-receiving layer, interference due to the reflected light at the interface between each layer is added, so that the degree of interference fringe pattern development becomes more complicated than that of a light-receiving member with a single-layer structure. OBJECTS OF THE INVENTION It is an object of the present invention to provide a new light-sensitive electrophotographic light-receiving member which eliminates the above-mentioned drawbacks. Another object of the present invention is to provide a light-receiving member for electrophotography that is suitable for image formation using coherent monochromatic light and that is easy to manage. 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 speckles during reversal development. . Another object of the present invention is to provide an electrophotographic light-receiving member that has high electrical pressure resistance and photosensitivity, and has excellent electrophotographic properties. Yet another object of the present invention is that the concentration is high;
Another object of the present invention is to provide a light-receiving member for electrophotography that is suitable for electrophotography and is capable of obtaining high-quality images with clear halftones and high resolution. [Summary of the Invention] The light-receiving member for electrophotography of the present invention (hereinafter referred to as "light-receiving member") has a cross-sectional shape at a predetermined cutting position with a pitch of 0.3 μm to 500 μm, and a maximum depth of 0.1 μm to 5 μm. An amorphous material consisting of a support having a large number of convex portions formed on its surface in which a sub-peak is superimposed on a main peak, and a silicon atom, a germanium atom, and a hydrogen atom and/or a halogen atom. A photoreceptive layer consisting of a first layer made of a material, a second layer made of an amorphous material made of silicon atoms, hydrogen atoms and/or halogen atoms, The photoreceptive layer also contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and also contains a substance that controls conductivity in at least one of the first layer and the second layer. and the distribution state of the substance is uniform in the layer thickness direction in the layer region where the substance is contained, and the photoreceptive layer has at least one pair of non-parallel interfaces within the short range. do. The present invention will be specifically described below with reference to the drawings. FIG. 6 is an explanatory diagram for explaining the basic principle of the present invention. The present invention has a light-receiving layer having a multilayer structure along the slope of the unevenness on a support (not shown) having an uneven shape smaller than the required resolution of the device, and the light-receiving layer is shown in FIG. As shown in the enlarged part of
Since the layer thickness of the second layer 602 changes continuously from _d5 to _d6 , the interface 603 and the interface 604 have an inclination to each other. Therefore, the coherent light incident on this minute portion (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 and the emitted light R ₃ with respect to the incident light I _p have different traveling directions, as shown in A in FIG. 7, 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. It becomes uniform (see "D" in Figure 6). Furthermore, to describe the effects of the present invention in the case where coherent light is transmitted from the irradiation side to the second layer when the light-receiving layer has a multilayer structure, as shown in FIG. For I _p , the reflected lights R ₁ , R ₂ , R ₃ ,
R ₄ and R ₅ exist. Therefore, in each layer, what has been described above similar to FIG. 7 occurs. Therefore, when considering the entire photoreceptive layer, interference is a synergistic effect in each layer, so according to the present invention, as the number of layers constituting the photoreceptive layer increases, the interference effect is further prevented. I can do it. Further, interference fringes generated within a minute portion do not appear in the image because the size of the minute portion is smaller than the irradiation light spot diameter, that is, smaller than the resolution limit. Moreover, even if it appears in the image, it will not cause any substantial trouble because it is below the resolution of the eye. In the present invention, the uneven inclined surface is desirably mirror-finished in order to reliably align the reflected light in one direction. The size 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 the microscopic portion l of the multilayer photoreceptive layer (hereinafter referred to as "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. In order to more effectively and easily achieve the object of the present invention, plasma gas is used to form the first layer and second layer constituting the photoreceptive layer because the layer thickness can be controlled accurately at the optical level. Phase method (PCVD method), light
CVD method and thermal CVD method are adopted. As methods for processing the support to achieve the objects of the present invention, chemical methods such as chemical etching and electroplating, physical methods such as vapor deposition and sputtering, and mechanical methods such as lathe processing can be used. However, in order to easily manage production, a mechanical processing method such as a lathe is preferred. For example, when processing the support with a lathe, etc., as shown in Fig. 31, 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 is precisely cut by fixing it in a predetermined position on a processing machine and moving it regularly in a predetermined direction while rotating the cylindrical support according to a program designed in advance as desired. This allows the desired uneven shape, pitch, and depth to be formed. The linear protrusion created by the unevenness formed by such a cutting method has a spiral structure centered on the central axis of the cylindrical support. The helical structure of the protrusion may be a double or triple helical structure, or a crossed helical structure. Alternatively, a linear structure along the central axis may be introduced in addition to the spiral structure. In order to enhance the effects of the present invention and to facilitate processing control, it is preferable that the convex portions within a predetermined cross section of the support of the present invention have the same shape in a linear approximation. Further, the convex portions are preferably arranged regularly or periodically in order to enhance the effects of the present invention. 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. The predetermined cutting position of the support in the present invention is
For example, in a support that has a cylindrical axis of symmetry and is provided with a convex portion with a spiral structure centered on the axis of symmetry, it refers to any plane that includes the axis of symmetry, and for example, In the case of a support having a planar shape such as a plate shape, the term refers to a plane that crosses at least two of the plurality of convex portions formed on the support. In the present invention, each dimension of the irregularities provided on the surface of the support in a controlled manner is set in such a way that the object of the present invention can be achieved as a result, taking into account the following points. That is, firstly, the a-Si layer constituting the photoreceptive layer is
The structure is sensitive to the condition of the surface on which the layer is formed, and the quality of the layer changes greatly depending on the surface condition. Therefore, it is necessary to set the dimensions of the irregularities provided on the surface of the support so as not to cause a deterioration in the layer quality of the a-Si layer. Secondly, if the free surface of the photoreceptive layer is extremely uneven, it becomes impossible to perform cleaning completely after image formation. Further, when cleaning the blade, there is a problem that the blade 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 be ~1 μm, most preferably 50 μm to 5 μm. Further, the maximum depth of the recess is preferably 0.1 μm to
5 μm, more preferably 0.3 μm to 3 μm, optimally
It is desirable that the thickness be 0.6 μm to 2 μm. When the pitch and maximum depth of the recesses on the surface of the support are within the above range, the slope of the slope of the recesses (or linear protrusions) is:
Preferably 1 degree to 20 degrees, more preferably 3 degrees to 15 degrees
degree, ideally between 4 degrees and 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 has good electrical, optical, and photoconductive properties.
Indicates electrical voltage resistance and operating environment characteristics. In particular, when applied as a light-receiving member for electrophotography, there is no influence of residual potential on image formation, its electrical properties are stable, it is highly sensitive, and it has high sensitivity.
It has a high signal-to-noise ratio, has excellent light 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 made of a-Si (hereinafter abbreviated as "a-SiGe (H, ) and a-Si containing hydrogen atoms and/or halogen atoms (X) as necessary.
(hereinafter abbreviated as "a-Si (H, In the light-receiving member 1004 of the present invention, at least the first layer (G) 1002 and/or the second layer (S) 1003 contains a substance (C) that controls conduction properties, and the substance The desired conductive properties are imparted to the layer containing (C). In the present invention, the first layer (G) 1002 or/
The substance (C) that controls the conductive properties contained in the second layer (S) 1003 may be contained evenly and uniformly in the entire layer region containing the substance (C), (C) may be contained so as to be unevenly distributed in a part of the layer region in which it is contained. In the present invention, the first layer (G) is made such that the substance (C) that controls the conduction characteristics is unevenly distributed in a part of the layer region of the first layer (G).
When it is contained in (G), the layer region (PN) containing the substance (C) is preferably provided as an end layer region of the first layer (G). In particular, the first layer
When the layer region (PN) is provided as the end layer region on the support side of (G), the layer region (PN)
Injection of a specific polar charge from the support into the second layer (S) can be effected by appropriately selecting the type and content of the substance (C) contained therein as desired. can be effectively prevented. In the light-receiving member of the present invention, the substance (C) capable of controlling conduction properties is added to the first layer (G) constituting a part of the light-receiving layer as described above. (G)
It is preferable to include it evenly over the entire area or unevenly distributed in the layer thickness direction. The substance (C) may also be contained in the second layer (S). In another preferred embodiment, the substance
(C) is not contained in the first layer (G), but is contained only in the second layer (S). In this case, the substance (C) may be evenly contained in the entire layer area of the second layer (S), or
It may be contained and unevenly distributed only in a part of the layer region of the second layer (S). When unevenly distributed, it is preferably contained in the end layer region of the second layer (S) on the first layer (G) side, and in this case, the type and content of the substance (C) By appropriately selecting , it is possible to prevent charges of a specific polarity from being injected from the support side to the second layer (S). When the substance (C) is contained in the second layer (S), the type, amount and manner of the substance (C) contained in the first layer (G) are , can be determined as appropriate in each case according to desire. In the present invention, when the substance (C) is contained in the second layer (S), the substance (C) is preferably contained in a layer region including at least the contact interface with the first layer (G). It is desirable to include C). When both the first layer (G) and the second layer (S) contain a substance (C) that controls conduction properties, the first layer (G)
a layer region containing the substance (C) in;
It is desirable that the second layer (S) and the layer region containing the substance (C) be provided in contact with each other. Further, the substance (C) contained in the first layer (G) and the second layer (S) is of the same type in the first layer (G) and the second layer (S). However, it is okay to be of a different type, and
The content may be the same or different in each layer. However, in the present invention, if the substance (C) contained in each layer is the same in both layers, the content in the first layer (G) may be sufficiently increased. Alternatively, it is preferable that each desired layer contains substances (C) having different electrical characteristics. In the present invention, by containing a substance (C) that controls conduction characteristics in at least the first layer (G) and/or the second layer (S) constituting the photoreceptive layer, Layer region containing the substance (C) [first layer
(G) or a part or all of the second layer (S)] can be arbitrarily controlled as desired. ) can include so-called impurities in the semiconductor field, and in the present invention, a-Si (H, X) and/or a-SiGe (H , Specifically, p-type impurities include atoms belonging to a group of the periodic table (group atoms), such as B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). Among them, B and Ga are particularly preferably used. Examples of n-type impurities include atoms belonging to a group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc.
In particular, P and As are preferably used. In the present invention, the content of the substance (C) that controls conduction properties in the layer region (PN) is determined by the conductivity required for the layer region (PN) or the content of the substance (C) that controls conduction characteristics. When (PN) is provided in direct contact with the support, it can be appropriately selected depending on the organic relationship, such as the relationship with the properties at the contact interface with the support. In addition, the relationship between other layer regions provided in direct contact with the layer region (PN) and the properties at the contact interface with the other layer regions is also taken into account, and the material ( The content of C) is selected appropriately. In the present invention, the content of the substance (C) that controls conduction properties contained in the layer region (PN) is as follows:
Preferably 0.01 to 5×10 ⁴ atomic ppm, more preferably 0.5 to 1×10 ⁴ atomic ppm, optimally 1 to
It is desirable that the amount is 5×10 ³ atomic ppm. In the present invention, the content of the substance (C) that controls conduction characteristics in the layer region (PN) containing the substance (C) is preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more. , optimally 100atomic
ppm or more, for example, when the substance (C) to be contained is the above-mentioned p-type impurity, when the free surface of the photoreceptive layer is subjected to polar charging treatment, the light reception from the support side is reduced. The substance to be contained can effectively prevent the injection of electrons into the layer.
When (C) is the above-mentioned n-type impurity, it effectively blocks the injection of holes from the support side into the photoreceptive layer when the free surface of the photoreceptor layer is subjected to polar charging treatment. I can do it. In the above case, as described above, the layer region (Z) excluding the layer region (PN) has the conductivity type of the substance that controls the conduction characteristics contained in the layer region (PN). A substance (C) that controls conduction characteristics with a conduction type different from that of the polarity may be contained, or a substance (C) that controls conduction characteristics with a conduction type of the same polarity may be included in the layer region (PN). It may be contained in an amount much smaller than the actual amount contained. In such a case, the content of the substance controlling the conduction characteristics contained in the layer region (Z) depends on the polarity and content of the substance (C) contained in the layer region (PN). Although it is determined appropriately according to the desired value, it is preferably 0.001 to 1000 atomic.
ppm, more preferably 0.05 to 500 atomic ppm, optimally 0.1 to 200 atomic ppm. In the present invention, when the layer region (PN) and the layer region (Z) contain the same type of substance (C) that controls conductivity, the content in the layer region (Z) is preferably is preferably 30 atomic ppm or less. In the present invention, the photoreceptive layer includes a layer region containing a substance controlling conductivity having a conductivity type of one polarity and a substance controlling conductivity having a conductivity type of the other polarity. It is also possible to provide a so-called depletion layer in the contact region by providing the layer region in direct contact with the contact region. For example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the photoreceptive layer so as to be in direct contact with each other, so-called p-n.
A junction can be formed to provide a depletion layer. The germanium atoms contained in the first layer (G) 1002 are continuous and uniform in the thickness direction of the first layer (G) 1002 and in the in-plane direction parallel to the surface of the support. The first layer is
(G) Contained in 1002. In the present invention, germanium atoms are not contained in the second layer (S) provided on the first layer (G), and a photoreceptive layer is formed in such a layer structure. As a result, a light-receiving member having excellent photosensitivity to light of all wavelengths from relatively short wavelengths to relatively long wavelengths including the visible light region can be obtained. In addition, the distribution state of germanium atoms in the first layer (G) is such that germanium atoms are continuously distributed in the entire layer region, so when a semiconductor laser or the like is used, the second layer (S ) can substantially completely absorb light on the long wavelength side, which is almost completely absorbed by the first layer (G), and can prevent interference due to reflection from the support surface. Further, in the light receiving member of the present invention, the first layer
Since the amorphous materials constituting (G) and the second layer (S) each have a common constituent element of silicon atoms, chemical stability can be sufficiently ensured at the laminated interface. has been done. In the present invention, the content of germanium atoms contained in the first layer (G) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 1. 9.5× ¹⁰⁵ atomic ppm,
More preferably, it is 100 to 8×10 ⁵ atomic ppm. In the present invention, the layer thickness of the first layer (G) and the second layer (S) is one of the important factors for effectively achieving the object of the present invention. Considerable care must be taken in the design of the light-receiving member to ensure that the desired properties are fully imparted to the light-receiving member. In the present invention, the layer thickness T _B of the first layer (G) is preferably 30 Å to 50 μ, more preferably 40 Å to
It is desirable that the thickness be 40μ, optimally 50Å to 30μ. Further, the layer thickness T of the second layer (S) is preferably
0.5~90μ, more preferably 1~80μ, optimally 2~
It is desirable to set it to 50μ. The sum (T _B +T) of the layer thickness T _B of the first layer (G) and the layer thickness T of the second layer (S) is based on the characteristics required for both layer regions and the characteristics required for the entire photoreceptive layer. It is determined as desired when designing the layers of the light-receiving member, based on the organic relationship between the properties of the light-receiving member. In the light receiving member of the present invention, the above (T _B
The numerical range of +T) is preferably 1 to
100μ, more preferably 1-80μ, optimally 2-50μ
It is desirable that this is done. In a more preferred embodiment of the present invention,
The above layer thickness T _B and layer thickness T are preferably
When satisfying the function T _B /T≦1, it is desirable that appropriate numerical values be selected for each. In selecting the numerical values of the layer thickness T _B and the layer thickness T in the above case, it is more preferable that T _B /T≦0.9,
Optimally, it is desirable that the values of layer thickness T _B and layer thickness T be determined so that the relationship T _B /T≦0.8 is satisfied. In the present invention, the content of germanium atoms contained in the first layer (G) is 1×10 ⁵ atomic ppm.
In the above case, the layer thickness T _B of the first layer (G) is
It is desirable to make it fairly thin, preferably 30μ
Hereinafter, it is more preferably 25μ or less, most preferably 20μ or less. In the present invention, the first layer constituting the photoreceptive layer
Specific examples of the halogen atom (X) contained in (G) and the second layer (S) as necessary include fluorine, chlorine, bromine, and iodine, particularly fluorine, Chlorine may be mentioned as suitable. In the present invention, the first layer (G) composed of a-SiGe (H, It is done by law. For example, by the glow discharge method, a
- To form the first layer (G) composed of SiGe (H, A raw material gas for Ge supply that can supply Ge, and a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) as necessary, are placed in the desired deposition chamber where the internal pressure can be reduced. 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 , 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) consisting of a-SiGe containing halogen atoms can be formed on the desired support without using silicon hydride gas.
can be formed. 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 electrobeam method (EB method), etc., and the flying evaporates are brought into a desired gas plasma atmosphere. This can be done by passing it through. At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion plating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient to introduce the gas to form a plasma atmosphere of the gas. In addition, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, for example, H ₂ or gases such as the above-mentioned silanes and/or germanium hydride, is introduced into the deposition chamber for sputtering. It is sufficient to form a plasma atmosphere of the gases. In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ ,
Halogen-substituted silicon hydrides such as SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and GeHF ₃ ,
GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ ,
GeH ₃ Cl, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br,
Halides containing hydrogen atoms as one of their constituent elements, such as germanium hydrogenated halides such as GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ ,
Germanium halides such as GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and other gaseous or gasifiable substances can also be mentioned as useful starting materials for forming the first layer (G). Among these substances, halides containing hydrogen atoms introduce halogen atoms into the layer when forming the first layer (G), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen. In order to structurally introduce hydrogen atoms into the first layer (G), in addition to the above, H ₂ , SiH ₄ , Si ₂ H ₆ ,
Silicon hydride such as Si ₃ H ₈ , Si ₄ H ₁₀ with germanium or germanium compound for supplying Ge, or GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ ,
It is also possible to cause a discharge by coexisting germanium hydride such as Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ and silicon or a silicon compound for supplying Si in the deposition chamber. I can do it. In a preferred example of the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the first layer (G) constituting the photoreceptive layer to be formed, or the amount of hydrogen atoms and halogen atoms The sum of the amounts (H+X) is preferably 0.01 to 40 atomic%, more preferably 0.05 to 40 atomic%.
It is desirable that it be 30 atomic%, optimally 0.1 to 25 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the first layer (G), for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms ( The amount of the starting material used to contain X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, in order to form the second layer (S) composed of a-Si (H,
From among the starting materials () for forming the layer (G), the starting materials (starting materials for forming the second layer (S)) excluding the starting material that becomes the raw material gas for supplying Ge are used. This can be carried out according to the same method and conditions as in the case of forming the first layer (G). That is, in the present invention, to form the second layer (S) composed of a-Si(H,X), a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method is used. It is made by vacuum deposition method. For example, a second layer (S) composed of a-Si(H,X) is formed by a glow discharge method.
In order to form, basically, in addition to the above-mentioned raw material gas for supplying Si that can supply silicon atoms (Si), hydrogen atoms (H) and/or halogen atoms (X) are introduced as necessary. A raw material gas for a-Si(H, ) may be formed. In addition, when forming by sputtering, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, hydrogen atoms (H ) or/and a gas for introducing halogen atoms (X) may be introduced into the deposition chamber for sputtering. A layer region (PN) containing a substance (C) that controls conduction properties, such as a group group atom or a group group atom, is structurally introduced into the layer constituting the photoreceptive layer. In order to form a photoreceptive layer, the starting material for introducing the group atom or the starting material for introducing the group atom may be introduced in a gaseous state into the deposition chamber together with the starting material for forming the photoreceptive layer during layer formation. Good.
As a starting material for introducing such group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ B ₅ H ₁₁ , B ₆ H ₁₀ ,
Boron hydride such as B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ BCl ₃ , BBr ₃
Examples include boron halides such as. In addition,
AlCl ₃ , GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TCl ₃ and the like may also be mentioned. In the present invention, the starting materials for introducing group atoms that are effectively used for introducing phosphorus atoms include hydrogenated phosphorus such as PH ₃ , P ₂ H ₄ , PH ₄ I, PF ₃ ,
Examples include phosphorus halides such as _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 , _PI3 . In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , SiH ₃ , SiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. In the light-receiving member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the light-receiving layer, the light-receiving layer contains , oxygen atoms, carbon atoms, and nitrogen atoms are contained in a uniform or non-uniform distribution state in the layer thickness direction. Such atoms (OCN) contained in the photoreceptive layer may be contained in the entire layer area of the photoreceptive layer, or they may be unevenly distributed by being contained in only some layer areas of the photoreceptive layer. You can let me. The distribution state of atoms (OCN) is the distribution concentration C (OCN)
However, it is desirable that the photoreceptive layer be uniform in a plane parallel to the surface of the support. In the present invention, the layer region (OCN) containing atoms (OCN) provided in the photoreceptive layer is
When the main purpose is to improve photosensitivity and dark resistance, it is provided so as to occupy the entire layer area of the photoreceptive layer.
When the main purpose is to strengthen the adhesion between the support and the photoreceptive layer, it is provided so as to occupy the end layer region of the photoreception layer on the side of the support. In the former case, the content of atoms (OCN) contained in the layer region (OCN) is kept relatively low in order to maintain high photosensitivity, while in the latter case, the content of atoms (OCN) contained in the layer region (OCN) is kept relatively low to maintain high photosensitivity; It is desirable to use a relatively large amount to ensure accuracy. In the present invention, the content of atoms (OCN) contained in the layer region (OCN) provided in the photoreceptive layer is as follows:
The characteristics required for the layer region (OCN) itself, or when the layer region (OCN) is provided in contact with a support, the relationship with the characteristics at the contact interface with the support, etc. It can be selected as appropriate depending on the relationship. In addition, when another layer region is provided in direct contact with the layer region (OCN), the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The content of atoms (OCN) is selected appropriately, taking into account the following. Atoms contained in the layer region (OCN)
The amount can be determined as desired depending on the characteristics required of the light receiving member to be formed, but is preferably 0.001 to 50 atomic%, more preferably,
0.002-40atomic%, optimally 0.003-30atomic%
It is desirable that this is done. In the present invention, whether the layer region (OCN) occupies the entire area of the photoreceptive layer or even if it does not occupy the entire area of the photoreceptor layer, the layer thickness T of the photoreceptor layer is When the proportion of atoms (OCN) in the layer region (OCN) is sufficiently large, it is desirable that the upper limit of the content of atoms (OCN) contained in the layer region (OCN) is sufficiently smaller than the above value. In the case of the present invention, the layer thickness To of the layer region (OCN)
In cases where the proportion of atomic percent (OCN) in the layer thickness T of the photoreceptive layer is two-fifths or more, the upper limit of the atoms (OCN) contained in the layer region (OCN) is preferably 30 atomic%. The following, more preferably
It is desirable that it be 20 atomic % or less, optimally 10 atomic % or less. According to a preferred embodiment of the present invention, atoms (OCN) are preferably contained at least in the first layer provided directly on the support. By containing atoms (OCN) in the support-side end layer region of the light-receiving layer, it is possible to strengthen the adhesion between the support and the light-receiving layer. Furthermore, in the case of nitrogen atoms, for example, in the coexistence with boron atoms, it is possible to further improve dark resistance and ensure high photosensitivity, so it is desirable to contain a desired amount in the photoreceptive layer. Further, a plurality of types of these atoms (OCN) may be contained in the photoreceptive layer. That is, for example, oxygen atoms may be contained in the first layer, or oxygen atoms and nitrogen atoms may be contained coexisting in the same layer region. 11 to 19 show typical examples where the distribution state of atoms (OCN) contained in the layer region (OCN) of the light-receiving member in the present invention in the layer thickness direction is non-uniform. . In Figures 11 to 19, the horizontal axis represents the distribution concentration C of atoms (OCN), and the vertical axis represents the layer region (OCN).
indicates the layer thickness, and t _B is the layer area on the support side (OCN)
t _T indicates the position of the end surface of the layer region (OCN) on the opposite side to the support side. In other words, the layer region (OCN) containing atoms (OCN) is from the t _B side.
t Layer formation occurs toward _{the T} side. FIG. 11 shows a first typical example where the distribution state of atoms (OCN) contained in the layer region (OCN) in the layer thickness direction is non-uniform. In the example shown in FIG. 11, the interface position t _B where the surface where the layer region (OCN) containing atoms (OCN) is formed and the surface of the layer region (OCN) are in contact with each other.
Up to the position t ₁ , the distribution concentration C of atoms (OCN) takes a constant value C ₁ and is contained in the layer region (OCN) where atoms ₍ OCN) are formed,
The concentration is gradually and continuously decreased from C ₂ to the interface position t _T . At the interface position _tT , the distribution concentration C of atoms (OCN) is assumed to be the concentration _C3 . In the example shown in FIG. 12, the distribution concentration C of the contained atoms (OCN) gradually and continuously decreases from the concentration _C4 from position _tB to _tT , and at position _tT the concentration _C5 decreases. The distribution state is formed as follows. In the case of Fig. 13, the distribution concentration C of atoms (OCN) from position t _B to position t ₂ is a constant value of concentration C ₆ , and gradually becomes continuous between position t ₂ and position t _T. The distribution concentration C is substantially reduced to zero at the position _tT (substantially zero here means that it is less than the detection limit amount). In the case of FIG. 14, the distribution concentration C of atoms (OCN) is gradually decreased from the concentration C ₈ from position t _B to position t _T , and at position t _T it becomes substantially zero. has been done. In the example shown in Figure 15, atoms (OCN)
The distribution concentration C is the concentration between position _tB and position _t3 .
_C9 is a constant value, and the concentration is _C10 at position _tT . Between position _t3 and position _tT , the distribution concentration C
decreases linearly from position _t3 to position _tT . In the example shown in FIG. 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
Until then, the distribution is said to decrease linearly. In the example shown in Fig. 17, the _position
Until _tT , the distributed concentration C of atoms (OCN) decreases linearly from the concentration _C14 to substantially zero. In FIG. 18, from position _tB to position _t5 , the distribution concentration C of atoms (OCN) decreases linearly from the concentration _C15 to _C16 , and from position _t5 to position _tT. An example is shown in which the concentration C ₁₆ is kept at a constant value. In the example shown in FIG. 19, the distribution concentration C of atoms (OCN) is the concentration C at position _tB .
The concentration C ₁₇ is initially gradually decreased from this concentration C ₁₇ until reaching the position t ₆ , and around the position t ₆ , it is rapidly decreased to the concentration C ₁₈ at the position t ₆ . Between position t ₆ and position t ₇ , the concentration is first rapidly decreased, and then gradually decreased to reach C ₁₉ at position t ₇ , and between position t ₇ and t ₈ , is gradually reduced very slowly to reach the concentration C ₂₀ at t ₈ . Between position _t8 and position _tT , the concentration is reduced from _C20 to substantially zero according to a curve shaped as shown in the figure. As described above with reference to FIGS. 11 to 19, some of the typical cases where the distribution state of atoms (OCN) contained in the layer region (OCN) in the layer thickness direction is non-uniform, this book is as follows. In the invention, the support side has a portion where the distribution concentration C of atoms (OCN) is high, and the interface _tT side has a portion where the distribution concentration C is considerably lower than that on the support side. A distribution state of OCN) is provided in the layer region (OCN). Layer region containing atoms (OCN)
As mentioned above, there are atoms (OCN) toward the support side.
It is preferable to provide a localized region (B) containing a relatively high concentration of I can do it. The localized region (B) is desirably provided within 5μ from the interface position _tB , if explained using the symbols shown in FIGS. 11 to 19. In the present invention, the localized region (B) may be the entire region (L _T ) up to 5μ thick from the interface position t _B , or it may be a part of the layer region (L _T ). In some cases. Whether the localized region (B) is a part or all of the layer region (L _T ) is appropriately determined depending on the characteristics required of the photoreceptive layer to be formed. The localized region (B) is the atom (OCN) contained therein.
The maximum value Cmax of the atomic (OCN) distribution concentration C in the layer thickness direction is preferably 500 atomic
ppm or more, more preferably 800 atomic ppm or more,
Optimally, it is desirable to form a layer so that a distribution state of 1000 atomic ppm or more can be obtained. That is, in the present invention, the layer region (OCN) containing atoms (OCN) has a distribution concentration C within 5 μm in layer thickness from the support side (layer region 5 μ thick from t _B ).
It is desirable that the maximum value Cmax exists. In the present invention, when the layer region (OCN) is provided so as to occupy a part of the layer region of the photoreceptive layer, at the interface between the layer region (OCN) and other layer regions,
Atomic (OCN) so that the refractive index changes gradually
It is desirable to form a distribution state in the layer thickness direction. By doing so, it is possible to prevent the light incident on the photoreceptive layer from being reflected at the layer contact interface, and to more effectively prevent the appearance of interference fringes. Further, it is preferable that the change line of the distribution concentration C of the atoms (OCN) in the layer region (OCN) continuously and gently change in order to provide a smooth change in the refractive index. From this point of view, it is desirable that the atoms (OCN) be contained in the layer region (OCN) so as to have the distribution states shown, for example, in FIGS. 11 to 14, 17, and 19. In the present invention, in order to provide a layer region (OCN) containing atoms (OCN) in the photoreceptive layer, a starting material for introducing atoms (OCN) is added to the above-mentioned photoreceptor when forming the photoreceptor layer. It may be used together with the starting material for forming the layer, and may be incorporated in the formed layer in a controlled amount. When a glow discharge method is used to form the layer region (OCN), a starting material for introducing atoms (OCN) is added to a material selected as desired from among the starting materials for forming the photoreceptive layer described above. As such, most gaseous substances whose constituent atoms are at least atoms (OCN) or gasified substances that can be gasified are used. Specifically, for example, oxygen (O ₂ ), ozone (O ₃ )
Nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrogen monooxide (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H) as constituent atoms, such as disiloxane (H ₃ SiOSiH ₃ ), tricycloxane (H Lower cycloxanes such as ₃ SiOSiH ₂ OSiH ₃ ), methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H Saturated hydrocarbons having 1 to 5 carbon atoms such as ₁₂ ), ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-
1 (C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), etc. with 2 to 5 carbon atoms
Ethylene hydrocarbons, acetylene hydrocarbons with 2 to 4 carbon atoms such as acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N) etc. can be mentioned. In the case of sputtering method, atomic (OCN)
As starting materials for introduction, in addition to the above-mentioned gasifiable starting materials listed for the glow discharge method, examples of solidified starting materials include SiO ₂ , Si ₃ N ₄ , carbon black, etc. . These are used as targets for sputtering together with targets such as Si. In the present invention, when a layer region (OCN) containing atoms (OCN) is provided when forming a photoreceptive layer, the distribution concentration C of atoms (OCN) contained in the layer region (OCN) is In order to form a layer region (OCN) having a desired distribution state (depth profile) in the layer thickness direction by changing C in the layer thickness direction, in the case of a glow discharge, the distribution concentration C of the atoms (OCN) whose distribution should be changed is This is accomplished by introducing the starting material gas for introduction into the deposition chamber while appropriately varying the gas flow rate according to a desired rate of change curve. For example, the opening of a predetermined needle valve provided in the middle of the gas flow system may be temporarily changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like may be used to control the flow rate according to a rate of change curve designed in advance to obtain a desired content rate curve. When forming a layer region (OCN) by a sputtering method, the distribution concentration C of atoms (OCN) in the layer thickness direction is changed in the layer thickness direction.
In order to form the desired depth profile in the layer thickness direction, firstly, as in the case of the glow discharge method, the starting material for introducing atoms is used in a gaseous state, and the gas is introduced into the deposition chamber. This is accomplished by appropriately changing the flow rate of the gas introduced into the interior as desired. Second, if a target for sputtering is used, for example a mixed target of Si and SiO ₂ , the mixing ratio of Si and SiO ₂ should be varied in advance in the layer thickness direction of the target. This is accomplished by placing The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al , Ag, Pb, Zn, Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the light-receiving member 1004 in FIG. If used as a receiving member, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is determined appropriately so that a desired light-receiving member is formed, but if flexibility is required as a light-receiving member, the thickness of the support may be determined appropriately. It is made as thin as possible within the range. However, in such a case, the thickness is preferably 10μ or more in terms of manufacturing and handling of the support and functional strength. Next, an outline of an example of the method for manufacturing the light receiving member of the present invention will be explained. FIG. 20 shows an example of a light-receiving member manufacturing apparatus. Gas cylinders 2002 to 2006 in the figure are sealed with raw material gas for forming the light-receiving member of the present invention.
SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ )
Cylinder, 2003 is GeH ₄ gas (99.999% purity,
₂₀₀₄ is NO gas (purity 99.999%, hereinafter abbreviated as NO) cylinder, 200
5 is _B2H6 gas diluted with _H2 (99.999% _purity ,
₂₀₀₆ is _a H ₂ gas (purity 99.999% ₎ cylinder. In order to flow these gases into the reaction chamber 2001, valves 202 of gas cylinders 2002 to 2006 are used.
2-2026, check that the leak valve 2035 is closed, and also check that the inflow valve 2012-
2016, after confirming that the outflow valves 2017 to 2021 and the auxiliary valves 2032 and 2033 are open, first open the main valve 2034 to exhaust the reaction chamber 2001 and each gas pipe. Next, when the reading on the vacuum gauge 2036 reaches approximately 5×10 ⁻⁶ torr, the auxiliary valves 2032 and 2033 and the outflow valves 2017 to 2021 are closed. Next, to give an example of forming a light-receiving layer on the cylindrical substrate 2037, the gas cylinder 2037
SiH ₄ gas from 02, gas cylinder from 2003
GeH ₄ gas, NO gas from gas cylinder 2004,
B ₂ H ₆ /H ₂ gas from gas cylinder 2005, 200
_H2 gas from 6 valves 2022, 2023, 2
Open 024, 2025, 2026 and outlet pressure gauges 2027, 2028, 2029, 2030, 2
Adjust the pressure of 031 to 1Kg/cm ² and open the inflow valve 20.
12, 2013, 2014, 2015, 2016
Gradually open the mass flow controller 200.
7, 2008, 2009, 2010, and 2011, respectively. Subsequently, the outflow valve 201
7, 2018, 2019, 2020, 2021,
The auxiliary valves 2032 and 2033 are gradually opened to allow each gas to flow into the reaction chamber 2001. At this time, the outflow valve 201 is adjusted so that the ratio of the SiH ₄ gas flow rate, the GeH ₄ gas flow rate, and the NO gas flow rate becomes the desired value.
7, 2018, 2019, 2020, and 2021, and also adjust the opening of the main valve 2034 while checking the reading on the vacuum gauge 2036 so that the pressure inside the reaction chamber 2001 reaches the desired value. Then, the temperature of the base 2037 is increased by the heating heater 2038.
After confirming that the temperature is set within the range of 50 to 400° C., the power source 2040 is set to the desired power to generate glow discharge in the reaction chamber 2001. 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 according to the same conditions and procedures. By maintaining the glow discharge, it is possible to form a second layer (S) substantially free of germanium atoms on the first layer (G). In addition, by appropriately opening and closing the outflow valve 2019 or 2020, each layer of the first layer (G) and the second layer (S) can contain or not contain oxygen atoms or boron atoms, or each layer It is also possible to contain oxygen atoms or boron atoms only in a part of the layer region. Further, when nitrogen atoms or carbon atoms are contained in the layer instead of oxygen atoms, the layer may be formed by replacing the NO gas in the gas cylinder 2004 with, for example, NH ₃ gas or CH ₄ gas. Moreover, when increasing the types of gases to be used, it is sufficient to add a desired gas cylinder and perform layer formation in the same manner. During layer formation, the substrate 2037 is preferably rotated at a constant speed by a motor 2039 in order to ensure uniform layer formation. [Example] Examples will be described below. Example 1 An Al support [length (L) 357 mm, outer diameter (r) 80 mm] was machined using a lathe to give the surface properties as shown in FIG. 21B. Next, under the conditions shown in Table 1, using the film deposition apparatus shown in FIG. 20, an a-Si electrophotographic light-receiving member was produced according to a predetermined operating procedure. The surface condition of the light-receiving member thus produced was as shown in FIG. 21C. in this case,
The difference in average layer thickness between the center and both ends of the Al support was 2 μm. Regarding the above light-receiving member for electrophotography, the 24th
The image exposure device shown in the figure (laser light wavelength 780n)
imagewise exposure was carried out at a spot diameter of 80 μm), which was then 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 Next, in the same manner as in Example 1 except that the conditions shown in Table 2 were used, an a-Si electrophotographic light-receiving member was prepared using the film deposition apparatus shown in FIG. 20 according to various operating procedures. It was created. The electrophotographic light-receiving member formed as described above is subjected to image exposure using an image exposure device (laser light wavelength 780 nm, spot diameter 80 μm) shown in FIG. 24, and then developed and transferred to form an image. Obtained. No fringe pattern was observed in the obtained image.
It was sufficient for practical use. Example 3 An a-Si electrophotographic light-receiving member was produced in the same manner as in Example 1 using the film deposition apparatus shown in FIG. 20 according to various operating procedures except that the conditions shown in Table 3 were used. The electrophotographic light-receiving member formed as described above is subjected to image exposure using an image exposure device (laser light wavelength 780 nm, spot diameter 80 μm) shown in FIG. 24, and then developed and transferred to form an image. Obtained. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 4 The surface of an Al support (length (L) 357 mm, diameter (r) 80 mm) was machined using three types of lathes to give the surface properties as shown in FIG. 21B, FIG. 22, and FIG. 23. Next, under the conditions shown in Table 4, an a-Si electrophotographic light-receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures. Regarding these electrophotographic light receiving members, the second
Image exposure device shown in Figure 4 (laser light wavelength
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in any of the obtained images, which were sufficient for practical use. Example 5 An Al support (length (L) 357 mm, diameter (r) 80 mm) was
Three types of lathes were used to obtain the surface properties shown in FIG. 21B, FIG. 22, and FIG. 23. Next, in the same manner as in Example 4 except that the conditions shown in Table 5 were used, a-Si based electrophotographic light-receiving members were produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures. Each of the light-receiving members thus produced was subjected to image exposure using an image exposure apparatus shown in FIG. 24 (laser light wavelength: 780 nm, spot diameter: 80 μm), and then developed and transferred to obtain an image.
No interference fringe pattern was observed in any of the obtained images, which were sufficient for practical use. Example 6 Al support (length (L) 357 mm, diameter (r) 80 mm),
Three types of lathes were used to obtain the surface properties shown in FIG. 21B, FIG. 22, and FIG. 23. Next, in the same manner as in Example 4 except that the conditions shown in Table 6 were used, an a-Si electrophotographic light receiving member was produced using the film deposition apparatus shown in FIG. 20 according to various operating procedures. Each of the light-receiving members thus produced was subjected to image exposure using an image exposure apparatus shown in FIG. 24 (laser light wavelength: 780 nm, spot diameter: 80 μm), and then developed and transferred to obtain an image.
No interference fringe pattern was observed in any of the obtained images, which were sufficient for practical use. Example 7 Al support (length (L) 357 mm, diameter (r) 80 mm),
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, a-Si electrophotographic light was applied in the same manner as in Example 1 using the film deposition apparatus shown in FIG. 20 according to various operating procedures except that the conditions shown in Table 7 were used. A receiving member was produced. In addition, in forming the first layer, CH ₄ gas is
A mass flow controller 2009 for CH ₄ gas was controlled by a computer (HP9845B) so that the flow rate ratio to SiH ₄ gas was as shown in FIG. The electrophotographic light-receiving member formed as described above is subjected to image exposure using an image exposure device (laser light wavelength 780 nm, spot diameter 80 μm) shown in FIG. 24, and then developed and transferred to form an image. Obtained. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 8 Al support (length (L) 357 mm, diameter (r) 80 mm),
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, a-Si electrophotographic light was applied in the same manner as in Example 1 using the film deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 8 were used. A receiving member was produced. In addition, in forming the first layer, NO gas is
This was formed by controlling the NO gas mass flow controller 2009 with a computer (HP9845B) so that the flow rate ratio to the sum of GeH ₄ gas and SiH ₄ gas was as shown in FIG. Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 9 Al support (length (L) 357 mm, diameter (r) 80 mm),
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, electrophotographic light-receiving members were produced in the same manner as in Example 1 except that the conditions shown in Table 9 were used, using the deposition apparatus shown in FIG. 20 and following various operating procedures. In addition, in forming the first layer, NH ₃ gas is
The first layer was formed by controlling the mass flow controller 2009 of NH ₃ gas by a computer (HP9845B) so that the flow rate ratio to the sum of GeH ₄ gas and SiH ₄ gas was as shown in FIG. 27. Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 10 Al support (length (L) 357 mm, diameter (r) 80 mm),
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, an electrophotographic light-receiving member was produced in the same manner as in Example 1 using the deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 10 were used. The flow rate ratio of CH ₄ gas to the sum _of GeH ₄ gas and SiH ₄ gas is as shown in Figure 28.
was controlled by a computer (HP9845B). Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 11 Al support [length (L) 357 mm, diameter (r) 80 mm],
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, an electrophotographic light-receiving member was produced in the same manner as in Example 1 using the deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 11 were used. In addition, the flow rate ratio of NO gas to the sum of GeH ₄ gas and SiH ₄ gas is set as shown in Figure 29.
A NO gas mass flow controller 2009 was controlled by a computer (HP9845B). Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 12 Al support [length (L) 357 mm, diameter (r) 80 mm],
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, an electrophotographic light-receiving member was produced in the same manner as in Example 1 using the deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 12 were used. In addition, the flow rate ratio of NH ₃ gas to the sum of GeH ₄ gas and SiH ₄ gas is set as shown in Figure 30.
A NH ₃ gas mass flow controller 2009 was controlled by a computer (HP9845B). Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 13 Al support [length (L) 357 mm, diameter (r) 80 mm],
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, an electrophotographic light-receiving member was produced in the same manner as in Example 1 using the deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 13 were used. Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was performed at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 14 Al support [length (L) 357 mm, diameter (r) 80 mm],
The surface was machined using a lathe to obtain the surface properties shown in FIG. 21B. Next, using this support, an electrophotographic light-receiving member was produced in the same manner as in Example 1 using the deposition apparatus shown in FIG. 20 according to various operating procedures, except that the conditions shown in Table 14 were used. Regarding the light-receiving member produced in this way,
Image exposure device (laser light wavelength) shown in Figure 24
Image exposure was carried out at 780 nm (spot diameter: 80 μm), and the image was developed and transferred to obtain an image. No interference fringe pattern was observed in the obtained image, which was sufficient for practical use. Example 15 Regarding Example 1 to Example 14, H _2
H2 instead of _B2H6 gas diluted to 3000vol _ppm
Using _PH3 gas diluted to 3000vol ppm with
A light-receiving member for electrophotography was produced. The other manufacturing conditions are from Example 1 to Example 14.
I did the same thing as before. Each of the light-receiving members thus produced was subjected to image exposure using an image exposure apparatus shown in FIG. 24 (laser light wavelength: 780 nm, spot diameter: 80 μm), and then developed and transferred to obtain an image.
No interference fringe pattern was observed in any of the obtained images, which were sufficient for practical use.

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【table】 [Brief explanation of drawings]

FIG. 1 is a general explanatory diagram of interference fringes. FIG. 2 is an explanatory diagram of interference fringes in the case of a multilayer light receiving member. FIG. 3 is an explanatory diagram of interference fringes due to scattered light. FIG. 4 is an explanatory diagram of interference fringes due to scattered light in the case of a multilayer light receiving member. FIG. 5 is an explanatory diagram of interference fringes when the interfaces of each layer of the light receiving member are parallel. FIGS. 6A, B, C, and D are explanatory diagrams showing that no interference fringes appear when the interfaces of each layer of the light-receiving member are non-parallel. FIGS. 7A, B, and C are explanatory views for comparing the intensity of reflected light when the interfaces of each layer of the light-receiving member are parallel and non-parallel.
FIG. 8 is an explanatory diagram showing that no interference fringes appear when the interfaces of each layer are non-parallel. Figure 9A,
B is an explanatory diagram of the surface state of each typical support. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIGS. 11 to 19 are explanatory diagrams for explaining the distribution state of atoms (O, C, N) in the layer region (OCN), respectively. FIG. 20 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIGS. 21A and B FIGS. 22 and 23 are illustrations of the surface state of the Al support used in the examples, and FIG. 21C is an illustration of the surface conditions of the light-receiving layer formed in the examples. It is. FIG. 24 is an explanatory diagram of the image exposure apparatus used in the example. FIG. 25 to FIG. 30 each show the rate of change curve of gas flow rate in the example. FIG. 31 is an explanatory diagram for explaining the processing of the support body. 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.
m pitch, a support having many convex portions formed on its surface, each having a convex shape in which a sub peak is superimposed on a main peak at a maximum depth of 0.1 μm to 5 μm, silicon atoms, germanium atoms, and hydrogen atoms. and/or a halogen atom, and a second layer made of an amorphous material consisting of silicon atoms, hydrogen atoms, and/or halogen atoms, The photoreceptive layer also contains at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms, and the photoreceptive layer also contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms, and At least one of the photoreceptive layers also contains a substance that controls conductivity, and the distribution state of the substance is uniform in the layer thickness direction in the layer region containing the substance, and the photoreceptive layer has at least one pair or more within the short range. A light-receiving member for electrophotography, characterized in that it has a non-parallel interface. 2. In the photoreceptive layer containing at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms, the distribution state of the contained atoms is uniform in the layer thickness direction. The electrophotographic light-receiving member according to item 1. 3. Claims in which, in the photoreceptive layer containing at least one type of atom selected from oxygen atoms, carbon atoms, and nitrogen atoms, the distribution state of the contained atoms is nonuniform in the layer thickness direction. 1st
2. The electrophotographic light-receiving member described in 1. 4. The light-receiving member for electrophotography according to claim 1, wherein the convex portions are regularly arranged. 5. The light-receiving member for electrophotography according to claim 1, wherein the convex portions are arranged periodically. 6. The light-receiving member for electrophotography according to claim 1, wherein each of the convex portions has the same shape in a linear approximation. 7. The electrophotographic light-receiving member according to claim 1, wherein the convex portion has a plurality of sub-peaks. 8. The electrophotographic light-receiving member according to claim 1, wherein the cross-sectional shape of the convex portion is symmetrical about the main peak. 9. 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. 10. The light-receiving member for electrophotography according to claim 1, wherein the convex portion is formed by mechanical processing. 11. The electrophotographic light-receiving member according to claim 1, wherein at least one of the first layer and the second layer contains hydrogen atoms. 12. The electrophotographic light-receiving member according to claim 1 or 11, wherein at least one of the first layer and the second layer contains a halogen atom. 13. The light-receiving member for electrophotography according to claim 1, wherein the substance controlling conductivity is an atom belonging to Group 1 of the periodic table. 14. The light-receiving member for electrophotography according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group 1 of the periodic table.