JPH0234030B2 - - 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 photosensitive layer is a single-layer A-Si layer, in order to maintain its high photosensitivity and ensure the dark resistance of 10 ¹² Ωcm or more required for electrophotography, hydrogen atoms and halogen Since it is necessary to structurally contain atoms or boron atoms in addition to these atoms in a specific amount range in a controlled manner in the layer, it is necessary to strictly control the 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,
As described in Patent Publications No. 52180, No. 58159, No. 58160, and No. 58161, a photoreceptive layer is provided between the support and the photosensitive layer, or/and a barrier layer is provided on the upper surface of the photosensitive layer. A light-receiving member with increased apparent dark resistance, such as a multilayer structure, has 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 multiphase 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 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 an A-Si photosensitive layer, a degassing phenomenon occurs from the resin layer, and the layer quality of the formed photosensitive layer is significantly deteriorated. There are disadvantages such as damage caused by plasma during the formation of the Si-based photosensitive layer, which reduces the original absorption function and adversely affects the subsequent formation of the A-Si-based photosensitive layer due to deterioration of the surface condition. be. The third method for irregularly roughening the surface of the support is the third method.
As shown in the figure, for example, the incident light I ₀ is transmitted to the light receiving layer 30.
A part of the light is reflected by the surface of the light receiving layer 302 and becomes reflected light R ₁ , and the rest enters the inside of the light-receiving layer 302 and becomes transmitted light I ₁ . A portion of the transmitted light I ₁ is scattered on the surface of the support 302 and becomes diffused light K ₁ ,
K ₂ , K ₃ ..., and the rest is specularly reflected and the reflected light
_R2 , and a part of it becomes emitted light _R3 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 first layer 402, the reflected light R ₁ on the second layer, and the regular reflection light R on the surface of the support 401. ₃
interfere with each other, and an interference fringe pattern is produced depending on the thickness of each layer of the light-receiving member. Therefore, in a multilayer light-receiving member, it has been impossible to completely prevent interference fringes by irregularly roughening the surface of the support 401. Furthermore, when the surface of the support is irregularly roughened by a method such as sandblasting, the degree of roughness varies greatly between lots, and even within the same lot, the degree of roughness is uneven. , there was a problem with manufacturing management. In addition, relatively large protrusions are frequently formed randomly, and such large protrusions cause local breakdown of the photoreceptive layer. Furthermore, if the surface of the support 501 is simply roughened regularly, 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, mounting, and 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 a light-receiving member for electrophotography that has 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, use environment characteristics, mechanical durability, and light reception characteristics in addition to the above-mentioned excellent characteristics. The object of the present invention is 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; A charge injection prevention layer made of an amorphous material containing a substance that controls conductivity, and a single-layer photosensitive layer made of an amorphous material containing silicon atoms and hydrogen atoms and/or halogen atoms. and a surface layer made of an amorphous material containing silicon atoms and carbon atoms, and the charge injection prevention layer is selected from oxygen atoms, carbon atoms, and nitrogen atoms. The light-receiving layer is characterized in that the light-receiving 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, a multilayer photoreceptive layer has one or more photosensitive layers on a support (not shown) having an uneven shape smaller than the required resolution of the apparatus along the slope of the unevenness. As shown in the enlarged view of FIG. 6A, since the layer thickness of the second layer 602 changes continuously from _d5 to _d6 , the interface 603 and the interface 604
and have a tendency toward each other. Therefore, the coherent light incident on this minute portion (shot range) causes interference in the minute portion, producing a minute interference fringe pattern. 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 ignored for "A" when they are non-parallel than for "B" even if there is interference. It gets smaller as much as you get. 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 non-uniform (d ₇ ≠ d ₈ ), so the amount of incident light becomes uniform in the entire layer area (see "D" in Figure 6). To describe the effects of the present invention when coherent light is transmitted from the irradiation side to the second layer in a multilayer structure, as shown in _FIG. Then, the reflected light 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 of the minute portion (one period of the uneven shape) suitable for the present invention is ≦L, where L is the spot diameter of the irradiated light. In addition, in order to more effectively achieve the object of the present invention, the difference in layer thickness (d ₅ - d ₆ ) in a minute portion should be determined as d ₅ - _{d 6} ≧λ, where λ is the wavelength of the irradiated light. /2n (n: refractive index of the second layer 602) is desirable. In the present invention, within the layer thickness of a microscopic portion of a multilayer photoreceptive layer (hereinafter referred to as a "microcolumn"), each layer is formed so that at least any two layer interfaces are in a non-parallel relationship. The layer thickness is controlled within the microcolumn, but as long as this condition is satisfied, any two layer interfaces may be in a parallel relationship within the microcolumn. However, the layers forming the parallel layer interface can be any two layers.
It is desirable that the layer be formed to have a uniform layer thickness over the entire region so that the difference in layer thickness at two positions is λ/2n (n: refractive index of the layer) or less. A photosensitive layer constituting a photoreceptive layer, a charge injection prevention layer,
In order to more effectively and easily achieve the purpose of the present invention, the plasma vapor phase method (PCVD method) is used to form each layer such as the barrier layer made of electrically insulating material because the layer thickness can be precisely controlled at the optical level. ), optical CVD method,
Thermal CVD method is adopted. As methods for processing the support to achieve the object of the present invention, chemical methods such as chemical etching and electroplating, physical methods such as vapor deposition and sputtering, and mechanical methods such as lathe processing can be used. However, in order to easily manage production, a mechanical processing method such as a lathe is preferred. For example, when processing the support with a lathe, etc., as shown in FIG. 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, in addition to the spiral structure, a slow line structure along the central axis may be introduced. In order to enhance the effects of the present invention and to facilitate processing control, it is preferable that the convex portions within a predetermined cross section of the support of the present invention have the same shape in a linear approximation. Further, the convex portions are preferably arranged regularly or periodically in order to enhance the effects of the present invention. Furthermore, it is preferable that the convex portion has a plurality of sub-peaks in order to further enhance the effect of the present invention and improve the adhesion between the light-receiving layer and the support. In addition to each of these, in order to efficiently scatter incident light in one direction, the convex portion may be symmetrical (FIG. 9A) or asymmetrical (FIG. 9B) around the main peak.
It is preferable that they be unified. However, in order to increase the degree of freedom in controlling the processing of the support, it is better to have both of them mixed together. In the present invention, each dimension of the irregularities provided on the surface of the support in a controlled manner is set 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 photosensitive layer is
The structure is sensitive to the condition of the surface on which the layer is formed, and the quality of the layer changes greatly depending on the surface condition. Therefore, it is necessary to set the dimension of the irregularities provided on the surface of the support so as not to cause a deterioration in the layer quality of the A-Si photosensitive 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. In the light-receiving member of the present invention, at least a part of the layer region is In the layer in which is photosensitive, oxygen atoms,
At least one type of atom selected from carbon atoms and nitrogen atoms is contained. Such atoms (OCN) contained in a layer in which at least a portion of the layer region is photosensitive may be uniformly contained in the entire layer region of the layer in which at least a portion of the layer region is photosensitive. Alternatively, it may be unevenly distributed by containing it only in some layer regions of a layer in which at least some of the layer regions are photosensitive. As for the distribution state of atoms (OCN), it is desirable that the distribution concentration C (OCN) is uniform in the layer thickness direction of the photoreceptive layer and in a plane parallel to the surface of the support. In the present invention, the layer region (OCN) containing atoms (OCN) provided in a layer in which at least a part of the layer region is photosensitive is mainly intended to improve photosensitivity and dark resistance. In this case, at least a part of the layer area is provided so as to occupy the entire layer area of the photosensitive layer, and the main purpose is to strengthen the adhesion between the support and the photoreceptive layer. is provided so that at least a part of the layer region occupies the support side end layer region of the photosensitive layer. In the former case, the content of atoms (OCN) contained in the layer region (OCN) is relatively reduced to maintain high photosensitivity, while in the latter case, it ensures enhanced adhesion with the support. It is desirable that the amount be relatively large in order to achieve this goal. In the present invention, the content of atoms (OCN) contained in a layer region (OCN) provided in a layer in which at least a part of the layer region is photosensitive is determined by the characteristics required for the layer region (OCN) itself. , or when the layer region (OCN) is provided in direct contact with the support, the layer region (OCN) is appropriately selected based on the organic relationship, such as the relationship with the characteristics at the contact interface with the support. I can do it. In addition, when another layer region is provided directly in 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 may also be determined. The content of atoms (OCN) is selected accordingly. The amount of atoms (OCN) contained in the layer region (OCN) is determined as desired depending on the required characteristics of the light-receiving member to be formed, but is preferably 0.001 to 50 atomic%,
More preferably 0.002-40atomic%, optimally
It is desirable that the content be 0.003 to 30 atomic%. 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 of the photoreceptor layer is equal to the layer thickness T ₀ of the layer area (OCN). When the proportion of T 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 invention, the layer thickness T ₀ 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 contained at least in the charge injection prevention layer and barrier layer provided directly on the support. Clogging, atoms (OCN) in the layer region at the end of the support side of the layer where at least some layer regions are photosensitive.
By containing it, it is possible to strengthen the adhesion between the support and the light-receiving layer. Further, in the case of nitrogen atoms, for example, in coexistence with boron atoms, it is possible to improve dark resistance and ensure high photosensitivity, so it is desirable to contain a desired amount in the photosensitive layer. Further, a plurality of types of these atoms (OCN) may be contained in a layer in which at least a part of the layer region is photosensitive. That is, for example, the charge injection prevention layer may contain oxygen atoms, the photosensitive layer may contain nitrogen atoms, or, for example, oxygen atoms and nitrogen atoms may coexist in the same layer region. It may also be included. In the present invention, A-Si (“A-Si(H,
The photosensitive layer composed of X) is formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion plating method. For example, in order to form a photosensitive layer composed of a-Si (H, , If necessary, a raw material gas for introducing hydrogen atoms (H) and/or a raw material gas for introducing halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and the deposition is performed. What is necessary is to generate a glow discharge indoors and form a layer made of a-Si (H, In addition, when forming by sputtering method, Si is formed in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases.
Using a target composed of, hydrogen atoms (H) and/or halogen atoms (X) introduction gas diluted with diluent gas such as He or Ar as necessary is introduced into the deposition chamber for sputtering. However, the target may be sputtered by forming a plasma atmosphere of a desired gas. In the case of the ion plating method, for example, polycrystalline silicon or single crystal silicon is placed in a deposition boat as an evaporation source, and this evaporation source is heated by a resistance heating method, an electron beam method (EB method), or the like. This can be carried out in the same manner as in the sputtering method, except for heating and evaporating and passing the flying evaporated material through a desired gas plasma atmosphere. 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 or gasifiable silicon hydride (silanes) such as Si ₄ H ₁₀ can be effectively used, especially because of its ease of handling during layer creation work and good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Many halides are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halogen compounds, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into 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 ₇ , ICl, and IBr. Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ . I can do it. When forming the characteristic light-receiving member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas is used as a raw material gas capable of supplying Si. Even if you don't,
A photosensitive layer made of a-Si containing halogen atoms can be formed on a desired support. When creating a photosensitive layer containing halogen atoms according to the glow discharge method, basically silicon halide, which serves as a raw material gas for supplying Si, and Ar, H ₂ ,
By introducing a gas such as He into a deposition chamber where a photosensitive layer is formed at a predetermined mixing ratio and gas flow rate, and generating a glow discharge to form a plasma atmosphere of these gases, Although a photosensitive layer can be formed on a desired support, hydrogen gas or a boron compound containing hydrogen atoms may be added to these gases in order to more easily control the ratio of hydrogen atoms introduced. A desired amount of gas may also be mixed to form a layer.
Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio. 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 the above-mentioned all-silicon compound containing halogen atoms is introduced into the deposition chamber. It is sufficient 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 ,
Alternatively, the above-mentioned silane gases may be introduced into a deposition chamber for sputtering 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 the raw material gas for introducing halogen atoms, but in addition, HF, HCl,
Hydrogen halides such as HBr, HI, SiH ₂ F ₂ , SiH ₂ I,
SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiH ₂ Br ₂ , SiHBr ₃
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides can also be mentioned as effective starting materials for forming the photosensitive layer. 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 photosensitive layer. In the present invention, it is used as a suitable raw material for introducing halogen. In the charge injection prevention layer constituting the photoreceptive layer, in order to structurally introduce a substance (C) that controls conduction characteristics, such as group group atoms or group atoms, into the photosensitive layer, it is necessary to introduce a substance (C) that controls conduction characteristics into the photosensitive layer during the formation of each 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 other starting materials for forming the photoreceptive layer. Possible starting materials for introducing such group atoms are:
It is desirable to use 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 such group group atom introduction include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₅ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
Boron hydrides such as BF ₃ , BCl ₃ , BBr ₃ and the like can be mentioned. In addition, AlCl ₃ ,
GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the present invention, effective starting materials for introducing group 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 ,
AsCCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ ,
SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for introducing group atoms. In the present invention, in order to provide a layer region (OCN) containing atoms (OCN) in a layer in which at least a part of the layer region is photosensitive, a layer region in which at least a part of the layer region is photosensitive is provided. During formation, a starting material for introducing atoms (OCN) may be used together with the above-mentioned starting material for forming a photoreceptive layer, and the amount thereof may be controlled and contained in the layer to be formed. When the 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. is added. As a starting material for introducing such atoms (OCN),
Most of gaseous substances whose constituent atoms are at least atoms (OCN) or gasified substances that can be gasified can be 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 ) whose constituent atoms are silicon atoms (Si), oxygen atoms (O), and hydrogen atoms (H), such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ Lower siloxanes such as SiOSiH ₂ OSiH ₃ ),
Saturated carbon atoms with 1 to 5 carbon atoms such as methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), etc. Hydrocarbons, 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 N) ₃ , ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ) and so on.
In the case of the sputtering method, as starting materials for the introduction of atoms (OCNs), in addition to the above-mentioned gasifiable starting materials listed for the glow discharge method, SiO ₂ , Si ₃ N are used as solidified starting materials. ₄ , carbon black, etc. Si or the like is used together with a target such as Si as a sputtering target. Next, specific examples of the multilayered light receiving member according to the present invention will be shown. A light-receiving member 1000 shown in FIG. 10 has a light-receiving layer 1002 on a support 1001 whose surface has been machined to achieve the object of the present invention, and the light-receiving layer 1002 is on the side of the support 1001. Charge injection prevention layer 1003, photosensitive layer 1004, surface layer 10
It consists of 05. The support 1001 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au,
Examples include metals such as Nb, Ta, V, Ti, Pt, and Pd, or 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 the surface is glass, NiCr, Al, etc.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd,
Conductivity can be imparted by providing a thin film made of In 2 O ₂ , 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, Pd, Zn, Ni, Au,
A thin film of metal such as 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 1000 in FIG. If used as a forming member for continuous copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined as appropriate so that the desired light-receiving member is formed, but if flexibility is required as a light-receiving member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such a case, the thickness is preferably 10 μm or more in view of manufacturing and handling of the support, mechanical strength, etc. The charge injection prevention layer 1003 is provided for the purpose of preventing charge injection into the photosensitive layer 1004 from the support 1001 side and increasing the apparent resistance. The charge injection prevention layer 1003 is composed of A-Si (hereinafter referred to as "A-Si (H, C) is contained. The substance (C) that controls conductivity contained in the charge injection prevention layer 1003 can be impurities known in the semiconductor field, and in the present invention, Si has p-type conductivity. Examples include a p-type impurity that provides a p-type impurity, and an n-type impurity that provides an n-type conductivity. Specifically, the p-type impurities include atoms belonging to the group of the periodic table (group atoms) such as B (boron), Al (aluminum), Ga (gallium),
There are In (indium), Tl (thallium), etc., and B and Ga are particularly preferably used. N-type impurities include atoms belonging to the group of the periodic table (group atoms), such as P (phosphorus), As (arsenic), and Sb.
(antimony), Bi (bismuth), etc., and particularly preferably used are P and As. In the present invention, the content of the substance (C) that controls conductivity contained in the charge injection prevention layer 1003 is as follows:
The required charge injection prevention properties, or when the charge injection prevention layer 1003 is provided in direct contact with the support 1001, the relationship with the properties at the contact interface with the support 1001, etc. It can be selected as appropriate depending on the relationship. In addition, the characteristics of other layer regions provided in direct contact with the charge injection prevention layer and the relationship with the characteristics at the contact interface with the other layer regions are also taken into consideration, and the substance that controls the conduction characteristics is selected. The content of is selected as appropriate. In the present invention, the content of the substance controlling conductivity contained in the charge injection prevention layer is preferably 0.001 to 5×10 4 atomic ppm, more preferably 0.001 to 5×10 ⁴ atomic ppm.
0.5 to 1×10 ⁴ atomic ppm, optimally 1 to 5×
It is desirable to set it to 10 ³ atomic ppm. In the present invention, the content of the substance (C) in the charge injection prevention layer 1003 is preferably as follows:
30atomic ppm or more, preferably 50atomic
ppm or more, optimally 100 atomic ppm or more, for example, when the substance (C) to be contained is the above-mentioned p-type impurity, the free surface of the photoreceptive layer is supported when subjected to polar charging treatment. The movement of electrons injected from the body side into the photosensitive layer can be more effectively blocked, and when the substance (C) to be contained is the n-type impurity, the free surface of the photoreceptive layer It is possible to more effectively prevent the movement of holes injected from the support side into the photosensitive layer when the photosensitive layer is subjected to polar charging treatment. The thickness of the charge injection prevention layer 1003 is preferably
30Å to 10μ, more preferably 40Å to 8μ, optimally 50
It is desirable that the thickness be Å to 5μ. The photosensitive layer 1004 is made of A-Si (H, The thickness of the photosensitive layer 1004 is preferably as follows:
It is desirable that the thickness be 1 to 100 μm, more preferably 1 to 80 μm, and optimally 2 to 50 μm. The photosensitive layer 1004 includes a charge injection prevention layer 1003.
The charge injection prevention layer 1003 may contain a substance that controls conduction properties with a polarity different from the polarity of the substance that controls conduction properties contained in the charge injection prevention layer 1003. It may be contained in an amount much smaller than the actual amount contained in. In such a case, the content of the substance controlling the conduction properties contained in the photosensitive layer 1004 may be determined as desired depending on the polarity and content of the substance contained in the charge injection prevention layer 1003. It is determined as appropriate, but preferably 0.001~
1000atomic ppm, more preferably 0.05~
500atomic ppm, optimally 0.1-200atomic ppm
It is desirable that this is done. In the present invention, when the charge injection prevention layer 1003 and the photosensitive layer 1004 contain the same type of substance that controls conductivity, the content in the photosensitive layer 1004 is preferably 30 atomic ppm or less. is desirable. 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 (H+X) contained in the charge injection prevention layer 1003 and the photosensitive layer 1004 is preferably is 1~
It is desirable that it be 40 atomic %, more preferably 5 to 30 atomic %. Halogen atoms (X) include F, Cl, Br,
Among them, F and Cl are preferred. In the light receiving member shown in FIG. 10, a so-called barrier layer made of an electrically insulating material may be provided instead of the charge injection prevention layer 1003. Alternatively, the barrier layer and the charge injection prevention layer 1003 may be used together. Barrier layer forming materials include Al ₂ O ₃ , SiO ₂ ,
Examples include inorganic electrically insulating materials such as Si ₃ N ₄ and organic electrically insulating materials such as polycarbonate. In the light receiving member 1000 shown in FIG. 10, the surface layer 10 formed on the photosensitive layer 1004 is
05 has a free surface and is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repetition characteristics, electrical pressure resistance, usage 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≦1
Consists of. 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. Glow discharge has advantages such as relatively easy control of manufacturing conditions for manufacturing a light-receiving member having silicon atoms, and easy introduction of carbon atoms and halogen atoms together with silicon atoms into the surface layer 1005 to be manufactured. A sputtering method or a sputtering method is preferably employed. 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 , The mixture is mixed at a mixing ratio and introduced into a vacuum deposition chamber where a support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge.
What is necessary is to deposit a-(Si _x C _1-x ) _y (H,X) _1-y on the layer formed on the support. In the present invention, a-(Si _x C _1-x ) _y (H,X) _1-y
As raw material gas for formation, silicon atoms (Si),
Most gaseous substances or gasified substances containing at least one of carbon atoms (C), hydrogen atoms (H), and halogen atoms (X) as constituent atoms are used. obtain. 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 normal temperature and normal pressure. . In the present invention, gases that are effectively used as raw material gases for forming the surface layer 1005 include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. whose constituent atoms are Si and H. Silicon hydride gas such as silanes, C and H
For example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons having 2 to 3 carbon atoms, simple halogen, hydrogen halide, interhalogen Compound,
Examples include 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 ₆ ), and n-butane (n-
C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₆ ), butene-2
(C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), halogens include fluorine,
Halogen gases such as chlorine, bromine, and iodine, hydrogen halides include FH, HI, HCl, HBr, and 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, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₃ ,
SiH ₃ Cl, SiH ₃ Br, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ ,
Examples of silicon hydride include SiH ₄ , Si ₂ H ₈ , Si ₃ H ₈ ,
Examples include silanes such as Si ₄ H ₁₀ , and the like. 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 silicon atoms, carbon atoms, halogen atoms, and optionally hydrogen atoms are contained in the formed surface layer 1005 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. SiH ₂ Cl ₂ , SiCl ₄ , or
By making SiH ₃ Cl or the like at a predetermined mixing ratio and introducing it in a gas state into an apparatus for forming the surface layer 1005 to generate a glow discharge, a-( _Six C _1-x ) _y (Cl
+H) A surface layer 1005 consisting of _1-y can be formed. The surface layer 1005 is formed by the sputtering method by targeting single crystal or polycrystalline Si wafers, C wafers, or wafers containing a mixture of Si and C, and forming 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 and H or/and X are diluted as necessary and introduced into a deposition chamber for sputtering. The Si wafer may be sputtered by forming gas 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 diluting gas used when forming the surface layer 1005 by a glow discharge method or a sputtering method is so-called. Noble gases, e.g.
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 ) _y with desired characteristics depending on the purpose
In order to form (H,X) _1-y , the preparation conditions are strictly selected as desired. For example, if the surface layer 1005 is provided with the main purpose of improving electrical withstand voltage, a-(Si _x C _1-x ) _y (H,X) _1-y is electrically insulating in the usage environment. Created as an amorphous material with remarkable behavior. In addition, if 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 degree of electrical insulation described above 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. When forming the surface layer 1005 consisting of a-(Si _x C _1-x ) _y ( _H , It is an important factor that influences the characteristics, and in the present invention, a-(Si _x C _1-x ) _y (H,X) ₁ having the desired characteristics
It is desirable that the temperature of the support during layer formation be tightly controlled so that _-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. The temperature is preferably 400°C, more preferably 50-350°C, most preferably 100-300°C. For forming the surface layer 1005, glow discharge method and sputtering method are used because fine 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 ) _y
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 (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-y
The amorphous material represented by can be roughly divided into an amorphous material composed of silicon atoms and carbon atoms (hereinafter referred to as "a-Si _a C _1-a ". However, 0<a<1 ),
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
When composed of 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 ) _c H _1-c , the amount of carbon atoms contained in the surface layer 1005 is preferably 1×10 ⁻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, if expressed as a-(Si _b C _1-b ) _c H _1-c above, 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 1×10 ⁻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 from 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, optimally 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 is necessary to appropriately determine the desired relationship based on the occurrence relationship depending on the characteristics. In addition, it is desirable to consider the economical aspects including 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, the refractive index of the photosensitive layer is
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 optimal as an antireflection layer. . When a-Si:H is used as a photosensitive 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 have a refractive index of such a value by adjusting the amount of C,
It also satisfies mechanical durability, interlayer adhesion, and electrical properties, making it the most suitable material for the surface layer. In addition, when placing emphasis on the role of the surface layer 105 as an antireflection layer, the layer thickness of the surface layer is as follows:
More preferably, the thickness is 0.05 to 2 μm. Examples of the present invention will be described below. Example 1 In this example, a spot type 80 μm semiconductor laser (wavelength: 780 nm) was used. Therefore A-
A spiral groove was created using a lathe on a cylindrical Al support (length (L) 357 mm, diameter (r) 80 mm) on which Si:H was to be deposited. The cross-sectional shape of the groove at this time is
Shown in Figure B. A charge injection prevention layer and a photosensitive layer were deposited on this Al support using the apparatus shown in FIG. 12 in the following manner. First, the configuration of the device will be explained. 1201 is a high frequency power supply, 1202 is a matching box, 1203
120 is a diffusion pump and a mechanical booster pump, 1204 is a motor for rotating the Al support, 120
5 is an Al support, 1206 is a heater for heating the Al support, 1207 is a gas introduction tube, 1208 is a cathode electrode for high frequency introduction, 1209 is a shield plate, 12
10 is a heater power supply, 1221 to 1225, 12
41 to 1245 are valves, 1231 to 1235 are mass flow controllers, 1251 to 1255 are regulators, 1261 is a hydrogen (H ₂ ) cylinder,
1262 is a silane (SiH ₄ ) cylinder, 1263 is a diborane (B ₂ H ₆ ) cylinder, 1264 is a nitrogen oxide (NO) cylinder, and 1265 is a methane (CH ₄ ) cylinder. Next, the manufacturing procedure will be explained. 1261-1265
All cylinder main valves were closed, all mass flow controllers and valves were opened, and the pressure inside the deposition apparatus was reduced to 10 ^-7 Torr using a 1203 diffusion pump. At the same time, 1206 heaters
The 205 Al support was heated to 250°C and kept constant at 250°C. The temperature of the Al support of 1205 is 250℃
After becoming constant at 1221-1225, 1241
~1245, close the valves 1251-1255, open the main valves of cylinders 1261-1265,
Replace the diffusion pump in 1203 with a mechanical booster pump. The secondary pressure of the regulator-equipped valves 1251 to 1255 was set to 1.5 Kg/cm ² .
1231 mass flow controller 300SCCM
The valves 1241 and 1221 were opened in sequence to introduce H ₂ gas into the deposition apparatus. Next, set the 1262 SiH ₄ gas to 1232 mass flow controller setting to 150SCCM,
SiH ₄ gas was introduced into the deposition apparatus in the same manner as the introduction of H ₂ gas. Next, set the B ₂ H ₆ gas flow rate of 1263 to
A 1233 mass flow controller was set so that the SiH ₄ gas flow rate was 1600 Vol ppm, and B ₂ H ₆ gas was introduced into the deposition apparatus in the same manner as the introduction of H ₂ gas. Next, set the mass flow controller of 1234 so that the NO gas flow rate of 1264 is 3.4 Vol% with respect to the SiH ₄ gas flow rate, and introduce NO gas into the deposition apparatus using the same operation as introducing H ₂ gas. did. When the internal pressure inside the deposition device stabilizes at 0.2 Torr, turn on the high frequency power supply of 1201 and turn on the 1201 high frequency power supply.
The matching box No. 02 was adjusted to evacuate the apparatus, the temperature of the Al support was lowered to room temperature, and the support on which the photoreceptive layer was formed was taken out. In this light-receiving member, the surface of the photosensitive layer and the surface of the support were non-parallel as shown in FIGS. 11B and 11C. 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 members for electrophotography, the wavelength
Image exposure was performed using a 780 nm semiconductor laser with a spot diameter of 80 μm using the apparatus shown in Figure 13, and after the image formation, development, and cleaning steps were repeated approximately 50,000 times, image evaluation was performed, and no interference fringe pattern was observed. figure,
It exhibited electrophotographic properties sufficient for practical use. Example 2 In the same manner as in Example 1, seven samples were prepared in which a photosensitive layer was formed on a support. Next, the hydrogen (H ₂ ) cylinder No. 1261 was replaced with an argon (Ar) gas cylinder, the deposition apparatus was cleaned, and the surface layer material shown in Table 1 No. 101 was applied all over the cathode electrode. Al of the photosensitive layer 205
A glow discharge was generated between the support and the cathode electrode of 1208, and the high frequency power was 150W and the thickness was 5μm.
A -Si:H:B layer (to become a P-type A-Si:H layer containing B) was deposited (charge injection prevention layer). After depositing 5 μm thick A-Si:H:B (P type) in this way, the valve 1223 was closed without turning off the discharge.
Stop the inflow of B ₂ H ₆ . And 20μm thick A-Si:H with high frequency power of 150W.
A layer (non-doped) was deposited (photosensitive layer). After that, set the mass flow controller of 1232.
Changed to 35SCCM, CH ₄ gas flow rate of 1265
The flow rate ratio for SiH ₄ gas flow rate is SiH ₄ /CH ₄ =
12 which is preset to be 1/30
From mass flow controller 35, valve 12
25 was opened to introduce CH ₄ gas, and 0.5 μm thick a-SiC (H) was deposited with high frequency power of 150 W (surface layer). The high-frequency power supply and gas valves are all closed, one of the valves that has been formed until deposition is installed, and the inside of the deposition apparatus is sufficiently depressurized using a diffusion pump. After that, argon gas was introduced to 0.015 Torr, and high frequency power was
A glow discharge was generated at 150 W, and the surface material was sputtered and deposited on the support under the conditions shown in Table 1, No. 101 (Sample No. 101). Similarly, surface layers were deposited on the remaining six samples under the conditions shown in Table 1, Nos. 120 to 107 (Samples Nos. 102 to 107). As shown in FIGS. 11B and 11C, the surface of the photosensitive layer and the surface of the support were non-parallel. in this case
The difference in average layer thickness between the center and both ends of the Al support was 2 μm. For the above seven types of electrophotographic light-receiving materials, a semiconductor laser with a wavelength of 780 nm is used with a spot diameter of 780 nm.
Image exposure was performed at 80 μm using the apparatus shown in Figure 13,
After repeating the image forming, developing and cleaning steps about 50,000 times, image evaluation was performed and the results shown in Table 1 were obtained. 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 of silicon atoms and carbon atoms in the surface layer. Each of the light-receiving members for electrophotography was prepared 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 the process up to transfer was carried out for about 5 minutes.
After repeating this process 10,000 times, we performed an image evaluation and found that
The results shown in Table 2 were obtained. Example 4 When forming the surface layer, SiH ₄ gas, SiF ₄ gas, CH ₄
Each of the light-receiving members for electrophotography was prepared in the same manner as in Example 1 except that the content of silicon atoms and carbon atoms in the surface layer was varied by changing the gas flow rate ratio. 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 results like this. Example 5 Each of light-receiving members for electrophotography was produced in exactly the same manner as in Example 1 except that the layer thickness of the surface layer was changed. Each of the electrophotographic light-receiving members thus obtained was subjected to image exposure with a laser in the same manner as in Example 1, the steps up to transfer were repeated, and image evaluation was performed, 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 light-receiving member was 0.5 μm between the center and both ends. Also, the difference in layer thickness in minute parts is
It was 0.1 μm. In such an electrophotographic light-receiving member, no interference fringe pattern was observed, and although the image forming, developing, and cleaning steps were repeated using the same apparatus as in Example 1, the results were sufficient for practical use. . Example 7 The surface of the cylindrical Al support was polished using a lathe.
It was processed as shown in Figure 4. Example 1 Using this cylindrical Al support
An A-Si:H electrophotographic light-receiving member was produced under the same conditions as above. This electrophotographic light-receiving member was subjected to image exposure using the apparatus shown in FIG. 13 in the same manner as in Example 1, and was developed and transferred to obtain an image. No interference fringes were observed in the transferred image in this case, and the characteristics were sufficient for practical use. Example 8 A light-receiving member for electrophotography was produced using the cylindrical Al support having the surface properties shown in FIGS. 15 and 16 under the conditions shown in Table 5. 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. In this case, no interference fringes were observed in any of the images obtained, and the characteristics were sufficient for practical use. Moreover, there was no difference between the initial image and the 100,000th image, and the images were of high quality. Example 9 An electrophotographic light-receiving member was produced using the cylindrical Al support having the surface properties shown in FIGS. 15 and 16 under the conditions shown in Table 6. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and were developed, transferred, and fixed to obtain a visible image on plain paper. In the image obtained in this case, no interference fringes were observed, and the characteristics were sufficient for practical use. Example 10 Using the cylindrical Al support with the surface properties shown in FIGS. 15 and 16, an electrophotographic light-receiving member was produced under the conditions shown in Table 7. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure apparatus as in Example 1, and then developed, transferred, and fixed to obtain a visible image on plain paper. In the image obtained in this case, no interference fringes were observed, and the characteristics were sufficient for practical use. Example 11 Using the cylindrical Al support with the surface properties shown in FIGS. 15 and 16, an electrophotographic light-receiving member was produced under the conditions shown in Table 8. These electrophotographic light-receiving members were subjected to image exposure using the same image exposure method as in Example 1, and were developed, transferred, and fixed to obtain a visible image on plain paper. No interference fringes were observed in the image obtained in this case, and the characteristics were sufficient for practical use. [Effects of the Invention] As described above in detail, according to the present invention,
It is suitable for image formation using coherent monochromatic light, is easy to manage, and can simultaneously and completely eliminate the interference fringe pattern that appears during image formation and the appearance of spots during reversal development. has high photosensitivity, high signal-to-noise ratio characteristics, and good electrical contact with the support, and is suitable for digital image recording.
Furthermore, it is possible to provide a light-receiving member with excellent mechanical durability, particularly abrasion resistance, and light-receiving properties.

[Table] ◎: Very good ○: Good △: Adequate for practical use ×: Image defects occur

[Table] ◎: Very good ○: Good △: Adequate for practical use ×: Image defects occur

[Table] ◎: Very good ○: Good △: Sufficient for practical use
×: Image defects occur.

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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. 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. FIGS. 9A and 9B are explanatory diagrams of the surface conditions of typical supports, respectively. FIG. 10 is an explanatory diagram of the layer structure of the light receiving member. FIG. 12 is an explanatory diagram of a photoreceptive layer deposition apparatus used in Examples. FIG. 13 shows an image exposure apparatus used in the example. Figure 11, Figure 14, Figure 15, Figure 16
The figure is an explanatory diagram of the surface state of the Al support used in the examples. FIG. 17 is an explanatory diagram for explaining the processing of the support. 1000... Light-receiving member, 1002... Light-receiving layer,
DESCRIPTION OF SYMBOLS 1001... Al support, 1003... Charge injection prevention layer, 1004... Photosensitive layer, 1005... Surface layer, 13
01...Light receiving member for electrophotography, 1302...Semiconductor laser, 1303...Fθ lens, 1304...Polygon mirror, 1305...Plan view of exposure device, 13
06...Side view of the exposure apparatus.

Claims (1)

[Claims] 1. The cross-sectional shape at a predetermined cutting position is 0.3 μm to 500 μm.
A support having many convex portions formed on its surface, each having a convex shape in which sub-peaks are superimposed on a main peak having a maximum depth of 0.1 μm to 5 μm at m pitch, and silicon atoms, hydrogen atoms, and/or halogen atoms. A charge injection prevention layer made of an amorphous material consisting of a substance that controls conductivity, and a single layer photosensitive material made of an amorphous material containing silicon atoms and hydrogen atoms and/or halogen atoms. and a surface layer made of an amorphous material containing silicon atoms and carbon atoms, and the charge injection prevention layer contains oxygen atoms, carbon atoms, and nitrogen atoms. 1. A light-receiving member for electrophotography, characterized in that the light-receiving layer contains at least one selected one uniformly in the layer thickness direction, and the light-receiving layer has at least one pair of non-parallel interfaces within a short range. 2. The electrophotographic light-receiving member according to claim 1, wherein the photosensitive layer has photoconductivity. 3. The light-receiving member for electrophotography according to claim 1, wherein the light-receiving layer has a multilayer structure. 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.